CA1120176A - Process for preparing adhesive repellent coatings - Google Patents
Process for preparing adhesive repellent coatingsInfo
- Publication number
- CA1120176A CA1120176A CA000269185A CA269185A CA1120176A CA 1120176 A CA1120176 A CA 1120176A CA 000269185 A CA000269185 A CA 000269185A CA 269185 A CA269185 A CA 269185A CA 1120176 A CA1120176 A CA 1120176A
- Authority
- CA
- Canada
- Prior art keywords
- platinum
- complexes
- finely dispersed
- diorganopolysiloxanes
- vinyl groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
- C09J2483/005—Presence of polysiloxane in the release coating
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved process for preparing adhesive repellent coatings is provided. The process includes the steps of: applying to the surfaces which are to be rendered adhesive repellent, an aqueous emulsion contain-ing (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule [preferably wherein the organopolysiloxanes (2) are present in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1)], and (3) catalysts (known per se) which pro-mote the addition of Si-bonded hydrogen to vinyl groups, present in a catalytic amount preferably, where the catalyst is a platinum-containing compound of from 0.001 to 0.02 per cent by weight based on the weight of the diorganopolysiloxanes (1), and thereafter cross-linking the polysiloxanes (1). The improvement involves the step of mixing the cata-lyst (3) with the diorganopolysiloxanes (1) prior to the addition of water, preferably where the catalyst (3) is mixed with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter the resultant mixture is mixed with a dispersing agent and water. By this improvement, the solutions are more stable. Since the aqueous solurions can be preserved over a long period of time and still produce coatings as good as those obtained from freshly prepared emulsion, optimum utilization of continu-ously operated coating devices is achieved without migration of the repellent coatings. The coatings so prepared may be used as separating, cover and lining papers, boards, films and cloths.
An improved process for preparing adhesive repellent coatings is provided. The process includes the steps of: applying to the surfaces which are to be rendered adhesive repellent, an aqueous emulsion contain-ing (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule [preferably wherein the organopolysiloxanes (2) are present in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1)], and (3) catalysts (known per se) which pro-mote the addition of Si-bonded hydrogen to vinyl groups, present in a catalytic amount preferably, where the catalyst is a platinum-containing compound of from 0.001 to 0.02 per cent by weight based on the weight of the diorganopolysiloxanes (1), and thereafter cross-linking the polysiloxanes (1). The improvement involves the step of mixing the cata-lyst (3) with the diorganopolysiloxanes (1) prior to the addition of water, preferably where the catalyst (3) is mixed with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter the resultant mixture is mixed with a dispersing agent and water. By this improvement, the solutions are more stable. Since the aqueous solurions can be preserved over a long period of time and still produce coatings as good as those obtained from freshly prepared emulsion, optimum utilization of continu-ously operated coating devices is achieved without migration of the repellent coatings. The coatings so prepared may be used as separating, cover and lining papers, boards, films and cloths.
Description
"~ llZ01'~6 .
The present invention relates to adhesive repellent coatlngH, and more particularly to an improved'process for preparing adheslve 4i repellent coatings.
Heretofore, lt was known that adheqive repellent coatings can be prepared by applying to the'surfaces, solutions containing (l) dior-ganopolysiloxanes having Si-bonded'vinyl groups in their terminal units,
The present invention relates to adhesive repellent coatlngH, and more particularly to an improved'process for preparing adheslve 4i repellent coatings.
Heretofore, lt was known that adheqive repellent coatings can be prepared by applying to the'surfaces, solutions containing (l) dior-ganopolysiloxanes having Si-bonded'vinyl groups in their terminal units,
(2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and (3) platinum catalysts which promote the addition of Si-bonded hydrogen to vinyl groups and thereafter cross-linking the diorgano-polysiloxanes (l). (See German Patent Application No. 2,455,483 to General Electric Company.) In the process described in the German patent application, diorganopolysiloxanes having terminal vinyl groups and a platinum catalyst are slowly added to water which contains an emulsifying agent and the resultant mixture is thoroughly dispersed in the aqueous phase. However, German Patent No. 1,246,251 to Dow Corning Corporation ~.
discloses that Si-bonded hydrogen is rapidly split off in the presence of platinum compounds. Thus, the teachings of German Patent Application No. 2,455,483, that emulsifying in water precludes any reaction until the '~ water has been removed, appear to be inconsistent with the teachings of t 20 German Patent No. 1,246,251. Moreover, German Patent Application No.
2,455,483 also suggests that two separate emulsions should be prepared and then combined just prior to the application of the emulsion to the surfaces to be rendered~'adhesive repellent.
Therefore, it is an object of one aspect of this invention to provide adhesive repellent coatings.
An object of another aspect of this invention is to provide aqueous emulsions which may be applied to surfaces to impart adhesive repellency thereto.
~n object of still another aspect of this invention is to pro-30' vide aqueous emulsions which are stable over'a long period of time.
An object of a further'aspect of this invention is to provide stable aqueous emulsions which will readily cross-link to form adhesive 11;~0176 repellent coatings.
An ob~ect of a stlll further aspect of this inventlon ls to provide an improved process for preparing stable aqueaus emulslons which will form adhesive repellent coatings.
By a broad aspect of this invention, an improved process is provided for preparing adhesive repellent coatings by applying to a sur-face an aqueous emulsion consisting of (1~ diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydro-gen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3~ a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to fo m an aqueous emulsion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4N2O, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst
discloses that Si-bonded hydrogen is rapidly split off in the presence of platinum compounds. Thus, the teachings of German Patent Application No. 2,455,483, that emulsifying in water precludes any reaction until the '~ water has been removed, appear to be inconsistent with the teachings of t 20 German Patent No. 1,246,251. Moreover, German Patent Application No.
2,455,483 also suggests that two separate emulsions should be prepared and then combined just prior to the application of the emulsion to the surfaces to be rendered~'adhesive repellent.
Therefore, it is an object of one aspect of this invention to provide adhesive repellent coatings.
An object of another aspect of this invention is to provide aqueous emulsions which may be applied to surfaces to impart adhesive repellency thereto.
~n object of still another aspect of this invention is to pro-30' vide aqueous emulsions which are stable over'a long period of time.
An object of a further'aspect of this invention is to provide stable aqueous emulsions which will readily cross-link to form adhesive 11;~0176 repellent coatings.
An ob~ect of a stlll further aspect of this inventlon ls to provide an improved process for preparing stable aqueaus emulslons which will form adhesive repellent coatings.
By a broad aspect of this invention, an improved process is provided for preparing adhesive repellent coatings by applying to a sur-face an aqueous emulsion consisting of (1~ diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydro-gen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3~ a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to fo m an aqueous emulsion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4N2O, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst
(3) with the diorganopolysiloxanes (1~ before it is mixed with water.
By another aspect of this invention, an improved process is provided for rendering surfaces adhesive repellent which comprieses apply-ing to the surfaces an aqueous emulsion containing (1) diorganopoly-siloxanes having Si-bonded vinyl groups in their terminal units (2) from ~r ." ~ 2 -11'~0~76 20 to 50 per cent by weight of organopoly6iloxanes having nt least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they arè mixed with the mixture of (1) and (3), snd in whlch the organopoly-siloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, the cata-lyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14-4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carb,nyl, the improvement which comprises: mixing the catalyst (3) with the diorganopolysiloxanes (1) before it is mixed with water.
By a further aspect of this invention, an improved process is provided for preparing adhesive repellent compositions in which (1) dior-ganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2 before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.9 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emul~ion, _ - 3 11'~0176 the catalyst being selected from the group consisting of finely dlspersed platinum, finely dispersed ruthenium, flnely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H20, platinum-olefin complexes, platinum a cohol or alcoholate cnmplexes, platinum-ether complexes, platinum-aldehyde com-plexes, platinum-ketone complexes and platinum-vinylsiloxane complexes;
as well as irion, nickel and cobalt carbonyl, which process comprises:
mixing the catalyst (33 with at least one-ahlf of the total diorganopoly-siloxanes (1) in the absence of a dispersing agent and water to form ahomogeneous mixture and thereafter mixing the homogeneous mixture with a dispersing agent and water.
By a variant of these aspects of this invention, the diorgano-polysiloxanes (1) have the formula:
2 )x SiR3_xO (SiR20~n SiR3 x (CH=CH23 in which R is selected from the group consisting of substituted and unsub-stituted monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, and further being selected from the group consisting of alkyl radicals, cycloaliphatic radicals, aryl radicals, alkaryl radicals, aralkyl radicals, the substituted hydrocarbon radicals as being halogenated hydrocarbon radicals or cyanoalkyl radicals, n is a number sufficient to provide that the diorganopolysiloxanes (1) have a viscosity of from 100 to 750,000 cP
at 25C., and x is 1, 2 or 3.
By a further variant, the catalyst (3) is a platinum compound and the platinum catalyst (3) is present in an amount of from 0~001 to 0.02 per cent by weight based on the weight of the diorganopolysiloxanes (1) .
By still another variant, the diorganopolysiloxanes (1) are cross-linked at a temperature up to 250C.
F~ - 4 -)176 By another aspect of thls lnventlon, an lmproved process 1H
provlded for preparlng adhesive repellent composltlons ln which tl) dlor-ganopolysiloxanes having Si-bonded vinyl groups ln their termlnal unlts, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the welght of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promoye the addition of Si-bonded ~hydrogen to vinyl groups, are mixed with water to form an aqueous emul-sion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, sleected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H20, platinum-olefin complexes, platinum-alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst (3) with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
By yet another aspect of this invention, an improved process is provided for rendering surfaces adhesive repellent which comprises apply-ing to the surfaces an aqueous emulsion containing (1) diorganopolysilox-anes having Si-bonded vinyl groups in their terminal units, (2) from 2Q
to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2~ before they are - 4a -4r ~f . , , mixed with the mixtnre of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of cata-lysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements selected from platinum halides, PtC14, chloroplatinic acid and NaPtC14 4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises:
mixing catalyst (3) with at least one-half of the total diorganopolysil-oxanes ~1) in the absence of a dispersing agent and water to form a homo-geneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
Although the aqueous emulsions used in the process of aspects of this invention contain (1~ diorganopolysiloxanes having terminal Si-bonded vinyl groups, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and (3) catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, they are more stable than the emulsions employed heretofore to form adhesive repellent coatings. The improvement in stability is believed due primarily to the fact that catalyst ~3) which promotes the addition of Si-bonded hydrogen to vinyl groups is mixed with the diorganopolysiloxanes (1) before it is mixed with water. Also the coatings provided by the process of aspects of this invention exhibit adhesive repellent properties which are equal to coatings obtained from freshly prepared emulsions. Thus the aqueous emulsions used in the process of aspects of this invention can be pre-served over a long period of time and still produce coatings which rapidly cross-link at temperatures which are conventionally used in most applications. This results in the optimum utilization of continuously operated coating devices without any significant migration of the repel-lent coatings.
The diorganopolysiloxanes ~1) having Si-bonded vinyl groups in their ter~inal units which are employed in the aqueous emulsions used in the process of aspects of this invention are the same diorganopolysilox-anes which have been employed in the processes known heretofore for the preparation of adhesive revellent coatings by the application of an aqueous emulsion consisting of (1~ diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and (3) catalysts which promote the addition of Si-bonded hydrogen on vinyl groups. The organo-polysiloxanes (1) may be represented by the general formula:
( 2 CH)xSiR3_xO(SiR20)nSiR3 x(CH=CH2) , in which R may be the same or different and represents substituted or unsubstituted monovalent hydrocarbon radicals, x is 1, 2 or 3, preferably 1, and n is a number having a value sufficient to provide that the diorganopolysiloxanes (1) have a viscosity from 100 to 750,000 cP at 25C.
Although this is generally not indicated in the formulas of this type, the organopolysiloxane chain may contain other siloxane units in addition to the diorganosiloxane units, i.e., units of the formula SiR20. Examples of other siloxane units which are generally present only in the form of impurities are those corresponding to the formula RSiO~/2, R3SiOl/2and SiO4/2, where R is the same as above. These other siloxane units should not exceed 10 mol per cent and more preferably not more than - 4c -~, , `` 11'~;)176 1 mol per cent.
Examples of hydrocarbon radicals R linked to the diorganopoly-siioxanes (l) are alkyl radicals having from 1 to 18 carbon atoms, e.g., the methyl, ethyl, n-propyl, isopropyl, butyl, hexyl, octyl, decyl and octadecyl radicals; cycloaliphatic hydrocarbon radicals, e.g., the cyclo-hexyl and cycloheptyl radical; aryl radicals, e.g., the phenyl radical;
alkaryl radicals, e.g., the tolyl radical; and aralkyl radicals, e.g., the benzyl and the phenylethyl radical. Examples of substituted hydro-carbon radicals are halogenated hydrocarbon radicals, e.g., the 3,3,3-trifluoropropyl radical and 0-, o- and m-chlorophenyl radicals; and cyanoradicals~ e.g., 4d _ .
; ' 11;~0176 the cyanoethyl radical. The hydrocnrbon radicals R can ~lso be vinyl radicals or other alkenyl radicals, e.g., the allyl radical or decenyl radicais. Where flexible coatings are preferred, the substituted hydro-carbon radicals in the diorganopolysiloxanes (1) which are not bonded to terminal Si-atoms, should be free of aliphatic unsaturation. It is par-_ ticularly preferred that they be free of vinyl radicals. Because of their availability it is preferred that at least 50 percent of the number of R
radicals be methyl radicals.
The diorganopolysiloxanes (1) may consist of identical copoly-mers or of mixtures of several copolymers having the same degree of - polymerization, or mixtures of identical or different copolymers having different degrees of polymerization. When the diorganopolysiloxanes (1) contain various diorganopolysiloxane units, these units may be present either as random or as block copolymers.
When it is desired to obtain a particularly high degree of re-pellency to adhesive materials using readily available diorganopolysilox-anes (1), it is preferred that all the organic radicals which are present in the diorganopolysiloxanes (1) except the terminal vinyl group, be methyl groups. Conversely, when a lower degree of repellency to adhesive materials is desired, then it is preferred that from 3 to 30 mol percent and preferably from 5 to 20 mol percent of the non-terminal units in the diorganopolysiloxanes (1) be diphenylsiloxane units, and at least 50 mol percent of the hydrocarbon radicals in the non-terminal units in the diorganopolysiloxanes (1) be methyl groups. The greater the proportion of diphenylsiloxane units, the lower the degree of repellency to ad-hesive materials.
In order that the diorganopolyslloxanes (1) wlll be easlly emul-sified, it 19 preferred that the vigcoslty of the dlorganopolyslloxanes (1) be less than 10,000 cP at 25C., and more preferably from 500 to 6,000 cP at 25C.
It ls possible to use as organopolysiloxanes (2), i.e., those having at least 3 Si-bonded hydrogen atoms per molecule, the same organo-polysiloxanes which have been used heretofore in the preparation of adhe-sive repellent coatings which contain diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and catalysts which - promote the addition of Si-bonded hydrogen to vinyl groups.
In the organopolysiloxanes (2) having at least 3Si-bonded hy-drogen atoms per molecule, the silicon valences which are not satisfied with hydrogen and siloxane oxygen atoms are preferably satisfied with methyl, ethyl andlor phenyl radicals. These organopolysiloxanes (2) are preferably of the type represented by the general formula:
R~si(cH3)2o(siR 20)psi(CH3)2R , in which R' represents hydrogen or the methyl, ethyl and/or phenyl radi-cals, with the provision that only a single hydrogen atom may be bonded to a silicon atom and that 0.2 to 0.5 hydrogen atoms must be present for every SiR'20 unit and that p is a whole number having a value of from 10 to 500.
It is preferred that the proportion of Si-bonded hydrogen atoms be from 0.2 to 1.6 percent by weight and more preferably from 0.3 to 0.5 percent by weight based on the weight of the organopolysiloxanes (2).
It is preferred that p have a value of from 20 to 11'~()1~'6 lO0 and that the viscosity of the organopolyslloxanes (2) be from 30 to about 70 cP at 25C.
Suitable examples of organopolysiloxaneg (2) represented by the above formula are copolymers containing dimethylhydrogensiloxane, methyl-hydrogensiloxane, dimethylsiloxane and trimethylsiloxane units; copoly-mers containing trimethylsiloxane, dimethylhydrogensiloxane and methylhy-drogensiloxane units; copolymers containing trimethylsiloxane, dimethyl-siloxane and methylhydrogensiloxane units; copolymers containing methyl-hydrogensiloxane and trimethylsiloxane units; copolymers containing methylhydrogensiloxane, diphenylsiloxane and trimethylsiloxane units; co-polymers containing methylhydrogensiloxane, dimethylhydrogensiloxane and diphenylsiloxane units; copolymers consisting of methylhydrogensiloxane, phenylmethylsiloxane, trimethylsiloxane and/or dimethylhydrogensiloxane units; copolymers consisting of methylhydrogensiloxane, dimethylsiloxane, diphenylsiloxane and trimethylsiloxane and/or dimethylhydrogensiloxane units, as well as copolymers containing dimethylhydrogensiloxane, tri-methylsiloxane, phenylhydrogensiloxane, dimethylsiloxane and/or phenyl-methylsiloxane units~ It is preferred that all the silicon valences with hydrogen and siloxane oxygen atoms be satisfied with methyl radicals.
Thus, in the preceding formula, which represents the organopolysiloxanes (2), R' should preferably be a methyl radical when it is not hydrogen.
Diorganopolysiloxanes (1) and organopolysiloxanes (2), are well known and processes for preparing these organopolysiloxanes are well known in the art.
i~
0~6 The organopolysiloxanes ~2) are preferAbly employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si~bonded vlnyl groups ln the diorganopolysiloxnnes (l).
The organopolysiloxanes (2) are emulsified in water and then mixed with the product obtained by mixing the catalyst (3) with the diorganopolysiloxane (1). The techniques uged in emulsifying the organo-polysiloxanes are well known in the art. Examples of suitable ~ispersing agents which may be employed are protective colloids, e.g. polyvinyl alcohol having a degree of hydrolysis of from 85 to 99 mol percent, and/
or emulsifiers, e.g., polyglycol ethers of alcohols having from 8 to 18 carbon atoms or alkylphenols. It is preferred that during the emulsifi-cation of the organopolysiloxanes (2) the dispersing agents be employed in an amount of from 3 to 20 percent by weight and more preferably from 6 to 9 percent by weight based on the weight of the organopolysiloxanes (2). It is preferred that the aqueous emulsion contain from 20 to 50 percent by weight and more preferably from 25 to 40 percent by weight of the organopolysiloxanes (2) based on the weight of the organopolysiloxanes (2) before they are mixed with the mixture containing the catalyst t3) and the diorganopolysil~xanes (1~.
Catalysts which have been used heretofore to promote the addi-tion of Si-bonded hydrogen to vinyl groups may be used as catalysts (3) in the process of aspects of this invention to prepare adhesive repellent coatings from compositions containing diorganopolysiloxanes having ter-minal Si-bonded vinyl groups and organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule. Examples of suitable catalysts are finely dispersed platinum, finely dispersed 11;~0176 ruthenium, finely dlspersed rhodium, finely dlfipcrsed p~lladium, flnely dispersed iridium a~d compounds or complexes of these elements, e.g., platinum halides, e.g., PtC14, chloroplatlnic acid and NazPtCl4.4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl. Preferred platinum compounds are those having organic or silicon-organic radicals or those having organic or sllicon-organic ligands or the reaction products obtained from the react~on of platinum com-pounds with the diorganopolysiloxane ~1). Examples of preferred catalystsare platinum acetylacetonate, platinum halides, platinum-ketone complexes, particularly reaction products of chloroplatinic acid and ketones, e.g., cyclohexanone, methylethylketone, acetone, methyl-n-propylketone, methyl-isobutylketone, methyl-n-amylketone, diisobutylketone, acetophenone and mesityloxide. The platinum-ketone complexes are well known and may be pre-pared in accordance with U.S. Patent No. 3,814,731, to ~itzsche et al.
Among the preferred catalysts which promote the addition of S~-bonded hydro-gen to vinyl groups are the platinum-vinylsiloxane compleses, e.g., plati-num-divinyltetramethyldisiloxane complexes, with or without an ascertain-able halogen content.
When finely dispersed platinum, platinum compounds and/or plati-num complexes are used as catalysts (3), they may be employed in amounts of from 0.001 to 0.02 percent by weight and more preferably in amounts of from 0.004 to 0.01 percent by weight, of platinum based on the weight of the diorganopolysiloxanes (1).
In the process of aspects of this invention, catalyst (3) which promotes the addition of Si-bonded hydrogen to vinyl groups is _ 9 _ llZ~6 mixed with at least one half of the amount of the dlorganopolyslloxane~
(1~ employed before it is mixed with water. The catalyst (3) can be mlxed with the diorganopolysiloxanes (l) in any suitable mlxlng devlce whlch wlll form a homogeneous mixture. Any slmple stirring or agitation device may be employed.
After the catalyst (3) has been mixed with the diorganopolysilox-anes (l), the product thus obtained is then emulsified in water. Any technique including the addition of dispersing agents which have been used heretofore to prepare organopolysiloxane-water emulsions may be used.
Examples of suitable dispersing agents which may be employed are protec-lO tive colloids, e.g., polyvinyl alcohols having a hydrolysis level of from 85 to 99 mol percent and/or emulsifiers, e.g., polyglycol ethers of alcohols having from 8 to 18 carbon atoms or alkylph~enols. It is preferred that during the emulsification of the mixture containing diorganopolys;loxanes (1) and catalyst (3) in water, that the dispersing agents be employed in an amount of from 3 to 20 percent by weight and more preferably from 6 to 9 percent by weight based on the weight of the diorganopolysiloxanes (l).
The emu:lsion obtained by emulsifying the mixture containing the diorgano-polysiloxanes (1) and catalyst (3) with water preferably contains from 20 to 75 percent by weight of diorganopolysiloxanes (1) and more preferably from 40 to 60 percent by weight of the diorganopolysiloxanes (l), based on the total weight of the emulsion. These emulsions can be further di-luted with water until the amount of diorganopolysiloxanes (l) present in the emulsion is from 0.1 to 20 percent by weight and more preferably from
By another aspect of this invention, an improved process is provided for rendering surfaces adhesive repellent which comprieses apply-ing to the surfaces an aqueous emulsion containing (1) diorganopoly-siloxanes having Si-bonded vinyl groups in their terminal units (2) from ~r ." ~ 2 -11'~0~76 20 to 50 per cent by weight of organopoly6iloxanes having nt least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they arè mixed with the mixture of (1) and (3), snd in whlch the organopoly-siloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, the cata-lyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14-4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carb,nyl, the improvement which comprises: mixing the catalyst (3) with the diorganopolysiloxanes (1) before it is mixed with water.
By a further aspect of this invention, an improved process is provided for preparing adhesive repellent compositions in which (1) dior-ganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2 before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.9 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emul~ion, _ - 3 11'~0176 the catalyst being selected from the group consisting of finely dlspersed platinum, finely dispersed ruthenium, flnely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H20, platinum-olefin complexes, platinum a cohol or alcoholate cnmplexes, platinum-ether complexes, platinum-aldehyde com-plexes, platinum-ketone complexes and platinum-vinylsiloxane complexes;
as well as irion, nickel and cobalt carbonyl, which process comprises:
mixing the catalyst (33 with at least one-ahlf of the total diorganopoly-siloxanes (1) in the absence of a dispersing agent and water to form ahomogeneous mixture and thereafter mixing the homogeneous mixture with a dispersing agent and water.
By a variant of these aspects of this invention, the diorgano-polysiloxanes (1) have the formula:
2 )x SiR3_xO (SiR20~n SiR3 x (CH=CH23 in which R is selected from the group consisting of substituted and unsub-stituted monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, and further being selected from the group consisting of alkyl radicals, cycloaliphatic radicals, aryl radicals, alkaryl radicals, aralkyl radicals, the substituted hydrocarbon radicals as being halogenated hydrocarbon radicals or cyanoalkyl radicals, n is a number sufficient to provide that the diorganopolysiloxanes (1) have a viscosity of from 100 to 750,000 cP
at 25C., and x is 1, 2 or 3.
By a further variant, the catalyst (3) is a platinum compound and the platinum catalyst (3) is present in an amount of from 0~001 to 0.02 per cent by weight based on the weight of the diorganopolysiloxanes (1) .
By still another variant, the diorganopolysiloxanes (1) are cross-linked at a temperature up to 250C.
F~ - 4 -)176 By another aspect of thls lnventlon, an lmproved process 1H
provlded for preparlng adhesive repellent composltlons ln which tl) dlor-ganopolysiloxanes having Si-bonded vinyl groups ln their termlnal unlts, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the welght of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promoye the addition of Si-bonded ~hydrogen to vinyl groups, are mixed with water to form an aqueous emul-sion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, sleected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H20, platinum-olefin complexes, platinum-alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst (3) with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
By yet another aspect of this invention, an improved process is provided for rendering surfaces adhesive repellent which comprises apply-ing to the surfaces an aqueous emulsion containing (1) diorganopolysilox-anes having Si-bonded vinyl groups in their terminal units, (2) from 2Q
to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2~ before they are - 4a -4r ~f . , , mixed with the mixtnre of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of cata-lysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, the catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements selected from platinum halides, PtC14, chloroplatinic acid and NaPtC14 4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises:
mixing catalyst (3) with at least one-half of the total diorganopolysil-oxanes ~1) in the absence of a dispersing agent and water to form a homo-geneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
Although the aqueous emulsions used in the process of aspects of this invention contain (1~ diorganopolysiloxanes having terminal Si-bonded vinyl groups, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and (3) catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, they are more stable than the emulsions employed heretofore to form adhesive repellent coatings. The improvement in stability is believed due primarily to the fact that catalyst ~3) which promotes the addition of Si-bonded hydrogen to vinyl groups is mixed with the diorganopolysiloxanes (1) before it is mixed with water. Also the coatings provided by the process of aspects of this invention exhibit adhesive repellent properties which are equal to coatings obtained from freshly prepared emulsions. Thus the aqueous emulsions used in the process of aspects of this invention can be pre-served over a long period of time and still produce coatings which rapidly cross-link at temperatures which are conventionally used in most applications. This results in the optimum utilization of continuously operated coating devices without any significant migration of the repel-lent coatings.
The diorganopolysiloxanes ~1) having Si-bonded vinyl groups in their ter~inal units which are employed in the aqueous emulsions used in the process of aspects of this invention are the same diorganopolysilox-anes which have been employed in the processes known heretofore for the preparation of adhesive revellent coatings by the application of an aqueous emulsion consisting of (1~ diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and (3) catalysts which promote the addition of Si-bonded hydrogen on vinyl groups. The organo-polysiloxanes (1) may be represented by the general formula:
( 2 CH)xSiR3_xO(SiR20)nSiR3 x(CH=CH2) , in which R may be the same or different and represents substituted or unsubstituted monovalent hydrocarbon radicals, x is 1, 2 or 3, preferably 1, and n is a number having a value sufficient to provide that the diorganopolysiloxanes (1) have a viscosity from 100 to 750,000 cP at 25C.
Although this is generally not indicated in the formulas of this type, the organopolysiloxane chain may contain other siloxane units in addition to the diorganosiloxane units, i.e., units of the formula SiR20. Examples of other siloxane units which are generally present only in the form of impurities are those corresponding to the formula RSiO~/2, R3SiOl/2and SiO4/2, where R is the same as above. These other siloxane units should not exceed 10 mol per cent and more preferably not more than - 4c -~, , `` 11'~;)176 1 mol per cent.
Examples of hydrocarbon radicals R linked to the diorganopoly-siioxanes (l) are alkyl radicals having from 1 to 18 carbon atoms, e.g., the methyl, ethyl, n-propyl, isopropyl, butyl, hexyl, octyl, decyl and octadecyl radicals; cycloaliphatic hydrocarbon radicals, e.g., the cyclo-hexyl and cycloheptyl radical; aryl radicals, e.g., the phenyl radical;
alkaryl radicals, e.g., the tolyl radical; and aralkyl radicals, e.g., the benzyl and the phenylethyl radical. Examples of substituted hydro-carbon radicals are halogenated hydrocarbon radicals, e.g., the 3,3,3-trifluoropropyl radical and 0-, o- and m-chlorophenyl radicals; and cyanoradicals~ e.g., 4d _ .
; ' 11;~0176 the cyanoethyl radical. The hydrocnrbon radicals R can ~lso be vinyl radicals or other alkenyl radicals, e.g., the allyl radical or decenyl radicais. Where flexible coatings are preferred, the substituted hydro-carbon radicals in the diorganopolysiloxanes (1) which are not bonded to terminal Si-atoms, should be free of aliphatic unsaturation. It is par-_ ticularly preferred that they be free of vinyl radicals. Because of their availability it is preferred that at least 50 percent of the number of R
radicals be methyl radicals.
The diorganopolysiloxanes (1) may consist of identical copoly-mers or of mixtures of several copolymers having the same degree of - polymerization, or mixtures of identical or different copolymers having different degrees of polymerization. When the diorganopolysiloxanes (1) contain various diorganopolysiloxane units, these units may be present either as random or as block copolymers.
When it is desired to obtain a particularly high degree of re-pellency to adhesive materials using readily available diorganopolysilox-anes (1), it is preferred that all the organic radicals which are present in the diorganopolysiloxanes (1) except the terminal vinyl group, be methyl groups. Conversely, when a lower degree of repellency to adhesive materials is desired, then it is preferred that from 3 to 30 mol percent and preferably from 5 to 20 mol percent of the non-terminal units in the diorganopolysiloxanes (1) be diphenylsiloxane units, and at least 50 mol percent of the hydrocarbon radicals in the non-terminal units in the diorganopolysiloxanes (1) be methyl groups. The greater the proportion of diphenylsiloxane units, the lower the degree of repellency to ad-hesive materials.
In order that the diorganopolyslloxanes (1) wlll be easlly emul-sified, it 19 preferred that the vigcoslty of the dlorganopolyslloxanes (1) be less than 10,000 cP at 25C., and more preferably from 500 to 6,000 cP at 25C.
It ls possible to use as organopolysiloxanes (2), i.e., those having at least 3 Si-bonded hydrogen atoms per molecule, the same organo-polysiloxanes which have been used heretofore in the preparation of adhe-sive repellent coatings which contain diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and catalysts which - promote the addition of Si-bonded hydrogen to vinyl groups.
In the organopolysiloxanes (2) having at least 3Si-bonded hy-drogen atoms per molecule, the silicon valences which are not satisfied with hydrogen and siloxane oxygen atoms are preferably satisfied with methyl, ethyl andlor phenyl radicals. These organopolysiloxanes (2) are preferably of the type represented by the general formula:
R~si(cH3)2o(siR 20)psi(CH3)2R , in which R' represents hydrogen or the methyl, ethyl and/or phenyl radi-cals, with the provision that only a single hydrogen atom may be bonded to a silicon atom and that 0.2 to 0.5 hydrogen atoms must be present for every SiR'20 unit and that p is a whole number having a value of from 10 to 500.
It is preferred that the proportion of Si-bonded hydrogen atoms be from 0.2 to 1.6 percent by weight and more preferably from 0.3 to 0.5 percent by weight based on the weight of the organopolysiloxanes (2).
It is preferred that p have a value of from 20 to 11'~()1~'6 lO0 and that the viscosity of the organopolyslloxanes (2) be from 30 to about 70 cP at 25C.
Suitable examples of organopolysiloxaneg (2) represented by the above formula are copolymers containing dimethylhydrogensiloxane, methyl-hydrogensiloxane, dimethylsiloxane and trimethylsiloxane units; copoly-mers containing trimethylsiloxane, dimethylhydrogensiloxane and methylhy-drogensiloxane units; copolymers containing trimethylsiloxane, dimethyl-siloxane and methylhydrogensiloxane units; copolymers containing methyl-hydrogensiloxane and trimethylsiloxane units; copolymers containing methylhydrogensiloxane, diphenylsiloxane and trimethylsiloxane units; co-polymers containing methylhydrogensiloxane, dimethylhydrogensiloxane and diphenylsiloxane units; copolymers consisting of methylhydrogensiloxane, phenylmethylsiloxane, trimethylsiloxane and/or dimethylhydrogensiloxane units; copolymers consisting of methylhydrogensiloxane, dimethylsiloxane, diphenylsiloxane and trimethylsiloxane and/or dimethylhydrogensiloxane units, as well as copolymers containing dimethylhydrogensiloxane, tri-methylsiloxane, phenylhydrogensiloxane, dimethylsiloxane and/or phenyl-methylsiloxane units~ It is preferred that all the silicon valences with hydrogen and siloxane oxygen atoms be satisfied with methyl radicals.
Thus, in the preceding formula, which represents the organopolysiloxanes (2), R' should preferably be a methyl radical when it is not hydrogen.
Diorganopolysiloxanes (1) and organopolysiloxanes (2), are well known and processes for preparing these organopolysiloxanes are well known in the art.
i~
0~6 The organopolysiloxanes ~2) are preferAbly employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si~bonded vlnyl groups ln the diorganopolysiloxnnes (l).
The organopolysiloxanes (2) are emulsified in water and then mixed with the product obtained by mixing the catalyst (3) with the diorganopolysiloxane (1). The techniques uged in emulsifying the organo-polysiloxanes are well known in the art. Examples of suitable ~ispersing agents which may be employed are protective colloids, e.g. polyvinyl alcohol having a degree of hydrolysis of from 85 to 99 mol percent, and/
or emulsifiers, e.g., polyglycol ethers of alcohols having from 8 to 18 carbon atoms or alkylphenols. It is preferred that during the emulsifi-cation of the organopolysiloxanes (2) the dispersing agents be employed in an amount of from 3 to 20 percent by weight and more preferably from 6 to 9 percent by weight based on the weight of the organopolysiloxanes (2). It is preferred that the aqueous emulsion contain from 20 to 50 percent by weight and more preferably from 25 to 40 percent by weight of the organopolysiloxanes (2) based on the weight of the organopolysiloxanes (2) before they are mixed with the mixture containing the catalyst t3) and the diorganopolysil~xanes (1~.
Catalysts which have been used heretofore to promote the addi-tion of Si-bonded hydrogen to vinyl groups may be used as catalysts (3) in the process of aspects of this invention to prepare adhesive repellent coatings from compositions containing diorganopolysiloxanes having ter-minal Si-bonded vinyl groups and organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule. Examples of suitable catalysts are finely dispersed platinum, finely dispersed 11;~0176 ruthenium, finely dlspersed rhodium, finely dlfipcrsed p~lladium, flnely dispersed iridium a~d compounds or complexes of these elements, e.g., platinum halides, e.g., PtC14, chloroplatlnic acid and NazPtCl4.4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl. Preferred platinum compounds are those having organic or silicon-organic radicals or those having organic or sllicon-organic ligands or the reaction products obtained from the react~on of platinum com-pounds with the diorganopolysiloxane ~1). Examples of preferred catalystsare platinum acetylacetonate, platinum halides, platinum-ketone complexes, particularly reaction products of chloroplatinic acid and ketones, e.g., cyclohexanone, methylethylketone, acetone, methyl-n-propylketone, methyl-isobutylketone, methyl-n-amylketone, diisobutylketone, acetophenone and mesityloxide. The platinum-ketone complexes are well known and may be pre-pared in accordance with U.S. Patent No. 3,814,731, to ~itzsche et al.
Among the preferred catalysts which promote the addition of S~-bonded hydro-gen to vinyl groups are the platinum-vinylsiloxane compleses, e.g., plati-num-divinyltetramethyldisiloxane complexes, with or without an ascertain-able halogen content.
When finely dispersed platinum, platinum compounds and/or plati-num complexes are used as catalysts (3), they may be employed in amounts of from 0.001 to 0.02 percent by weight and more preferably in amounts of from 0.004 to 0.01 percent by weight, of platinum based on the weight of the diorganopolysiloxanes (1).
In the process of aspects of this invention, catalyst (3) which promotes the addition of Si-bonded hydrogen to vinyl groups is _ 9 _ llZ~6 mixed with at least one half of the amount of the dlorganopolyslloxane~
(1~ employed before it is mixed with water. The catalyst (3) can be mlxed with the diorganopolysiloxanes (l) in any suitable mlxlng devlce whlch wlll form a homogeneous mixture. Any slmple stirring or agitation device may be employed.
After the catalyst (3) has been mixed with the diorganopolysilox-anes (l), the product thus obtained is then emulsified in water. Any technique including the addition of dispersing agents which have been used heretofore to prepare organopolysiloxane-water emulsions may be used.
Examples of suitable dispersing agents which may be employed are protec-lO tive colloids, e.g., polyvinyl alcohols having a hydrolysis level of from 85 to 99 mol percent and/or emulsifiers, e.g., polyglycol ethers of alcohols having from 8 to 18 carbon atoms or alkylph~enols. It is preferred that during the emulsification of the mixture containing diorganopolys;loxanes (1) and catalyst (3) in water, that the dispersing agents be employed in an amount of from 3 to 20 percent by weight and more preferably from 6 to 9 percent by weight based on the weight of the diorganopolysiloxanes (l).
The emu:lsion obtained by emulsifying the mixture containing the diorgano-polysiloxanes (1) and catalyst (3) with water preferably contains from 20 to 75 percent by weight of diorganopolysiloxanes (1) and more preferably from 40 to 60 percent by weight of the diorganopolysiloxanes (l), based on the total weight of the emulsion. These emulsions can be further di-luted with water until the amount of diorganopolysiloxanes (l) present in the emulsion is from 0.1 to 20 percent by weight and more preferably from
4 to 15 percent by weight based on the total weight of the emulsion, before it is mixed with the aqueous emulsion of diorganopolysiloxane (2).
Undiluted emul8ions containing the diorganopolys1loxanes (1) can be stored at room temperature for several months and can be pumped from one container to another without any observable demulsiflcatlon, e.g., cream-ing and without any decrease in their ability to cross-link.
In addition to the components described above, the emulsions em-ployed in the process of aspects of this invention may also contain other components which are customarily used in the formation of coatings which are repellent to adhesive substances. Examples of such other components are anti-foaming agents, anti-freezing an" anti-corrosion agents, thicken-ing agents, e.g., carboxymethylcellulose and polyvinyl alcohols in excess - of the amou~f required for the emulsification of the organopolysiloxanes, alginates and starch, agents which impede or delay the addition of Si-bonded hydrogen to vinyl groups at room temperature, e.g., dialkylformamide, as well as buffering agents, e.g., sodium acetate which maintain the pH in the range of from 5 to 7.
The aqueous emulsion containing catalyst (3), the diorganopoly-siloxanes (1), the organopolysiloxanes (2) and dispersing agents as well as the additional components, if desired, can be applied to the surfaces which are to be rendered adhesive repellent by any suitable means known in the art, e.g., by immersion, brushing, pouring or sprayîng. Also the aqueous emulsion may be applied with a roller, a knife or a Meyer Rod or with an airbrush.
The surfaces of any normally solid substance may be made adhesive repellent by the process of aspects of this invention. Examples of suita-ble surfaces are those of paper, cardboard, asbestos, wood, cork, plastic foils, natural or synthetic fibers, textiles, ceramic ob~ects, glass and metals. The paper can be either of low grade or absorptive, including raw, i.e., kraft paper ~hich has not been treated with ~y - 11 -~1~0176 chemical and/or polymeric substances, havlng a weight of from 50 to 150 ~m/
m , unsized paper, paper wlth a low grindlng degree, paper wlth a hlgh wood content, non-calendered paper, uncoated paper or recycled paper. In the case of low-quality paper, lt is preferred that one or more of the above mentioned thickening agents be used in order to keep the absorpticn of or-ganopolysiloxanes as low as possible. The process can of course be equally applied to high-grade papers, for example non-absorptive papers, slzed papers, wood-free papers, calendered or satinated papers, parchment paper or coated paper. Both low and high grade cardboards may also be used.
The cross-linking of the diorganopolysiloxanes (1) may be carried out in the same manner as used heretofore in preparing coatings which are repellent to adhesive substances which were based on the use of diorgano-polysiloxanes having Si-bonded vinyl groups in their terminal units, organo-polysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and catalysts which promote the addition of Si-bonded hydrogen to vinyl groups.
Cross-linking is achieved by heating to at least 80C., for example in an oven, in a heated conduit or by means of a heated calender or heated plate, with the water evaporating simultaneously with or ~ust prior to cross-lin~-ing. In order to avoid damaging the surfaces which are to be-made adhesive repellent and/or the coatings which provide adhesive repellency, it is pre-ferred that temperatures in excess of 250C. be avoided during the heating step. Temperatures in the range of from 100 to 160C. are preferred.
Generally from 5 to 180 seconds of heating are sufficient to achieve com-plete cross-linking. At a temperature of 120C. from 8 to 12 seconds are sufficient to obtain complete cross-linking. At a temperature of r - 12 -llZ~ 6 150C., complete cross-linking can be nchieved wlthin 5 to 10 ~econds.
The purpose of aspects of this inventlon may be used to prepare papers which may be used for example in the manufacture of molded or decor-ative films and foams. Also, the process may be used to prepare separatlng, cover and lining papers, boards, films and cloths, for covering the backs of self-adhesive tapes and self-adhesive films or to cover the printed sides of self-adhesive labels. Moreover, the process of aspects of this invention can be used to manufacture packaging materials consisting of paper, cardboard boxes, metal films and barrels consisting of paper, plastic, wood or iron, when containers made of such materials are to be used for the storage and/or trans-portation of adhesive substances, e.g., adhesives, foodstuffs which have a tendency to adhere to containers, e.g., cake, honey, candy and meat, bitumen, asphalt, greased metal parts and raw rubber as well as in transfer~processes in which adhesive coatings are transferred to another surface.
In the following examples, all parts and percentages are by weight unless otherwise specified.
A solution of a platinum-ketone complex which is used in the fol-lowing examples, was prepared as follows: 1 gm of chloroplatinic acid is added to 200 gm of cyclohexanone which has been heated to 80C. The Polution obtained is then maintained at a temperature of 80C. for 45 minutes and ~hen dried with the aid of anhydrous sodium sulfate.
EXAMPT~ I
a) 900 gm of a dimethylpolysiloxane having terminal vinyldimethyl-siloxane units and a viscosity of 1125 cP at 25C. and ~6~ - 13 -11~Z()176 13.2 gm of the platinum-ketone complex solutlon prepared above, correspondlng to 100 ppm of platinum based on the weight of the dimethylpolysiloxane are added to a glass stoppered flask. The flask is then closed and rotated for 12 hours at 30 revolutions per minute. The contents of the flask and 8.5 percent based on the weight of the dimethylpolysiloxane of an etherified polyglycol which has been prepared by reacting isotridecanols with lO mols of ethylene oxide and water are placed in colloid mill to form an emulsion which contains 35 percent diorganopolysiloxane based on the weight of the emulsion.
(b) A second emulsion is prepared in colloid mill from a copolymer consisting of 4 mol percent of trimethylsiloxane, 24 mol percent of methyl-hydrogensiloxane and 72 mol percent of dimethylsiloxane units having a viscosi-ty of 50 cP at 25C. and a content of 0.36 percent Si-bonded hydrogen and 8.5 percent (based on the weight of the organopolysiloxane having Si-bonded hydro-gen) of etherfied polygolcol described above. The emulsion contains 35 per-centr of an organopolysiloxane having Si-bonded hydrogen based on the weight of the emulsion.
(c) 28.5 parts of the emulsion prepared in accordance with l(a) are diluted with 70 parts of distilled water and then mixed with l~part ofi:~he emulsion prepared in accordance with Example l (b). The mixture is allowed to stand for a period of time as shown in Table l, and then applied to super-calendered, so called "satinated" paper having a weight of 67 gm/m with a doctor blade consisting of a stainless steel rod having 0 2 mm thick stainless steel wire wound thereon.
The coated paper is suspended for 5 to 10 seconds over X~ - 14 -1~0176 a metal plate in a circulating air over at a temperature of 150C. to cro8s-link the organopolysiloxanes. Immedlately following the cross-llnklng of the organopolysiloxanes, the paper's coating is tested to determ$ne its nonad-hesive properties.
Two strips of self-adhesive (pressure-sensitive) adhesive tape ("Tesafilm rot" No. 154, Beiersdorf AG, ~lamburg, German Federal Republic;
"Tesa" is a registered trademark) having a width of 3 cm is applied to the coated paper. The self-adhesive tape has an adhesive force of 150 p/cm when applied to uncoated imitation parchment paper.
With the aid of a rubber roller the adhesive tape strips are pressed down with a force of 15 kp/cm2. After 20 hours of heating at a tem-perature of 70C. under a pressure of 20 p/cm2 and after cooling at 20~C., the two adhesive tapes are removed at an angle of 180C. and at a speed of 30 cm per minute. The force required to remove the tape is measured. In the following table the average force required to remove both strips from the coated ~paper is designated as "separation force". The percentages indi-cated as Residual Adhesive Strength refer to the adhesiYe strength of the tape before the tape was pressed on the coated paper. The adhesive strength prior to coating was calculated as 100 percent.
Elapsed time between preparation of emul-sion mixture and appli-cation to the paper Separation force Residual adhesive (hours) p/cm strength 4 0.7 75 6 0.7 75 ()176 (a) 900 gm of dimethylpolyslloxane having 8 vlscoslty of 1750 cP at 25C. which has terminal vinyldimethylsiloxane units and 21.6 gm of the platinum-ketone complex solution prepared above and which corresponds to 50 ppm of platinum based on the weight of the diorganopolysiloxane are added to a glass stoppered flask. The flask is stoppered and turned at 30 revolutions per minute (based on the weight of the diorganopolysiloxane) of ohe~etherified polyglycol of Example 1 (a) and water and then emulsified in a colloid mill.
The emulsion contains 35 percent by weight of diorganopolysiloxane. 1995 parts of the emulsion thus obtained are diluted with 4935 parts of distilled water.
(b) The diluted emulsion which contains 8.25 percent by weight of diorganopolysiloxane, is mixed with 700 parts of a 10 percent aqueous solution of polyvinyl alcohol having a saponsification number of 140 and a viscosity of 25 + 4 cP in a 4 percent aqueous solution at 20C., and 70 parts of the aqueous emulsion of the organopolysiloxane described in Example 1 (b) which has Si-bonded hydrogen atoms.
The mixture thus obtained is applied to waterproofed kraft paper with the ald of a doctor blade which consists of a stainless steel rod having wound thereon a 0.2 mm thick stainless steel wire. The organopolysiloxanes are cross-linked by conducting the coated kraft paper through a drying cham-ber having an air temperature of from 120C. to 130C. The coated area is in the drying chamber for 25 seconds.
l~V176 Specimens of the coated paper are then tested ln ~ccordance with Example 1 to determine their repellency to adhesive substances.
In four series of measurements each consisting of 5 indlvidual measurements, the average separation force, l,e., the force required to separ-ate the tape from the coated paper, is 15 p/cm. In two series of measurements each consisting of 10 individual measurements, the residual adhesi~e strength of the adhesive tape is 87 percent.
5930 parts of the diluted aqueous emulsion prepared in Example 2 (a) are mixed with 70 parts of the aqueous emulsion of the organopolysiloxane containing Si-bonded hydrogen atoms, prepared in Example 1 (b). The mixture thus obtained is applied to imitation parchment paper by means of the doctor blade described in Example 1 after various time periods have elapsed.
The coated paper is suspended for from 10 to 20 seconds over a metal plate in a circulating air over which is maintained at temperature of about 120C.
The adhesive repellency of the paper~s coating is then determined in accordance with Example 1. The results of the tests are shown in Table 2.
20 Elapsed time between pre-paration of emulsion mix-ture and application to the Separation force Residual adhesive paper (hours) p/cm strength %
0 0.6 92 2 4 ~ 82 4 1 78.5 24 0.5 95 llZ0176 (a) Into a glass flask which can be closed by a glass stopper are added 500`gm of dimethylpolysiloxane having a vlscosity of 1750 cP at 25C., which has terminal vinyldimethylsiloxane unlts, and 12.5 gm of 0.2 percent solution of chloroplatinic acid in butanol, corresponding to 50 ppm platinum, b ased on the weight of the diorganopolysiloxane. The closed flask is rotated for 12 hours at 30 revolutions per minute. About 175 gm of the product from the flask, 15 gms (8.5 percent based on the weight of the diorganopolysiloxane) of an etherified polyglycol which has been prepared by reacting isotridecanols with about 10 mols of ethylene oxide and 310 gm of water are added to a col-loid mill to produce an emulsion which contains 35 percent of diorganopolysil-oxane based on the weight of the emulsion. About 28.5 gm of the resultant emulsion is then diluted with 71.5 gm of distilled water.
(b) About 99 gm of the diluted emulsion prepared in Example 4 (a) are mixed with 1 gm of the aqueous emulsion of organopolysiloxane prepared in Example 1 (b) which has Si-bonded hydrogen atoms. This mixture is applied to parchment paper with the aid of the doctor blade (described in Example 1) in accordance with the time shown in Table 3. The coated parchment papers are hung over a metal plate at 120C. in an air circulating oven for 10 seconds to cross-link the diorganopolysiloxane. The coatings are tested in accordance with Example 1 to determine their repellency to adhesive sub-stances.
The results are shown in Table 3.
li;~O1~6 Elapsed time between preparation of emul-sion mixture and app- Separation force Residual adhesive lication to paper (hours) p/cm strength %
o 4.5 61.5 2 6.5 67 3 5.5 69 6 3,5 64 ~ 24 7 68 Comparative Test The method described in Example 4 (a) is repeated except that the dimethylpolysiloxane, which has terminal vinyldimethylsiloxane units and the solution of chloroplatinic acid are added simultaneouslv to a solution containing 15 gm of an etherified polyglycol prepared by reacting isotride-canols with about 10 mols of ethylene oxide, and then mixed with 310 gm of water. The mixture is then added to a colloid mill to prepare an emulsion.
The resultant emulsion is then ~ixed w~th the aqueous emulsion prepared in Example 1 (b), applied to parchment paper and then cross-linked in accordance with the process described in Example 4 (b). The results are illustrated in Table 4.
Elapsed time between preparation of emulsion mixture and application Separation force Residual adhesive to paper (hours) p/cm strength %
1 9.5 69 2 9.5 71 3 7.5 69 4 5.5 72 11;~01~6 Although speclflc examples have been descrlbed her~ln, lt ls not lntended to limit the invention solely thereto, but to include all the modl-fications falling wlthin the spirlt and scope of the appended clalm~.
Undiluted emul8ions containing the diorganopolys1loxanes (1) can be stored at room temperature for several months and can be pumped from one container to another without any observable demulsiflcatlon, e.g., cream-ing and without any decrease in their ability to cross-link.
In addition to the components described above, the emulsions em-ployed in the process of aspects of this invention may also contain other components which are customarily used in the formation of coatings which are repellent to adhesive substances. Examples of such other components are anti-foaming agents, anti-freezing an" anti-corrosion agents, thicken-ing agents, e.g., carboxymethylcellulose and polyvinyl alcohols in excess - of the amou~f required for the emulsification of the organopolysiloxanes, alginates and starch, agents which impede or delay the addition of Si-bonded hydrogen to vinyl groups at room temperature, e.g., dialkylformamide, as well as buffering agents, e.g., sodium acetate which maintain the pH in the range of from 5 to 7.
The aqueous emulsion containing catalyst (3), the diorganopoly-siloxanes (1), the organopolysiloxanes (2) and dispersing agents as well as the additional components, if desired, can be applied to the surfaces which are to be rendered adhesive repellent by any suitable means known in the art, e.g., by immersion, brushing, pouring or sprayîng. Also the aqueous emulsion may be applied with a roller, a knife or a Meyer Rod or with an airbrush.
The surfaces of any normally solid substance may be made adhesive repellent by the process of aspects of this invention. Examples of suita-ble surfaces are those of paper, cardboard, asbestos, wood, cork, plastic foils, natural or synthetic fibers, textiles, ceramic ob~ects, glass and metals. The paper can be either of low grade or absorptive, including raw, i.e., kraft paper ~hich has not been treated with ~y - 11 -~1~0176 chemical and/or polymeric substances, havlng a weight of from 50 to 150 ~m/
m , unsized paper, paper wlth a low grindlng degree, paper wlth a hlgh wood content, non-calendered paper, uncoated paper or recycled paper. In the case of low-quality paper, lt is preferred that one or more of the above mentioned thickening agents be used in order to keep the absorpticn of or-ganopolysiloxanes as low as possible. The process can of course be equally applied to high-grade papers, for example non-absorptive papers, slzed papers, wood-free papers, calendered or satinated papers, parchment paper or coated paper. Both low and high grade cardboards may also be used.
The cross-linking of the diorganopolysiloxanes (1) may be carried out in the same manner as used heretofore in preparing coatings which are repellent to adhesive substances which were based on the use of diorgano-polysiloxanes having Si-bonded vinyl groups in their terminal units, organo-polysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule and catalysts which promote the addition of Si-bonded hydrogen to vinyl groups.
Cross-linking is achieved by heating to at least 80C., for example in an oven, in a heated conduit or by means of a heated calender or heated plate, with the water evaporating simultaneously with or ~ust prior to cross-lin~-ing. In order to avoid damaging the surfaces which are to be-made adhesive repellent and/or the coatings which provide adhesive repellency, it is pre-ferred that temperatures in excess of 250C. be avoided during the heating step. Temperatures in the range of from 100 to 160C. are preferred.
Generally from 5 to 180 seconds of heating are sufficient to achieve com-plete cross-linking. At a temperature of 120C. from 8 to 12 seconds are sufficient to obtain complete cross-linking. At a temperature of r - 12 -llZ~ 6 150C., complete cross-linking can be nchieved wlthin 5 to 10 ~econds.
The purpose of aspects of this inventlon may be used to prepare papers which may be used for example in the manufacture of molded or decor-ative films and foams. Also, the process may be used to prepare separatlng, cover and lining papers, boards, films and cloths, for covering the backs of self-adhesive tapes and self-adhesive films or to cover the printed sides of self-adhesive labels. Moreover, the process of aspects of this invention can be used to manufacture packaging materials consisting of paper, cardboard boxes, metal films and barrels consisting of paper, plastic, wood or iron, when containers made of such materials are to be used for the storage and/or trans-portation of adhesive substances, e.g., adhesives, foodstuffs which have a tendency to adhere to containers, e.g., cake, honey, candy and meat, bitumen, asphalt, greased metal parts and raw rubber as well as in transfer~processes in which adhesive coatings are transferred to another surface.
In the following examples, all parts and percentages are by weight unless otherwise specified.
A solution of a platinum-ketone complex which is used in the fol-lowing examples, was prepared as follows: 1 gm of chloroplatinic acid is added to 200 gm of cyclohexanone which has been heated to 80C. The Polution obtained is then maintained at a temperature of 80C. for 45 minutes and ~hen dried with the aid of anhydrous sodium sulfate.
EXAMPT~ I
a) 900 gm of a dimethylpolysiloxane having terminal vinyldimethyl-siloxane units and a viscosity of 1125 cP at 25C. and ~6~ - 13 -11~Z()176 13.2 gm of the platinum-ketone complex solutlon prepared above, correspondlng to 100 ppm of platinum based on the weight of the dimethylpolysiloxane are added to a glass stoppered flask. The flask is then closed and rotated for 12 hours at 30 revolutions per minute. The contents of the flask and 8.5 percent based on the weight of the dimethylpolysiloxane of an etherified polyglycol which has been prepared by reacting isotridecanols with lO mols of ethylene oxide and water are placed in colloid mill to form an emulsion which contains 35 percent diorganopolysiloxane based on the weight of the emulsion.
(b) A second emulsion is prepared in colloid mill from a copolymer consisting of 4 mol percent of trimethylsiloxane, 24 mol percent of methyl-hydrogensiloxane and 72 mol percent of dimethylsiloxane units having a viscosi-ty of 50 cP at 25C. and a content of 0.36 percent Si-bonded hydrogen and 8.5 percent (based on the weight of the organopolysiloxane having Si-bonded hydro-gen) of etherfied polygolcol described above. The emulsion contains 35 per-centr of an organopolysiloxane having Si-bonded hydrogen based on the weight of the emulsion.
(c) 28.5 parts of the emulsion prepared in accordance with l(a) are diluted with 70 parts of distilled water and then mixed with l~part ofi:~he emulsion prepared in accordance with Example l (b). The mixture is allowed to stand for a period of time as shown in Table l, and then applied to super-calendered, so called "satinated" paper having a weight of 67 gm/m with a doctor blade consisting of a stainless steel rod having 0 2 mm thick stainless steel wire wound thereon.
The coated paper is suspended for 5 to 10 seconds over X~ - 14 -1~0176 a metal plate in a circulating air over at a temperature of 150C. to cro8s-link the organopolysiloxanes. Immedlately following the cross-llnklng of the organopolysiloxanes, the paper's coating is tested to determ$ne its nonad-hesive properties.
Two strips of self-adhesive (pressure-sensitive) adhesive tape ("Tesafilm rot" No. 154, Beiersdorf AG, ~lamburg, German Federal Republic;
"Tesa" is a registered trademark) having a width of 3 cm is applied to the coated paper. The self-adhesive tape has an adhesive force of 150 p/cm when applied to uncoated imitation parchment paper.
With the aid of a rubber roller the adhesive tape strips are pressed down with a force of 15 kp/cm2. After 20 hours of heating at a tem-perature of 70C. under a pressure of 20 p/cm2 and after cooling at 20~C., the two adhesive tapes are removed at an angle of 180C. and at a speed of 30 cm per minute. The force required to remove the tape is measured. In the following table the average force required to remove both strips from the coated ~paper is designated as "separation force". The percentages indi-cated as Residual Adhesive Strength refer to the adhesiYe strength of the tape before the tape was pressed on the coated paper. The adhesive strength prior to coating was calculated as 100 percent.
Elapsed time between preparation of emul-sion mixture and appli-cation to the paper Separation force Residual adhesive (hours) p/cm strength 4 0.7 75 6 0.7 75 ()176 (a) 900 gm of dimethylpolyslloxane having 8 vlscoslty of 1750 cP at 25C. which has terminal vinyldimethylsiloxane units and 21.6 gm of the platinum-ketone complex solution prepared above and which corresponds to 50 ppm of platinum based on the weight of the diorganopolysiloxane are added to a glass stoppered flask. The flask is stoppered and turned at 30 revolutions per minute (based on the weight of the diorganopolysiloxane) of ohe~etherified polyglycol of Example 1 (a) and water and then emulsified in a colloid mill.
The emulsion contains 35 percent by weight of diorganopolysiloxane. 1995 parts of the emulsion thus obtained are diluted with 4935 parts of distilled water.
(b) The diluted emulsion which contains 8.25 percent by weight of diorganopolysiloxane, is mixed with 700 parts of a 10 percent aqueous solution of polyvinyl alcohol having a saponsification number of 140 and a viscosity of 25 + 4 cP in a 4 percent aqueous solution at 20C., and 70 parts of the aqueous emulsion of the organopolysiloxane described in Example 1 (b) which has Si-bonded hydrogen atoms.
The mixture thus obtained is applied to waterproofed kraft paper with the ald of a doctor blade which consists of a stainless steel rod having wound thereon a 0.2 mm thick stainless steel wire. The organopolysiloxanes are cross-linked by conducting the coated kraft paper through a drying cham-ber having an air temperature of from 120C. to 130C. The coated area is in the drying chamber for 25 seconds.
l~V176 Specimens of the coated paper are then tested ln ~ccordance with Example 1 to determine their repellency to adhesive substances.
In four series of measurements each consisting of 5 indlvidual measurements, the average separation force, l,e., the force required to separ-ate the tape from the coated paper, is 15 p/cm. In two series of measurements each consisting of 10 individual measurements, the residual adhesi~e strength of the adhesive tape is 87 percent.
5930 parts of the diluted aqueous emulsion prepared in Example 2 (a) are mixed with 70 parts of the aqueous emulsion of the organopolysiloxane containing Si-bonded hydrogen atoms, prepared in Example 1 (b). The mixture thus obtained is applied to imitation parchment paper by means of the doctor blade described in Example 1 after various time periods have elapsed.
The coated paper is suspended for from 10 to 20 seconds over a metal plate in a circulating air over which is maintained at temperature of about 120C.
The adhesive repellency of the paper~s coating is then determined in accordance with Example 1. The results of the tests are shown in Table 2.
20 Elapsed time between pre-paration of emulsion mix-ture and application to the Separation force Residual adhesive paper (hours) p/cm strength %
0 0.6 92 2 4 ~ 82 4 1 78.5 24 0.5 95 llZ0176 (a) Into a glass flask which can be closed by a glass stopper are added 500`gm of dimethylpolysiloxane having a vlscosity of 1750 cP at 25C., which has terminal vinyldimethylsiloxane unlts, and 12.5 gm of 0.2 percent solution of chloroplatinic acid in butanol, corresponding to 50 ppm platinum, b ased on the weight of the diorganopolysiloxane. The closed flask is rotated for 12 hours at 30 revolutions per minute. About 175 gm of the product from the flask, 15 gms (8.5 percent based on the weight of the diorganopolysiloxane) of an etherified polyglycol which has been prepared by reacting isotridecanols with about 10 mols of ethylene oxide and 310 gm of water are added to a col-loid mill to produce an emulsion which contains 35 percent of diorganopolysil-oxane based on the weight of the emulsion. About 28.5 gm of the resultant emulsion is then diluted with 71.5 gm of distilled water.
(b) About 99 gm of the diluted emulsion prepared in Example 4 (a) are mixed with 1 gm of the aqueous emulsion of organopolysiloxane prepared in Example 1 (b) which has Si-bonded hydrogen atoms. This mixture is applied to parchment paper with the aid of the doctor blade (described in Example 1) in accordance with the time shown in Table 3. The coated parchment papers are hung over a metal plate at 120C. in an air circulating oven for 10 seconds to cross-link the diorganopolysiloxane. The coatings are tested in accordance with Example 1 to determine their repellency to adhesive sub-stances.
The results are shown in Table 3.
li;~O1~6 Elapsed time between preparation of emul-sion mixture and app- Separation force Residual adhesive lication to paper (hours) p/cm strength %
o 4.5 61.5 2 6.5 67 3 5.5 69 6 3,5 64 ~ 24 7 68 Comparative Test The method described in Example 4 (a) is repeated except that the dimethylpolysiloxane, which has terminal vinyldimethylsiloxane units and the solution of chloroplatinic acid are added simultaneouslv to a solution containing 15 gm of an etherified polyglycol prepared by reacting isotride-canols with about 10 mols of ethylene oxide, and then mixed with 310 gm of water. The mixture is then added to a colloid mill to prepare an emulsion.
The resultant emulsion is then ~ixed w~th the aqueous emulsion prepared in Example 1 (b), applied to parchment paper and then cross-linked in accordance with the process described in Example 4 (b). The results are illustrated in Table 4.
Elapsed time between preparation of emulsion mixture and application Separation force Residual adhesive to paper (hours) p/cm strength %
1 9.5 69 2 9.5 71 3 7.5 69 4 5.5 72 11;~01~6 Although speclflc examples have been descrlbed her~ln, lt ls not lntended to limit the invention solely thereto, but to include all the modl-fications falling wlthin the spirlt and scope of the appended clalm~.
Claims (9)
1. In an improved process for preparing adhesive repellent com-positions in which (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per mole-cule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopoly-siloxanes (1), and (3) a small, catalytic amount of catalysts which pro-mote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, said catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H2O platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst (3) with the diorganopolysiloxanes (1) before it is mixed with water.
2. In an improved process for rendering surfaces adhesive repellent which comprises applying to the surfaces an aqueous emulsion containing (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopoly-siloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, said catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and com-pounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14 4H2O, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst (3) with the diorganopolysiloxanes (1) before it is mixed with water.
3. An improved process for preparing adhesive repellent com-positions in which (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per mole-cule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopoly-siloxanes (1), and (3) a small, catalytic amount of catalysts which pro-mote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, said catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14-4H20, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, which process comprises: mixing the catalyst (3) with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter mixing the homogeneous mixture with a dispersing agent and water.
4. The improved process of claims 1 or 3 wherein said diorganopolysiloxanes (1) have the formula (CH2-CH)x SiR3-xO (SiR2O)n SiR3-x (CH=CH2)x in which R is selected from the group consisting of substituted and unsubstituted monovalent hydrocarbon radicals having from 1 to 18 carbon atoms, and further being selected from the group consisting of alkyl radicals, cycloaliphatic radicals, aryl radicals, alkaryl radicals, aralkyl radicals, said substituted hydrocarbon radicals as being halo-genated hydrocarbon radicals or cyanoalkyl radicals, n is a number suffi-cient to provide that the diorganopolysiloxanes (1) have a viscosity of from 100 to 750,000 cP at 25°C., and x is 1, 2 or 3.
5. The improved process of claims 1 or 3 wherein said catalyst (3) is a platinum compound.
6. The improved process of claims 1 or 3 wherein said catalyst (3) is a platinum compound and wherein said platinum catalyst (3) is present in an amount of from 0.001 to 0.02 per cent by weight based on the weight of said diorganopolysiloxanes (1).
7. The improved process of claim 2 wherein said diorganopoly-siloxanes (1) are cross-linked at a temperature up to 250°C.
8. An improved process for preparing adhesive repellent com-positions in which (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per mole-cule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopoly-siloxanes (1), and (3) a small, catalytic amount of catalysts which pro-mote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, said catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14.4H2O, platinum-olefin complexes, platinum-alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes and platinum-vinylsiloxane complexes; as well as iron, nickel and cobalt carbonyl, the improvement which comprises: mixing the catalyst (3) with at least one-half of the total diorganopolysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and there-after simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
9. An improved process for rendering surfaces adhesive repellent which comprises applying to the surfaces an aqueous emulsion containing (1) diorganopolysiloxanes having Si-bonded vinyl groups in their terminal units, (2) from 20 to 50 per cent by weight of organopolysiloxanes having at least 3 Si-bonded hydrogen atoms per molecule based on the weight of (2) before they are mixed with the mixture of (1) and (3), and in which the organopolysiloxanes (2) are preferably employed in an amount of 1 gram equivalent of Si-bonded hydrogen for each 0.3 to 0.8 gram molecule of Si-bonded vinyl groups in the diorganopolysiloxanes (1), and (3) a small, catalytic amount of catalysts which promote the addition of Si-bonded hydrogen to vinyl groups, are mixed with water to form an aqueous emulsion, said catalyst being selected from the group consisting of finely dispersed platinum, finely dispersed ruthenium, finely dispersed rhodium, finely dispersed palladium, finely dispersed iridium and compounds or complexes of these elements, selected from platinum halides, PtC14, chloroplatinic acid and Na2PtC14.4H2O, platinum-olefin complexes, platinum alcohol or alcoholate complexes, platinum-ether complexes, platinum-aldehyde com-plexes, platinum-ketone complexes and platinum-vinylsiloxane complexes;
as well as iron, nickel and cobalt carbonyl, the improvement which com-prises: mixing catalyst (3) with at least one-half of the total diorgano-polysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
as well as iron, nickel and cobalt carbonyl, the improvement which com-prises: mixing catalyst (3) with at least one-half of the total diorgano-polysiloxanes (1) in the absence of a dispersing agent and water to form a homogeneous mixture and thereafter simultaneously mixing a dispersing agent, water and the homogeneous mixture to form an emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2601159A DE2601159C3 (en) | 1976-01-14 | 1976-01-14 | Process for the production of coatings which repel tacky substances |
| DEP2601159.6 | 1976-01-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1120176A true CA1120176A (en) | 1982-03-16 |
Family
ID=5967422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000269185A Expired CA1120176A (en) | 1976-01-14 | 1977-01-05 | Process for preparing adhesive repellent coatings |
Country Status (10)
| Country | Link |
|---|---|
| AT (1) | AT353604B (en) |
| BE (1) | BE850327A (en) |
| CA (1) | CA1120176A (en) |
| DE (1) | DE2601159C3 (en) |
| FI (1) | FI763355A (en) |
| FR (1) | FR2338316A1 (en) |
| GB (1) | GB1541801A (en) |
| IT (1) | IT1083155B (en) |
| NL (1) | NL7614352A (en) |
| SE (1) | SE421322B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672428A (en) * | 1995-10-17 | 1997-09-30 | Hoechst Celanese Corporation | Silicone release coated polyester film and a process for coating the film |
| US5728339A (en) * | 1991-10-11 | 1998-03-17 | Hoechst Celanese Corporation | In-line silicone coated polyester film and a process for coating the film |
| US6410134B1 (en) * | 1999-08-09 | 2002-06-25 | Skc Limited | Aqueous silicone coating composition and polyester release films coated therewith |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4190688A (en) * | 1978-03-15 | 1980-02-26 | General Electric Company | Silicone paper release compositions |
| DE2845541C3 (en) * | 1978-10-19 | 1981-04-02 | Beiersdorf Ag, 2000 Hamburg | Process for the production of adhesive-repellent coatings on flat, sheet or web-shaped material |
| US4248751A (en) * | 1979-08-31 | 1981-02-03 | Dow Corning Corporation | Process for producing a silicone elastomer emulsion and use thereof |
| DE3105148A1 (en) * | 1981-02-12 | 1982-09-09 | Wacker-Chemie GmbH, 8000 München | "METHOD FOR COATING DOCUMENTS" |
| US4340647A (en) * | 1981-05-22 | 1982-07-20 | General Electric Company | Vinyl gum cure accelerators for addition-cure silicone |
| US4824877A (en) * | 1988-02-02 | 1989-04-25 | Dow Corning Corporation | High polymer content silicone emulsions |
| US4961963A (en) * | 1989-09-01 | 1990-10-09 | Dow Corning Corporation | Silicone release coatings containing rhodium |
| DE19528225A1 (en) * | 1995-08-01 | 1997-02-06 | Wacker Chemie Gmbh | Coated airbags, coating material and coating processes |
| DE19535005A1 (en) * | 1995-09-21 | 1997-03-27 | Wacker Chemie Gmbh | Aqueous organopolysiloxane emulsions and emulsifiers for their preparation |
| WO2005085357A1 (en) * | 2004-03-05 | 2005-09-15 | Dow Corning Toray Co., Ltd. | Emulsion composition for silicone rubber sponge, process for producing the same, and process for producing silicone rubber sponge |
| EP2145912A1 (en) | 2008-07-19 | 2010-01-20 | Momentive Performance Materials GmbH | Method of coating substrates |
| WO2015077912A1 (en) * | 2013-11-26 | 2015-06-04 | Dow Corning (China) Holding Co., Ltd. | Novel silicone emulsion, water-based anchorage additive thereof and silicone release coating composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3900617A (en) * | 1973-11-27 | 1975-08-19 | Gen Electric | Method of rendering flexible sheet material non-adherent and article produced thereby |
-
1976
- 1976-01-14 DE DE2601159A patent/DE2601159C3/en not_active Expired
- 1976-11-23 FI FI763355A patent/FI763355A/fi not_active Application Discontinuation
- 1976-12-23 NL NL7614352A patent/NL7614352A/en not_active Application Discontinuation
-
1977
- 1977-01-05 CA CA000269185A patent/CA1120176A/en not_active Expired
- 1977-01-07 GB GB552/77A patent/GB1541801A/en not_active Expired
- 1977-01-12 IT IT47601/77A patent/IT1083155B/en active
- 1977-01-13 FR FR7700841A patent/FR2338316A1/en active Granted
- 1977-01-13 SE SE7700337A patent/SE421322B/en unknown
- 1977-01-13 AT AT15577A patent/AT353604B/en not_active IP Right Cessation
- 1977-01-13 BE BE174030A patent/BE850327A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728339A (en) * | 1991-10-11 | 1998-03-17 | Hoechst Celanese Corporation | In-line silicone coated polyester film and a process for coating the film |
| US5672428A (en) * | 1995-10-17 | 1997-09-30 | Hoechst Celanese Corporation | Silicone release coated polyester film and a process for coating the film |
| US6410134B1 (en) * | 1999-08-09 | 2002-06-25 | Skc Limited | Aqueous silicone coating composition and polyester release films coated therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2601159C3 (en) | 1982-02-04 |
| IT1083155B (en) | 1985-05-21 |
| SE7700337L (en) | 1977-07-15 |
| NL7614352A (en) | 1977-07-18 |
| FR2338316B1 (en) | 1978-10-20 |
| BE850327A (en) | 1977-07-13 |
| DE2601159B2 (en) | 1980-12-04 |
| DE2601159A1 (en) | 1977-07-21 |
| SE421322B (en) | 1981-12-14 |
| ATA15577A (en) | 1979-04-15 |
| GB1541801A (en) | 1979-03-07 |
| FI763355A (en) | 1977-07-15 |
| AT353604B (en) | 1979-11-26 |
| FR2338316A1 (en) | 1977-08-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |