US20040260045A1 - Cyanoacrylate compositions - Google Patents
Cyanoacrylate compositions Download PDFInfo
- Publication number
- US20040260045A1 US20040260045A1 US10/463,461 US46346103A US2004260045A1 US 20040260045 A1 US20040260045 A1 US 20040260045A1 US 46346103 A US46346103 A US 46346103A US 2004260045 A1 US2004260045 A1 US 2004260045A1
- Authority
- US
- United States
- Prior art keywords
- cyanoacrylate
- accelerator
- composition according
- composition
- component
- 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.)
- Granted
Links
- 0 *C.CCC(=O)OCCOCCOc1ccccc1 Chemical compound *C.CCC(=O)OCCOCCOc1ccccc1 0.000 description 12
- LYLPRUYJPLDJEU-BYYHNAKLSA-N CCCCCCCCCC1=CC=C(OCCOCCOC(=O)/C=C/C(=O)OCCOCCOC2=CC=C(CCCCCCCCC)C=C2)C=C1 Chemical compound CCCCCCCCCC1=CC=C(OCCOCCOC(=O)/C=C/C(=O)OCCOCCOC2=CC=C(CCCCCCCCC)C=C2)C=C1 LYLPRUYJPLDJEU-BYYHNAKLSA-N 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N C=C(C)C(=O)OCCOC(=O)C(=C)C Chemical compound C=C(C)C(=O)OCCOC(=O)C(=C)C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- UXWKDYXFUUBISW-UHFFFAOYSA-N C[Si]1(C)OCCOCCOCCO1 Chemical compound C[Si]1(C)OCCOCCOCCO1 UXWKDYXFUUBISW-UHFFFAOYSA-N 0.000 description 1
- JIOBGPYSBDFDAB-UHFFFAOYSA-N C[Si]1(C)OCCOCCOCCOCCO1 Chemical compound C[Si]1(C)OCCOCCOCCOCCO1 JIOBGPYSBDFDAB-UHFFFAOYSA-N 0.000 description 1
- VYPNMUSYTNBGQH-UHFFFAOYSA-N C[Si]1(C)OCCOCCOCCOCCOCCO1 Chemical compound C[Si]1(C)OCCOCCOCCOCCOCCO1 VYPNMUSYTNBGQH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/30—Nitriles
- C08F22/32—Alpha-cyano-acrylic acid; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/30—Nitriles
- C08F222/32—Alpha-cyano-acrylic acid; Esters thereof
- C08F222/322—Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Definitions
- This invention relates to cyanoacrylate-containing compositions that include, in addition to the cyanoacrylate component, a certain accelerator to improve fixture speeds on certain substrates.
- Cyanoacrylate adhesive compositions are well known, and widely used as quick setting, instant adhesives with a wide variety of uses. See H. V. Coover, D. W. Dreifus and J. T. O'Connor, “Cyanoacrylate Adhesives” in Handbook of Adhesives, 27, 463-77, I. Skeist, ed., Van Nostrand Reinhold, N.Y., 3rd ed. (1990). See also G. H. Millet “Cyanoacrylate Adhesives” in Structural Adhesives: Chemistry and Technology , S. R. Hartshorn, ed., Plenun Press, New York, p. 249-307 (1986).
- Henkel Loctite Corporation [then Loctite Corporation, at least in part through its Loctite (Ireland) Ltd. affiliate] developed a technology based on calixarene and oxacalixarene compounds. Generally, the addition of such materials to a cyanoacrylate allow for accelerated fixturing of substrates to-be-bonded together. See U.S. Pat. Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461.
- Henkel Loctite Corporation also developed technology based on the addition of silacrown compounds to cyanoacrylate adhesive compositions to accelerate fixturing.
- U.S. Pat. No. 4,906,317 (Liu) is directed to cyanoacrylate adhesive compositions which include silacrown compounds as additives to give substantially reduced fixture and cure times on de-activating substrates such as wood.
- the silacrown compounds are preferably employed at levels of about 0.1-5% by weight of the composition.
- cyanoacrylate adhesive composition is provided with a first accelerator component selected from calixarenes and oxacalixarenes, silacrowns, cyclodextrins, crown ethers, and combinations thereof; and a second accelerator component selected from poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds, and combinations thereof.
- first accelerator component selected from calixarenes and oxacalixarenes, silacrowns, cyclodextrins, crown ethers, and combinations thereof
- second accelerator component selected from poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds, and combinations thereof.
- Henkel Loctite Corporation developed a cyanoacrylate adhesive composition, based on a cyanoacrylate component; and an accelerator component consisting essentially of (i) calixarenes, oxcalixarenes, or a combination thereof, and (ii) at least one crown ether, where the composition exhibits a fixturing speed of less than 20 seconds for bonding two substrates, at least one of which is constructed of a material selected from steel, epoxy glass or balsawood, as described in U.S. Pat. No. 6,475,331 (O'Connor).
- the present invention is directed to a cyanoacrylate-based composition, which includes beyond the cyanoacrylate component,
- R is hydrogen, alkyl, alkyloxy, alkyl thioethers, haloalkyl, carboxylic acid and esters thereof, sulfinic, sulfonic and sulfurous acids and esters, phosphinic, phosphonic and phosphorous acids and esters thereof, X is optional, but when present is an aliphatic or aromatic hydrocarbyl linkage, which may be substituted by oxygen or sulfur, and Z is a single or double bond, such as
- a particularly desirable chemical within this class as an accelerator component is
- This invention is also directed to a method of bonding together two substrates, at least one of which is constructed of certain woods, and ceramic, and combinations thereof.
- the method includes applying to at least one of the substrates a composition as described above, and thereafter mating together the substrates.
- the present invention is directed to reaction products of the inventive compositions.
- the invention is directed to a method of preparing the inventive compositions.
- FIG. 1 shows a comparative chart of Samples A-D, where MDF is medium density fiberboard, ABS is acrylonitrile butadiene styrene copolymer, Al is aluminum and SS is stainless steel.
- this invention is directed to a cyanoacrylate-based composition, which includes beyond the cyanoacrylate component,
- R is hydrogen, alkyl, alkyloxy, alkyl thioethers, haloalkyl, carboxylic acid and esters thereof, sulfinic, sulfonic and sulfurous acids and esters, phosphinic, phosphonic and phosphorous acids and esters thereof, X is optional, but when present is an aliphatic or aromatic hydrocarbyl linkage, which may be substituted by oxygen or sulfur, and Z is a single or double bond, such as
- a particularly desirable chemical within this class as an accelerator component is
- the cyanoacrylate component includes cyanoacrylate monomers which may be chosen with a raft of substituents, such as those represented by H 2 C ⁇ C(CN)—COOR, where R is selected from C 1-15 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups.
- the cyanoacrylate monomer is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates (such as n-butyl-2-cyanoacrylate), octyl cyanoacrylates, allyl cyanoacrylate, ⁇ -methoxyethyl cyanoacrylate and combinations thereof.
- a particularly desirable one is ethyl-2-cyanoacrylate.
- the cyanoacrylate component should be included in the compositions in an amount within the range of from about 50% to about 99.98% by weight, with the range of about 90% to about 99% by weight being desirable, and about 95% by weight of the total composition being particularly desirable.
- accelerators may also be included in the composition.
- Such accelerators may be selected from calixarenes and oxacalixarenes, silacrowns, crown ethers, cyclodextrins, poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds and combinations thereof.
- R 1 is alkyl, alkoxy, substituted alkyl or substituted alkoxy
- R 2 is H or alkyl
- n is 4, 6 or 8.
- TBTEOCA tetrabutyl tetra[2-ethoxy-2-oxoethoxy]calix-4-arene
- a host of crown ethers are known.
- examples which may be used herein either individually or in combination, or in combination with other first accelerators include 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphtyl-16-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1,2-t-butyl-18-c
- silacrowns again many are known, and are reported in the literature.
- a typical silacrown may be represented within the following structure (VI):
- R 3 and R 4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer
- R 5 is H or CH 3 and n is an integer of between 1 and 4.
- suitable R 3 and R 4 groups are R groups, alkoxy groups, such as methoxy, and aryloxy groups, such as phenoxy.
- the R 3 and R 4 groups may contain halogen or other substituents, an example being trifluoropropyl.
- groups not suitable as R 4 and R 5 groups are basic groups, such as amino, substituted amino and alkylamino.
- silacrown compounds useful in the inventive compositions include:
- cyclodextrins may be used in connection with the present invention.
- those described and claimed in U.S. Pat. No. 5,312,864 (Wenz), the disclosure of which is hereby expressly incorporated herein by reference, as hydroxyl group derivatives of an ⁇ , ⁇ or ⁇ -cyclodextrin which is at least partly soluble in the cyanoacrylate would be appropriate choices for use herein as the first accelerator component.
- poly(ethylene glycol) di(meth)acrylates suitable for use herein include there within structure X below:
- n is greater than 3, such as within the range of 3 to 12, with n being 9 as particularly desirable. More specific examples include PEG 200 DMA, (where n is about 4) PEG 400 DMA (where n is about 9), PEG 600 DMA (where n is about 14), and PEG 800 DMA (where n is about 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule, excluding the two methacrylate groups, expressed as grams/mole (i.e., 400 g/mol).
- a particularly desirable PEG DMA is PEG 400 DMA.
- ethoxylated hydric compounds or ethoxylated fatty alcohols that may be employed
- appropriate ones may be chosen from those within structure XI:
- C m can be a linear or branched alkyl or alkenyl chain
- m is an integer between 1 to 30, such as from 5 to 20
- n is an integer between 2 to 30, such as from 5 to 15, and R may be H or alkyl, such as C 1-6 alkyl.
- the accelerator embraced by structures I-IV should be included in the compositions in an amount within the range of from about 0.01% to about 10% by weight, with the range of about 0.1 to about 0.5% by weight being desirable, and about 0.4% by weight of the total composition being particularly desirable.
- additives may be included in the inventive compositions to confer additional physical properties, such as improved shelf-life stability, flexibility, thixotropy, increased viscosity, color, improved toughness, and enhanced resistance to thermal degradation.
- additives therefore may be selected from free radical stabilizers, anionic stabilizers, gelling agents, thickeners [such as polymethyl methacrylate (PMMA)], thixotropy conferring agents (such as fumed silica), dyes, toughening agents, thermal degradation enhancers, plasticizers and combinations thereof.
- a method of bonding together two substrates at least one of which is constructed of materials, such as certain woods, cotton and cork.
- the method includes applying to at least one of the substrates a composition as described above, and thereafter mating together the substrates for a time sufficient to permit the adhesive to fixture.
- the substrate should become fixed in less than 30 seconds, and depending on substrate as little as 1-3 seconds.
- reaction products of the so-described compositions there is provided reaction products of the so-described compositions.
- a method of preparing the so-described compositions includes providing a cyanoacrylate component, and combining therewith with mixing a first and second accelerator component.
- a method of bonding together two substrates at least one of which is constructed of a material selected from the group consisting of wood, cotton and cork, using the compositions of this invention.
- the method includes applying the compositions to at least one of the substrates and mating together the substrates for a time sufficient to permit the composition to fixture.
- Samples A and B (cyanoacrylate with compound IV) demonstrates improved fixture speeds on certain substrates, namely the woods, obechi; ash and limba, and ceramic, as compared with Sample D, which is the cyanoacrylate with the combination of the noted calixarenes and polyethylene glycol dimethacrylate.
Abstract
Description
- 1. Field of the Invention
- This invention relates to cyanoacrylate-containing compositions that include, in addition to the cyanoacrylate component, a certain accelerator to improve fixture speeds on certain substrates.
- 2. Brief Description of Related Technology
- Cyanoacrylate adhesive compositions are well known, and widely used as quick setting, instant adhesives with a wide variety of uses. See H. V. Coover, D. W. Dreifus and J. T. O'Connor, “Cyanoacrylate Adhesives” inHandbook of Adhesives, 27, 463-77, I. Skeist, ed., Van Nostrand Reinhold, N.Y., 3rd ed. (1990). See also G. H. Millet “Cyanoacrylate Adhesives” in Structural Adhesives: Chemistry and Technology, S. R. Hartshorn, ed., Plenun Press, New York, p. 249-307 (1986).
- Nonetheless, various techniques have been used to improve further the fixture times of such adhesive compositions for certain applications where it is important to be able to secure one substrate to another quickly, while allowing the bond strength to develop over time. In addition, substrates constructed of certain materials have proven in the past difficult to bond, irrespective of the application to which the adhesive and the substrate are to be placed.
- To combat these issues, Henkel Loctite Corporation [then Loctite Corporation, at least in part through its Loctite (Ireland) Ltd. affiliate] developed a technology based on calixarene and oxacalixarene compounds. Generally, the addition of such materials to a cyanoacrylate allow for accelerated fixturing of substrates to-be-bonded together. See U.S. Pat. Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461.
- In addition to calixarene compounds, Henkel Loctite Corporation also developed technology based on the addition of silacrown compounds to cyanoacrylate adhesive compositions to accelerate fixturing. For instance, U.S. Pat. No. 4,906,317 (Liu) is directed to cyanoacrylate adhesive compositions which include silacrown compounds as additives to give substantially reduced fixture and cure times on de-activating substrates such as wood. The silacrown compounds are preferably employed at levels of about 0.1-5% by weight of the composition.
- Henkel KGaA developed technology based on the addition to cyanoacrylate compositions of cyclodextrins to accelerate fixturing. In U.S. Pat. No. 5,312,864 (Wenz), the acceleration of the setting properties of a cyanoacrylate adhesive composition by adding thereto a hydroxyl group derivative of an α-, β- or γ-cyclodextrin which is at least partly soluble in the cyanoacrylate is described.
- Other approaches have also been investigated, such as in U.S. Pat. No. 4,837,260 (Sato), in which it is reported the use of crown ethers in cyanoacrylate adhesive compositions.
- More recently, Loctite (R&D) Ltd. investigated other ways in which to accelerate the curing of cyanoacrylate adhesive compositions. In U.S. Pat. No. 6,294,629 (O'Dwyer), a cyanoacrylate adhesive composition is provided with a first accelerator component selected from calixarenes and oxacalixarenes, silacrowns, cyclodextrins, crown ethers, and combinations thereof; and a second accelerator component selected from poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds, and combinations thereof.
- And Henkel Loctite Corporation developed a cyanoacrylate adhesive composition, based on a cyanoacrylate component; and an accelerator component consisting essentially of (i) calixarenes, oxcalixarenes, or a combination thereof, and (ii) at least one crown ether, where the composition exhibits a fixturing speed of less than 20 seconds for bonding two substrates, at least one of which is constructed of a material selected from steel, epoxy glass or balsawood, as described in U.S. Pat. No. 6,475,331 (O'Connor).
- Notwithstanding the state-of-the-technology it would be desirable to provide alternative technologies to improve the fixturing speed of cyanoacrylates.
-
- I, as an accelerator, where R is hydrogen, alkyl, alkyloxy, alkyl thioethers, haloalkyl, carboxylic acid and esters thereof, sulfinic, sulfonic and sulfurous acids and esters, phosphinic, phosphonic and phosphorous acids and esters thereof, X is optional, but when present is an aliphatic or aromatic hydrocarbyl linkage, which may be substituted by oxygen or sulfur, and Z is a single or double bond, such as
- II, where R and X are as defined above, and n is 1-12, m is 1-4, and p is 1-3.
-
- III, where R, Z and n are as defined above, and R′ is the same as R, where g is the same as n.
-
- IV, where n and m combined is greater than or equal to 12.
- The inclusion of these accelerators into a cyanoacrylate composition provides for a demonstrated improved fixture speeds, particularly on substrates constructed of certain woods, and ceramic and combinations thereof, without sacrificing shelf life.
- This invention is also directed to a method of bonding together two substrates, at least one of which is constructed of certain woods, and ceramic, and combinations thereof. The method includes applying to at least one of the substrates a composition as described above, and thereafter mating together the substrates.
- In addition, the present invention is directed to reaction products of the inventive compositions.
- Also, the invention is directed to a method of preparing the inventive compositions.
- The invention will be more fully understood by a reading of the section entitled “Detailed Description of the Invention”, which follows.
- FIG. 1 shows a comparative chart of Samples A-D, where MDF is medium density fiberboard, ABS is acrylonitrile butadiene styrene copolymer, Al is aluminum and SS is stainless steel.
-
- I, as an accelerator, where R is hydrogen, alkyl, alkyloxy, alkyl thioethers, haloalkyl, carboxylic acid and esters thereof, sulfinic, sulfonic and sulfurous acids and esters, phosphinic, phosphonic and phosphorous acids and esters thereof, X is optional, but when present is an aliphatic or aromatic hydrocarbyl linkage, which may be substituted by oxygen or sulfur, and Z is a single or double bond, such as
- II, where R and X are as defined above.
-
- III, where R, Z and n are as defined above, and R′ is the same as R, and g is the same as n.
-
- IV, where n and m combined are greater than or equal to 12.
- The inclusion of such an accelerator into a cyanoacrylate composition provides for a demonstrated improved fixture speeds, particularly on substrates constructed of certain woods, such as obechi, and ceramic, and combinations thereof, without sacrificing shelf life.
- The cyanoacrylate component includes cyanoacrylate monomers which may be chosen with a raft of substituents, such as those represented by H2C═C(CN)—COOR, where R is selected from C1-15 alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl and haloalkyl groups. Desirably, the cyanoacrylate monomer is selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylates, butyl cyanoacrylates (such as n-butyl-2-cyanoacrylate), octyl cyanoacrylates, allyl cyanoacrylate, β-methoxyethyl cyanoacrylate and combinations thereof. A particularly desirable one is ethyl-2-cyanoacrylate.
- The cyanoacrylate component should be included in the compositions in an amount within the range of from about 50% to about 99.98% by weight, with the range of about 90% to about 99% by weight being desirable, and about 95% by weight of the total composition being particularly desirable.
- In addition to the accelerator embraced by the chemical structures above, one or more additional accelerators may also be included in the composition. Such accelerators may be selected from calixarenes and oxacalixarenes, silacrowns, crown ethers, cyclodextrins, poly(ethyleneglycol) di(meth)acrylates, ethoxylated hydric compounds and combinations thereof.
- Of the calixarenes and oxacalixarenes, many are known, and are reported in the patent literature. See e.g. U.S. Pat. Nos. 4,556,700, 4,622,414, 4,636,539, 4,695,615, 4,718,966, and 4,855,461, the disclosures of each of which are hereby expressly incorporated herein by reference.
-
- where R1 is alkyl, alkoxy, substituted alkyl or substituted alkoxy; R2 is H or alkyl; and n is 4, 6 or 8.
- One particularly desirable calixarene is tetrabutyl tetra[2-ethoxy-2-oxoethoxy]calix-4-arene (“TBTEOCA”).
- A host of crown ethers are known. For instance, examples which may be used herein either individually or in combination, or in combination with other first accelerators include 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5-dibenzo-24-crown-8, dibenzo-30-crown-10, tribenzo-18-crown-6, asym-dibenzo-22-crown-6, dibenzo-14-crown-4, dicyclohexyl-18-crown-6, dicyclohexyl-24-crown-8, cyclohexyl-12-crown-4, 1,2-decalyl-15-crown-5, 1,2-naphtho-15-crown-5, 3,4,5-naphtyl-16-crown-5, 1,2-methyl-benzo-18-crown-6, 1,2-methylbenzo-5, 6-methylbenzo-18-crown-6, 1,2-t-butyl-18-crown-6, 1,2-vinylbenzo-15-crown-5, 1,2-vinylbenzo-18-crown-6, 1,2-t-butyl-cyclohexyl-18-crown-6, asym-dibenzo-22-crown-6 and 1,2-benzo-1,4-benzo-5-oxygen-20-crown-7. See U.S. Pat. No. 4,837,260 (Sato), the disclosure of which is hereby expressly incorporated here by reference.
-
- where R3 and R4 are organo groups which do not themselves cause polymerization of the cyanoacrylate monomer, R5 is H or CH3 and n is an integer of between 1 and 4. Examples of suitable R3 and R4 groups are R groups, alkoxy groups, such as methoxy, and aryloxy groups, such as phenoxy. The R3 and R4 groups may contain halogen or other substituents, an example being trifluoropropyl. However, groups not suitable as R4 and R5 groups are basic groups, such as amino, substituted amino and alkylamino.
-
-
-
- and dimethylsila-17-crown-6 (IX).
- See e.g., U.S. Pat. No. 4,906,317 (Liu), the disclosure of which is hereby expressly incorporated herein by reference.
- Many cyclodextrins may be used in connection with the present invention. For instance, those described and claimed in U.S. Pat. No. 5,312,864 (Wenz), the disclosure of which is hereby expressly incorporated herein by reference, as hydroxyl group derivatives of an α, β or γ-cyclodextrin which is at least partly soluble in the cyanoacrylate would be appropriate choices for use herein as the first accelerator component.
-
- where n is greater than 3, such as within the range of 3 to 12, with n being 9 as particularly desirable. More specific examples include PEG 200 DMA, (where n is about 4) PEG 400 DMA (where n is about 9), PEG 600 DMA (where n is about 14), and PEG 800 DMA (where n is about 19), where the number (e.g., 400) represents the average molecular weight of the glycol portion of the molecule, excluding the two methacrylate groups, expressed as grams/mole (i.e., 400 g/mol). A particularly desirable PEG DMA is PEG 400 DMA.
-
- where Cm can be a linear or branched alkyl or alkenyl chain, m is an integer between 1 to 30, such as from 5 to 20, n is an integer between 2 to 30, such as from 5 to 15, and R may be H or alkyl, such as C1-6 alkyl.
- Commercially available examples of materials within structure XI include those offered under the DEHYDOL tradename from Cognis Deutschland GmbH & Co. KG, Dusseldorf, Germany, such as DEHYDOL 100.
- The accelerator embraced by structures I-IV should be included in the compositions in an amount within the range of from about 0.01% to about 10% by weight, with the range of about 0.1 to about 0.5% by weight being desirable, and about 0.4% by weight of the total composition being particularly desirable.
- Additives may be included in the inventive compositions to confer additional physical properties, such as improved shelf-life stability, flexibility, thixotropy, increased viscosity, color, improved toughness, and enhanced resistance to thermal degradation. Such additives therefore may be selected from free radical stabilizers, anionic stabilizers, gelling agents, thickeners [such as polymethyl methacrylate (PMMA)], thixotropy conferring agents (such as fumed silica), dyes, toughening agents, thermal degradation enhancers, plasticizers and combinations thereof.
- In another aspect of the invention, there is provided a method of bonding together two substrates, at least one of which is constructed of materials, such as certain woods, cotton and cork. The method includes applying to at least one of the substrates a composition as described above, and thereafter mating together the substrates for a time sufficient to permit the adhesive to fixture. For many applications, the substrate should become fixed in less than 30 seconds, and depending on substrate as little as 1-3 seconds.
- In yet another aspect of the invention, there is provided reaction products of the so-described compositions.
- In still another aspect of the invention, there is provided a method of preparing the so-described compositions. The method includes providing a cyanoacrylate component, and combining therewith with mixing a first and second accelerator component.
- In an additional aspect of the invention, there is provided a method of bonding together two substrates, at least one of which is constructed of a material selected from the group consisting of wood, cotton and cork, using the compositions of this invention. The method includes applying the compositions to at least one of the substrates and mating together the substrates for a time sufficient to permit the composition to fixture.
- These aspects of the invention will be further illustrated by the examples which follow.
- We prepared four samples to evaluate their fixture speeds on a variety of substrates. The samples were prepared by mixing together the constituents in any order for a sufficient period of time to ensure substantial homogeneity of the constituents. Ordinarily, about 30 minutes would suffice, depending of course on the quantity of the constituents used. The constituents of these samples are listed below in Table 1.
TABLE 1 Component Sample Type Identity A B C D CA Ethyl-2-CA 82.4983 82.4983 82.3983 82.3983 Accelerator Compound IV 0.5 0.5 0.4 — TBTEOCA — — 0.2 0.2 PEG 400 DMA — — — 0.4 Plasticizer Glycerol 12.5 12.5 12.5 12.5 triacetate Stabilizer HQ 0.5 0.5 0.5 0.5 Thickener PMMA 4.0 4.0 4.0 4.0 - We applied each of Samples A-D to the substrates listed below in Table 2, and measured their fixture speeds in bonding the substrates (each being made from the same material) to one another. The fixture speed is the time from joining the two substrates (each of which being about 1 inch wide and being aligned with about a 0.5 inch overlap) sufficient to hold a 3 kg weight. The results are illustrated below in Table 2 and shown in FIG. 1.
TABLE 2 Physical Sample/(secs) Properties Substrate A B C D Fixture Paper 40 40 10 10 Times MOF 40 40 25 40 Obechi 10 10 15 15 Yellow Pine 30 30 25 20 Ash 10 10 10 15 W. Deal 40 40 15 40 Limba 10 10 10 15 Ceramic/ butt 10 10 15 15 Balsa 3 3 3 3 Cardboard 10 10 5 5 Polycarbonate 25 25 25 25 ABS 3 3 3 3 Aluminum 3 3 3 3 Stainless 3 3 3 3 steel - As can be seen from Table 2 and FIG. 1, Samples A and B (cyanoacrylate with compound IV) demonstrates improved fixture speeds on certain substrates, namely the woods, obechi; ash and limba, and ceramic, as compared with Sample D, which is the cyanoacrylate with the combination of the noted calixarenes and polyethylene glycol dimethacrylate.
- In addition, the combination of the accelerator used in the present invention together with the noted calixarene (Sample C) improves fixture speed compared with the combination of the noted calixarene together with the noted polyethylene glycol dimethacrylate on certain substrates namely, MDF, ash, white deal and limba.
TABLE 3 Physical Sample Properties A B C D Viscosity (MPas) 32 32 34.4 34.1 GBMS Bond 13.57 +/− 12.70 +/− 13.86 +/− 12.70 +/− Strength 24 hr. 1.56 1.54 1.00 1.15 (N/mm2) - The results shown in Table 3 illustrate that the inventive compositions (Samples A-C) behave as adhesives, yielding bond strength comparable to the control composition (Sample D), while demonstrating with reference to Table 2 improved fixture speeds on certain substrates, namely the woods, obechi, ash and limba, and ceramic.
- In Table 4, stability data for Samples A-D filled in aluminum tubes and aged at 82° C. for the specified period of time is shown. The results in Table 4 demonstrate that the inventive compositions retain the benefits noted above even after ageing under the noted conditions.
TABLE 4 Aged Sample Data A B C D 3 days @ 82° C. Viscosity (Mps) 36 35.7 35.3 36.5 Ratio 1.13 1.12 1.04 1.07 Fixture time 40-50 40-50 5-10 10-15 (secs) on paper 6 days @ 82° C. Viscosity (Mps) 38.2 39.4 40.3 39.2 Ratio 1.19 1.23 1.17 1.15 Fixture time 80-100 80-100 15-20 30-40 (secs) on paper
Claims (14)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/463,461 US6835789B1 (en) | 2003-06-18 | 2003-06-18 | Cyanoacrylate compositions |
MXPA05012296A MXPA05012296A (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate compositions. |
JP2006516790A JP4624997B2 (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate composition |
PCT/IE2004/000086 WO2004111147A2 (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate compositions |
KR1020057024049A KR100964088B1 (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate Compositions |
CN2004800133648A CN1791649B (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate compositions |
BRPI0411472-8A BRPI0411472A (en) | 2003-06-18 | 2004-06-18 | cyanoacrylate adhesive composition, method of preparation thereof, and method of agglutination of two substrates together |
CA2525011A CA2525011C (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate compositions |
EP04737052A EP1633827A2 (en) | 2003-06-18 | 2004-06-18 | Cyanoacrylate compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/463,461 US6835789B1 (en) | 2003-06-18 | 2003-06-18 | Cyanoacrylate compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
US20040260045A1 true US20040260045A1 (en) | 2004-12-23 |
US6835789B1 US6835789B1 (en) | 2004-12-28 |
Family
ID=33517106
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/463,461 Expired - Fee Related US6835789B1 (en) | 2003-06-18 | 2003-06-18 | Cyanoacrylate compositions |
Country Status (9)
Country | Link |
---|---|
US (1) | US6835789B1 (en) |
EP (1) | EP1633827A2 (en) |
JP (1) | JP4624997B2 (en) |
KR (1) | KR100964088B1 (en) |
CN (1) | CN1791649B (en) |
BR (1) | BRPI0411472A (en) |
CA (1) | CA2525011C (en) |
MX (1) | MXPA05012296A (en) |
WO (1) | WO2004111147A2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007008971A1 (en) | 2005-07-11 | 2007-01-18 | Henkel Corporation | Toughened cyanoacrylate compositions |
US20100010159A1 (en) * | 2008-07-11 | 2010-01-14 | Tyco Healthcare Group Lp | Functionalized Inclusion Complexes As Crosslinkers |
CN103980397A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing composition, preparation and application methods and product thereof |
CN104193919A (en) * | 2014-08-26 | 2014-12-10 | 太仓碧奇新材料研发有限公司 | Polyethylene terephthalate composite material for 3D printing and preparation method thereof |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7270932B2 (en) * | 2004-02-06 | 2007-09-18 | Rohm And Haas Electronic Materials Llc | Imaging composition and method |
CN101305064A (en) * | 2005-11-10 | 2008-11-12 | 汉高两合股份公司 | Binding agent, sealant and paint containing glass particle as filling material |
WO2007054112A1 (en) * | 2005-11-10 | 2007-05-18 | Henkel Ag & Co. Kgaa | Adhesives, sealants and coatings containing glass particles as a filler |
US7659423B1 (en) | 2006-04-18 | 2010-02-09 | Loctite (R&D) Limited | Method of preparing electron deficient olefins in polar solvents |
ATE461255T1 (en) * | 2006-09-08 | 2010-04-15 | 3M Innovative Properties Co | COLOR-CHANGING CYANOACRYLATE ADHESIVES |
US7569719B1 (en) | 2006-10-25 | 2009-08-04 | Loctite (R&D) Limited | Method of preparing electron deficient olefins |
US7718821B1 (en) | 2006-12-19 | 2010-05-18 | Loctite (R&D) Limited | Method of preparing electron deficient olefins |
US8053589B1 (en) | 2007-10-24 | 2011-11-08 | Henkel Ireland Limited | Imines and methods of preparing electron deficient olefins using such novel imines |
CA2703603A1 (en) * | 2007-10-24 | 2009-04-30 | Loctite (R&D) Limited | Electron deficient olefins |
JP5518726B2 (en) * | 2007-10-24 | 2014-06-11 | ヘンケル アイルランド リミテッド | Active methylene reagent and curable composition produced therefrom |
US7973119B1 (en) | 2007-10-24 | 2011-07-05 | Loctite (R&D) Limited | Adhesive systems using imines and salts thereof and precursurs to electron deficient olefins |
EP2116126A1 (en) | 2008-05-06 | 2009-11-11 | Henkel AG & Co. KGaA | Method and apparatus for grafting plants with fast-curing adhesives |
KR20150083127A (en) * | 2008-09-26 | 2015-07-16 | 헨켈 아이피 앤드 홀딩 게엠베하 | Cyanoacrylate compositions in non-flowable forms |
US8399698B1 (en) | 2008-10-24 | 2013-03-19 | Henkel Ireland Limited | Substituted activated methylene reagents and methods of using such reagents to form electron deficient olefins |
US10196471B1 (en) | 2008-10-24 | 2019-02-05 | Henkel IP & Holding GmbH | Curable composition having an electron deficient olefin |
WO2010125195A1 (en) | 2009-05-01 | 2010-11-04 | Loctite (R&D) Limited | Cyanoacrylate compositions |
JP5618194B2 (en) * | 2010-09-09 | 2014-11-05 | 国立大学法人筑波大学 | Azacalix [3] pyridinium salt, method for producing the same, and method for producing polyalkylene glycol using the same |
PT2511355E (en) | 2011-04-12 | 2014-01-28 | Henkel Ireland Ltd | Cyanoacrylate adhesive with improved water resistance |
JP5878631B2 (en) * | 2011-07-15 | 2016-03-08 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Cyanoacrylate composition |
WO2013112315A1 (en) * | 2012-01-25 | 2013-08-01 | Henkel Corporation | Cyanoacrylate compositions |
GB2534548B (en) | 2014-12-29 | 2020-08-12 | Adv Med Solutions Ltd | Adhesive applicator |
TWI752043B (en) * | 2016-06-28 | 2022-01-11 | 日商東亞合成股份有限公司 | 2-cyanoacrylate-based adhesive composition |
GB2567868B (en) * | 2017-10-27 | 2020-05-06 | Henkel IP & Holding GmbH | Toughened low odour cyanoacrylate compositions |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010004655A1 (en) * | 1992-05-28 | 2001-06-21 | Shin Takahashi | Cyanoacrylate adhesive composition |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE792064A (en) * | 1971-12-02 | 1973-05-29 | Bayer Ag | ANTISTATIC POLYMERS OF ACRYLONITRILE |
DE3209238A1 (en) * | 1982-03-13 | 1983-09-15 | Henkel KGaA, 4000 Düsseldorf | ADHESIVES BASED ON CYANACRYLIC ACID ESTERS |
US4906317A (en) | 1983-11-10 | 1990-03-06 | Loctite Corporation | Instant adhesive composition and bonding method employing same |
US4622414A (en) | 1984-01-27 | 1986-11-11 | Loctite Limited | Novel calixarene compounds |
US4636539A (en) | 1984-01-30 | 1987-01-13 | Loctite (Ireland) Limited | Instant adhesive composition utilizing calixarene accelerators |
US4718966A (en) | 1984-01-30 | 1988-01-12 | Loctite (Ireland) Ltd. | Bonding method utilizing cyanoacrylate adhesive having calixarene accelerator |
US4556700A (en) | 1984-01-30 | 1985-12-03 | Loctite Limited | Instant adhesive composition utilizing calixarene accelerators |
US4695615A (en) | 1984-11-21 | 1987-09-22 | Loctite (Ireland) Limited | Instant adhesive composition utilizing mixed functionality calixarenes as accelerators |
IE59509B1 (en) | 1987-01-21 | 1994-03-09 | Loctite Ireland Ltd | Functionalised oxacalixarenes, their preparation and use in instant adhesive compositions |
US4837260A (en) | 1986-05-23 | 1989-06-06 | Toagosei Chemical Industry Co., Ltd. | Cyanoacrylate compositions |
DE4009621A1 (en) | 1990-03-26 | 1991-10-02 | Henkel Kgaa | (ALPHA) -CYANACRYLATE ADHESIVE COMPOSITIONS |
IES990974A2 (en) | 1998-11-23 | 2000-05-31 | Loctite R & D Ltd | Cyanoacrylate Compositions |
JP2000191600A (en) * | 1998-12-28 | 2000-07-11 | Toagosei Co Ltd | Cyclic compound, curing accelerator for 2-cyanoacrylate comprising the compound and 2-cyanoacrylate-based composition |
JP3613321B2 (en) * | 1999-04-07 | 2005-01-26 | 東亞合成株式会社 | 2-Cyanoacrylate composition |
JP2001164199A (en) * | 1999-12-09 | 2001-06-19 | Taoka Chem Co Ltd | Alpha-cyanoacrylate-based adhesive composition |
US6475331B1 (en) | 2001-06-26 | 2002-11-05 | Henkel Loctite Corporation | Cyanoacrylate compositions |
-
2003
- 2003-06-18 US US10/463,461 patent/US6835789B1/en not_active Expired - Fee Related
-
2004
- 2004-06-18 JP JP2006516790A patent/JP4624997B2/en not_active Expired - Fee Related
- 2004-06-18 CN CN2004800133648A patent/CN1791649B/en not_active Expired - Fee Related
- 2004-06-18 CA CA2525011A patent/CA2525011C/en not_active Expired - Fee Related
- 2004-06-18 WO PCT/IE2004/000086 patent/WO2004111147A2/en active Application Filing
- 2004-06-18 EP EP04737052A patent/EP1633827A2/en not_active Ceased
- 2004-06-18 KR KR1020057024049A patent/KR100964088B1/en not_active IP Right Cessation
- 2004-06-18 MX MXPA05012296A patent/MXPA05012296A/en active IP Right Grant
- 2004-06-18 BR BRPI0411472-8A patent/BRPI0411472A/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010004655A1 (en) * | 1992-05-28 | 2001-06-21 | Shin Takahashi | Cyanoacrylate adhesive composition |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007008971A1 (en) | 2005-07-11 | 2007-01-18 | Henkel Corporation | Toughened cyanoacrylate compositions |
US20080314519A1 (en) * | 2005-07-11 | 2008-12-25 | Henkel Corporation | Toughened Cyanoacrylate Compositions |
EP1907496A4 (en) * | 2005-07-11 | 2009-07-29 | Henkel Corp | Toughened cyanoacrylate compositions |
US20100010159A1 (en) * | 2008-07-11 | 2010-01-14 | Tyco Healthcare Group Lp | Functionalized Inclusion Complexes As Crosslinkers |
US8207264B2 (en) | 2008-07-11 | 2012-06-26 | Tyco Healthcare Group Lp | Functionalized inclusion complexes as crosslinkers |
CN103980397A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing composition, preparation and application methods and product thereof |
CN104193919A (en) * | 2014-08-26 | 2014-12-10 | 太仓碧奇新材料研发有限公司 | Polyethylene terephthalate composite material for 3D printing and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
KR100964088B1 (en) | 2010-06-16 |
JP4624997B2 (en) | 2011-02-02 |
KR20060024799A (en) | 2006-03-17 |
EP1633827A2 (en) | 2006-03-15 |
US6835789B1 (en) | 2004-12-28 |
CN1791649A (en) | 2006-06-21 |
JP2006527782A (en) | 2006-12-07 |
BRPI0411472A (en) | 2006-07-11 |
CA2525011A1 (en) | 2004-12-23 |
WO2004111147A3 (en) | 2005-03-24 |
CA2525011C (en) | 2012-07-31 |
CN1791649B (en) | 2010-05-26 |
WO2004111147A2 (en) | 2004-12-23 |
MXPA05012296A (en) | 2006-07-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6835789B1 (en) | Cyanoacrylate compositions | |
US6294629B1 (en) | Cyanoacrylate compositions | |
US20060094833A1 (en) | Shock resistant cyanoacrylate compositions | |
US6475331B1 (en) | Cyanoacrylate compositions | |
EP2732000B1 (en) | Cyanoacrylate compositions | |
US10947418B2 (en) | Cyanoacrylate compositions | |
EP2121777B1 (en) | Cyanoacrylate compositions incorporating graphite platelets | |
KR102593346B1 (en) | Cyanoacrylate composition | |
US20200255692A1 (en) | Cyanoacrylate compositions | |
KR102063507B1 (en) | Cyanoacrylate compositions | |
JP7374084B2 (en) | Enhanced low odor/low bloom cyanoacrylate composition | |
US7687561B1 (en) | Toughened cyanoacrylate compositions | |
US20040131827A1 (en) | Toughened cyanoacrylate compositions | |
US8303705B2 (en) | Cyanoacrylate compositions | |
US11725119B2 (en) | Cyanoacrylate compositions | |
KR102657838B1 (en) | Cyanoacrylate composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: LOCTITE (IRELAND) LTD., CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KNEAFSEY, BRENDAN J.;WOOLFSON, HARRY J.;BIRKETT, DAVID P.;AND OTHERS;REEL/FRAME:014212/0202 Effective date: 20030610 Owner name: LOCTITE (R&D) LTD., CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LOCTITE (IRELAND) LTD.;REEL/FRAME:014212/0116 Effective date: 20030617 |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
AS | Assignment |
Owner name: HENKEL IRELAND HOLDING B.V., IRELAND Free format text: MERGER;ASSIGNOR:LOCTITE (R&D) LIMITED;REEL/FRAME:029741/0063 Effective date: 20111121 Owner name: HENKEL IRELAND LIMITED, IRELAND Free format text: MERGER;ASSIGNOR:HENKEL IRELAND HOLDING B.V.;REEL/FRAME:029741/0205 Effective date: 20111122 |
|
AS | Assignment |
Owner name: HENKEL IRELAND LIMITED, GERMANY Free format text: CHANGE OF ADDRESS;ASSIGNOR:HENKEL IRELAND LIMITED;REEL/FRAME:032319/0955 Effective date: 20121113 |
|
AS | Assignment |
Owner name: HENKEL IP & HOLDING GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HENKEL AG & CO. KGAA;REEL/FRAME:032329/0172 Effective date: 20131121 Owner name: HENKEL AG & CO. KGAA, GERMANY Free format text: MERGER;ASSIGNOR:HENKEL IRELAND LIMITED;REEL/FRAME:032329/0132 Effective date: 20130829 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20161228 |