CA1125285A - Poly(ethylenically unsaturated alkoxy) heterocyclic compounds - Google Patents
Poly(ethylenically unsaturated alkoxy) heterocyclic compoundsInfo
- Publication number
- CA1125285A CA1125285A CA352,477A CA352477A CA1125285A CA 1125285 A CA1125285 A CA 1125285A CA 352477 A CA352477 A CA 352477A CA 1125285 A CA1125285 A CA 1125285A
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-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
-
- 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
- C08F16/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/28—Monomers containing nitrogen
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
Abstract of the Disclosure Ethylenically unsaturated crosslinking agents and polymerizable monomers are disclosed. These agents contain a heterocyclic nucleus and are capable of forming oxygen insensitive, radiation curable systems.
Description
~ ~ ~ 5~ ~ ~ 51,876-C~N/~lAL
POLY(ETHYLENICALLY UN5ATURATED ALKOXY) HETEROCYCLIC COMPOUNDS
Technical Field , The present invention relates to novel ethylenically unsaturated cros~linking agents and to radiation curable compositions containing these agents. The invention particularly relates to ethylenically unsaturated heterocyclic crosslinking agents, to radiation curable oxygen insensitive compositions containing such agents, to alcohol or aqueous alcohol developable imaging layers containing such compositions.
Background Art The generation of three-dimensional bonding or crosslinking in a composition or coating to reduce the solubility and improve th~ chemical resistance of a cured product is well known. This is u~ually effected by the addition of a crosslinking agent to an otherwise two dimensionally polymerizable composition from which the cured product is made. Crosslinking ha$ been produced in products from ethylenically unsaturated compositions such as acrylic compositions (e.g., a methyl methacrylate composition) by incorporation of from about 1 to about 10 percent by weight of a polyacrylic substituted compound as a crosslinking agent. It is well known that such acrylic compositions generally must be polymeriæed in an inert atmosphere, e.g., a nitrogen atmosphere. Otherwise, the oxygen present in air will retard or even prevent polymeri~ation of the acrylic composition so that desired levels oE polymerization cannot be achieved. At best, only a tacky, incompletely polymerized resin or a weak, low molecular weight polyacrylate resin can be obtained.
Curable, oxygen in.sensitive acrylic compositions are described in U~S. Patents 3,844,916, 3,914,165 and 3,925,349. These references teach that oxygen inhibition can be avoided by incorporation o a Michael adduct o a ;:
, polyacrylate and an amine having at least one amino hydrogen into acrylic compositions. The use of such an adduct in acrylic photopolymerizable compositions requires the use of a relatively high concentra~ion of polymeriza-tion photoinitiator (3~ by weight is disclosed at Col. 3,lines 50-51 of U.S. Patent 3,925,349). Although such compositions are useful for coatings and inks that can be cured in the presence of oxygen, these compo~itions are not satisfactory ~or coatings that are transparent and 10 where discoloration is undesirable since the use of large amounts of photoinitiator leads to yellowing of the cured coating.
Acrylic compositions, containing 0.5 to 10 percent triphenyl phosphine, that can be cured rapidly in 15 an atmosphere containing 300 to 1000 ppm of oxygen are disclosed in U.S. Patent 4tll3,893. Since the provision of atmosphere containing oxygen in any concentration less than that found in air requires use of special equipment, the use of phosphines to obtain rapid curing is also 20 unsatisfactory for many commercial processes.
U.S. Patent 3,968,305 describes acrylic compo-sitions comprising an aliphatic compound having three or more methacryloxy groups that can be polymerized to a crosslinked mar resistant coating. U.S. Patent 4,014,771 25 teaches that by the addition of 1) 30 to 95 percent of the adduct of methacrylic acid and 2) either a polyglycidyl ether oE an aromatic polyhydric compound or a polyglycidyl ester of an aromatic or aliphatic polycar-boxylic acid to a polymethacryloxy compound such as that 30 described in U.S. Patent 3,968,305, there is obtained a composition which evidently can be polymerized without the necessity of excluding air during the polymerization.
Protective coatings produced by irradiation in the absence of air of the adduct of methacrylic acid to 35 N-glycidylheterocyclic compounds are disclosed in U.S.
Patents 3,808,226 and 3,847,769. Polymerization o~ the dimethacrylic ester of N-oxyalkylated-heterocyclic ... .
, , , .
' - :. : ,' , - .. ..
.
:
' -.
.~Z528S
compounds is disclosed in United States Patents 3,821,098 and 3,852,302.
The compounds of United States Patent No. 3,80~,226 bear a similarity in structure to the compounds of the present application. The route of synthesis shown for those compounds can not produce the compounds of the present invention nor could the route of synthesis used in the present invention produce the compounds of that patent.
DISCLOSURE OF INVENTION
In accordance with the invention, there are provided novel ethylenically unsaturated crosslinking agents comprising poly(ethylenically unsaturated alkoxyalkyl)heterocyclic compounds and a process for their preparation.
l'he crosslinking agents of the inven~ion have the general formula:
Al-Z-A2 in which Al and A2 independently are groups having terminal ethylenic unsaturation and having the general formula:
oR2
POLY(ETHYLENICALLY UN5ATURATED ALKOXY) HETEROCYCLIC COMPOUNDS
Technical Field , The present invention relates to novel ethylenically unsaturated cros~linking agents and to radiation curable compositions containing these agents. The invention particularly relates to ethylenically unsaturated heterocyclic crosslinking agents, to radiation curable oxygen insensitive compositions containing such agents, to alcohol or aqueous alcohol developable imaging layers containing such compositions.
Background Art The generation of three-dimensional bonding or crosslinking in a composition or coating to reduce the solubility and improve th~ chemical resistance of a cured product is well known. This is u~ually effected by the addition of a crosslinking agent to an otherwise two dimensionally polymerizable composition from which the cured product is made. Crosslinking ha$ been produced in products from ethylenically unsaturated compositions such as acrylic compositions (e.g., a methyl methacrylate composition) by incorporation of from about 1 to about 10 percent by weight of a polyacrylic substituted compound as a crosslinking agent. It is well known that such acrylic compositions generally must be polymeriæed in an inert atmosphere, e.g., a nitrogen atmosphere. Otherwise, the oxygen present in air will retard or even prevent polymeri~ation of the acrylic composition so that desired levels oE polymerization cannot be achieved. At best, only a tacky, incompletely polymerized resin or a weak, low molecular weight polyacrylate resin can be obtained.
Curable, oxygen in.sensitive acrylic compositions are described in U~S. Patents 3,844,916, 3,914,165 and 3,925,349. These references teach that oxygen inhibition can be avoided by incorporation o a Michael adduct o a ;:
, polyacrylate and an amine having at least one amino hydrogen into acrylic compositions. The use of such an adduct in acrylic photopolymerizable compositions requires the use of a relatively high concentra~ion of polymeriza-tion photoinitiator (3~ by weight is disclosed at Col. 3,lines 50-51 of U.S. Patent 3,925,349). Although such compositions are useful for coatings and inks that can be cured in the presence of oxygen, these compo~itions are not satisfactory ~or coatings that are transparent and 10 where discoloration is undesirable since the use of large amounts of photoinitiator leads to yellowing of the cured coating.
Acrylic compositions, containing 0.5 to 10 percent triphenyl phosphine, that can be cured rapidly in 15 an atmosphere containing 300 to 1000 ppm of oxygen are disclosed in U.S. Patent 4tll3,893. Since the provision of atmosphere containing oxygen in any concentration less than that found in air requires use of special equipment, the use of phosphines to obtain rapid curing is also 20 unsatisfactory for many commercial processes.
U.S. Patent 3,968,305 describes acrylic compo-sitions comprising an aliphatic compound having three or more methacryloxy groups that can be polymerized to a crosslinked mar resistant coating. U.S. Patent 4,014,771 25 teaches that by the addition of 1) 30 to 95 percent of the adduct of methacrylic acid and 2) either a polyglycidyl ether oE an aromatic polyhydric compound or a polyglycidyl ester of an aromatic or aliphatic polycar-boxylic acid to a polymethacryloxy compound such as that 30 described in U.S. Patent 3,968,305, there is obtained a composition which evidently can be polymerized without the necessity of excluding air during the polymerization.
Protective coatings produced by irradiation in the absence of air of the adduct of methacrylic acid to 35 N-glycidylheterocyclic compounds are disclosed in U.S.
Patents 3,808,226 and 3,847,769. Polymerization o~ the dimethacrylic ester of N-oxyalkylated-heterocyclic ... .
, , , .
' - :. : ,' , - .. ..
.
:
' -.
.~Z528S
compounds is disclosed in United States Patents 3,821,098 and 3,852,302.
The compounds of United States Patent No. 3,80~,226 bear a similarity in structure to the compounds of the present application. The route of synthesis shown for those compounds can not produce the compounds of the present invention nor could the route of synthesis used in the present invention produce the compounds of that patent.
DISCLOSURE OF INVENTION
In accordance with the invention, there are provided novel ethylenically unsaturated crosslinking agents comprising poly(ethylenically unsaturated alkoxyalkyl)heterocyclic compounds and a process for their preparation.
l'he crosslinking agents of the inven~ion have the general formula:
Al-Z-A2 in which Al and A2 independently are groups having terminal ethylenic unsaturation and having the general formula:
oR2
2 1 in which R-O- is a monovalent residue (formed by removal of the active hydrogen from an -OH group) of an aliphatic terminally unsaturated primary alcohol, ROH, R having the formula:
H2C=f~CH2~a or preferably [E~CH2~b~mR ~CH2~c II
wherein: E is H2C=C~CH2~aO- or CH2=F-CO-R4 R4 ;~
a and c are independently an integer of 1 to 6,
H2C=f~CH2~a or preferably [E~CH2~b~mR ~CH2~c II
wherein: E is H2C=C~CH2~aO- or CH2=F-CO-R4 R4 ;~
a and c are independently an integer of 1 to 6,
3 ;
~ "' '~ .
. .
, , : ::
. ~ .
2~5
~ "' '~ .
. .
, , : ::
. ~ .
2~5
-4-b is zero or an integer of 1 to 6, Rl and R4 are independently hydrogen or methyl, R5 is an aliphatic group having 1 to 15 carbon atoms (preferably alkyl having m~l hydrogens removed, e.y., alkylene where m=l, most preferably of up to 8 carbon atoms) and optionally one or two catenary (i.e., backbone) oxygen atoms, or -C 0~ groups, a valence of m + 1, and m is an integer of 1 to 5, O O
R~ is preferably hydrogen but can be -C-R6 or -CNH-R7 wherein R6 is pre~erably alkenyl but can be alkyl (each preferably having 2 to 5 carbon atoms) and can be substituted by a phenyl or carboxyl group and R7 is an al iphatic group ( of up to eight carbon atoms, e.g., alkyl) or aromatic group (preEerably having up to 8 carbon atoms and more preferably a phenyl group) and R7 is most preferably an acryloyloxyalkyl or a methacryloyloxyalkyl group, R3 is an alkylene group having 1 to 6 carbon atoms and optionally one catenary oxygen atom; and Z is a heterocyclic group of the formula:
X-C;O
-N N-\C/
O
wherein:
X is a divalent group which is required to complete a
R~ is preferably hydrogen but can be -C-R6 or -CNH-R7 wherein R6 is pre~erably alkenyl but can be alkyl (each preferably having 2 to 5 carbon atoms) and can be substituted by a phenyl or carboxyl group and R7 is an al iphatic group ( of up to eight carbon atoms, e.g., alkyl) or aromatic group (preEerably having up to 8 carbon atoms and more preferably a phenyl group) and R7 is most preferably an acryloyloxyalkyl or a methacryloyloxyalkyl group, R3 is an alkylene group having 1 to 6 carbon atoms and optionally one catenary oxygen atom; and Z is a heterocyclic group of the formula:
X-C;O
-N N-\C/
O
wherein:
X is a divalent group which is required to complete a
5- or 6-membered heterocyclic ring, preferably X is -C- but X can be -C-, -C~C-, -C3C-~ -Cl Cl-~ or -C-N~
.
' , , ~S'~5 wherein R , R9, RlO, and Rll are independently hydrogen or lower alkyl of 1 to 12, preferably 1 to 4 carbon atoms), cycloalkyl (of 3 to 6 carbon atoms) or phenyl group (of 6 to 12 carbon atoms) and A3 is an alkoxyalkyl growp as defined above for Al and A .
The preferred compounds of Formula I are those wherein E is CH2=1C-IC-O-, m is 2 to 5, and X is ICH . R40 --C--These compounds are preferred because they provide not only a high crosslink density, resul~ing in improved solvent and abrasion resistance but also excellent adhesion and flexibility. Furthermore, these compounds are water/
alcohol soluble and are photocurable to tack free surfaces in the presence of atmosphere oxygen.
This invention further includes energy crosslinkable compositions particularly to photocurable compositions comprising the poly(ethylenically msaturated alkoxyalkyl)heterocyclic compounds of the present invention and a polymerization catalyst which liberates free radicals on application of energy.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the invention can be prepared by the Lewis acid catalyzed addition of n moles of an ethylenically unsaturated primary alcohol to an epoxy-substituted heterocycle in accordance with the equation:
~ \ 3 IH 3 nR-OH + (H2C C-R ~n~ (R-O-CH-I-R ~nZ II
R R
wherein R, Rl, R3, and Z are as defined for the compounds of Formula I, and n is 2 or 3.
Particularly, the (polyacrylyloxy)alkoxypropylheterocyclic compounds -~ of the invention are 5- or 6-membered ring heterocyclic compounds having preer-ably two (but may have three) nitrogen and preferably two (but .~,~,,~
~`
, : - . . .
. .
.
' , , ~S'~5 wherein R , R9, RlO, and Rll are independently hydrogen or lower alkyl of 1 to 12, preferably 1 to 4 carbon atoms), cycloalkyl (of 3 to 6 carbon atoms) or phenyl group (of 6 to 12 carbon atoms) and A3 is an alkoxyalkyl growp as defined above for Al and A .
The preferred compounds of Formula I are those wherein E is CH2=1C-IC-O-, m is 2 to 5, and X is ICH . R40 --C--These compounds are preferred because they provide not only a high crosslink density, resul~ing in improved solvent and abrasion resistance but also excellent adhesion and flexibility. Furthermore, these compounds are water/
alcohol soluble and are photocurable to tack free surfaces in the presence of atmosphere oxygen.
This invention further includes energy crosslinkable compositions particularly to photocurable compositions comprising the poly(ethylenically msaturated alkoxyalkyl)heterocyclic compounds of the present invention and a polymerization catalyst which liberates free radicals on application of energy.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the invention can be prepared by the Lewis acid catalyzed addition of n moles of an ethylenically unsaturated primary alcohol to an epoxy-substituted heterocycle in accordance with the equation:
~ \ 3 IH 3 nR-OH + (H2C C-R ~n~ (R-O-CH-I-R ~nZ II
R R
wherein R, Rl, R3, and Z are as defined for the compounds of Formula I, and n is 2 or 3.
Particularly, the (polyacrylyloxy)alkoxypropylheterocyclic compounds -~ of the invention are 5- or 6-membered ring heterocyclic compounds having preer-ably two (but may have three) nitrogen and preferably two (but .~,~,,~
~`
, : - . . .
. .
6-may have three) carbonyl groups, viz. 0, in the ring. At least one but preferably all of the ring nitrogens are substituted by a (polyacryloyloxy)alkoxypropyl group (e.g., Formula II). The substituted heterocyclic compounds can be prepared (as shown above~ by the Lewis acid catalyzed addition to a heterocyclic compound, as defined, that has one, two or three (where present) of its ring nitrogens substituted by a glycidyl group (e.g., a 2,3-epoxypropyl group), of one, two or three equivalents of a hydroxy compound that is the product of esterification of m hydroxyl groups of a polyol having (m + l) hydroxyl groups with acrylic or methacrylic acid in accordance with the equation:
o O\ X-C~0 0 GH X-C=0 (H2C=cl-lot-mR3-oH+H2c--C-CH2-/ NH ~ (H2C=C~ mR -0-CH2-~-CH2-~ NH
O O
IV
wherein Rl, R~, m, R3 and X are defined above.
The above e~uation illustrates the preparation where only one of the ring nitrogens has been substituted by the glycidyl group. Where two or three of the ring nitrogens have been substituted by glycidyl (as is most preferable), two or three equivalents of hydroxy compound can be added. The addition of the hydroxy compound to the glycidyl groups of the heterocyclic compound can be done in one step or in a sequence of steps in which first one and then a second and then a third glycidyl group is reacted. It is not necessary that the same hydroxyl compound be used in each of the steps. Where two or more diferent hydroxyl compounds are used, unsymmetrical compounds are obtained, that is, Al and ~2 (and A3 if three nitrogens on the ring) of Formula I are different.
Mixtures of hdyroxyl compounds can also be used. It is to be expected, however, when two or more hydroxyl compounds ' ,- , .
.
o O\ X-C~0 0 GH X-C=0 (H2C=cl-lot-mR3-oH+H2c--C-CH2-/ NH ~ (H2C=C~ mR -0-CH2-~-CH2-~ NH
O O
IV
wherein Rl, R~, m, R3 and X are defined above.
The above e~uation illustrates the preparation where only one of the ring nitrogens has been substituted by the glycidyl group. Where two or three of the ring nitrogens have been substituted by glycidyl (as is most preferable), two or three equivalents of hydroxy compound can be added. The addition of the hydroxy compound to the glycidyl groups of the heterocyclic compound can be done in one step or in a sequence of steps in which first one and then a second and then a third glycidyl group is reacted. It is not necessary that the same hydroxyl compound be used in each of the steps. Where two or more diferent hydroxyl compounds are used, unsymmetrical compounds are obtained, that is, Al and ~2 (and A3 if three nitrogens on the ring) of Formula I are different.
Mixtures of hdyroxyl compounds can also be used. It is to be expected, however, when two or more hydroxyl compounds ' ,- , .
.
-7-are used, whether in a sequence of steps or in a one-step mixture, the product obtained will be a mixture of (polyacryloyloxylalkoxypropylheterocyclic compounds. A11, howeverl are useful in the present invention~ particularly when at least about 30~ by weight of the polymerizable coating composition is a heterocyclic compound having at least two glycidyl groups reacted with hydroxy compounds in which m in Formula I is at least three; that is, the hydroxy compound to be reacted with the glycidyl group of the heterocyclic compound is preferably a tri- or higher acryloyloxy or methacryloyloxy-hydroxy compound.
The polyglycidyl heterocyclic intermediates useful in the preparation o any and all of the compounds o the present invention are disclosed in U.S. Patents Nos. 3,808,226 and 4,071,477. Preferably, the reaction is performed in solution. However, it also can be performed in the absence of solvent. Generally, a solution of an epoxy-substituted heterocycle can be added incrementally (over a period of time ranging from a few minutes to several hours) to a mixture of 1) an ethylenically unsaturated primary alcohol (or mixtures of ethylenically unsaturated primary alcohols), 2) an inhibitor for ther-mal polymerization, and 3) a Lewis acid while maintaining the temperature of the mixture at 50 to 120C, preferably about 80 to 100C, until the disappearance of the epoxy group, as indicated by chemical titration or nuclear magnetic resonance spectrometric analysis. Heating the mixture for from 2 to 40 hours usually suffices to complete the reaction, after which volatiles are removed by vacuum distillation.
The compounds of Formula II can then be acylated by reaction with an acylating agent, preferably an acyl halide, an acyl anhydride, or an isocyanate that contains polymèrizable ethylenically unsaturated groups. Preferred acylated compounds have the Formula:
- - . ~ ~, .
- : ,. . .
, : . .: . ~ . , "
~, il 6 OC~
~R-O-CH2-C R tnZ III
or o oC-NH-R7 (R-O-CH2-C-R 1nZ IV
R
10 wherein R, Rl, R3, R6, R7, z, m and n are as defined for Formula I.
Exemplary acyla~ing agen~s include acid chlorides such as acetyl chloride, propionyl chloride, valeryl chloride, dodecanyl chloride, acrylolyl chloride, methacryloyl chloride, alpha-chloroacryloyl chloride, crotyl chloride, benzoyl chloride, phenylacetyl chloride, 2,4 dichlorophenylacetyl chloride; and the corresponding carboxylic acids and anhydrides; other anhydrides include the anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, methylenesuccînic anhydride, phthalic anhydride, and 3-chlorophthalic anhydride; and organic isocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, phenyl isocyanate, 4-t-butyl isocyanate, acryloyloxyethyl isocyanate, metbacryloyloxyethyl isocyanate, ~-methacryloyloxybutyl isocyanate, 4-acryloylphenyl isocyanate and 4-vinylphe~yl isocyanate.
The compounds of Formulas III and IV of the invention are prepared by addition of a suitable acylating agent to the compound II, e~g. an organic acid anhydride or halide or an organic isocyanate.
Suitable ethylenically unsaturated primary alcohols ~or use in the preparation o~ the compounds of the invention are the hydroxyalkyl acrylate~ having the formula:
- :. .
~ - -.: . ~ ..... - , :: .. .
... ~ , . ~ , . .
~,5~5 g [ 2C C~4C~CH2~b]mR ~CH2t - coH V
in which R4, R5, m and c are the same as defined Eor compounds of Formula I. Included among suitable hydroxy-alkyl acrylates are the monoacrylate and monomethacrylate esters of aliphatic diols such as ethyleneglycol, propyleneglycol, butyleneglycol, hexamethyleneglycol, diethyleneglycol, and dimethylolcyclohexane; the diacrylates and dlmethacrylates of alipha~ic triols such as trimethylolmethane, l,l,1-trimethylolpropane, 1,2,3-trimethylolpropane; the triacrylates and trimethacrylates of aliphatic tetrols such as pentaerythritol, 1,1,2,2-tetramethylolethane and 1,1,3,3-tetramethylopropanei the tetraacrylates and te~ramethacrylates of polyols such as dipentaerythritol and 1,1~1,2,2~pentamethylolethane; and the pentaacrylates and pentamethacrylates of polyols such as tripentaerythritol and hexamethylolethane.
Other suitable ethylenically unsaturated primary alcohols for use in the preparation of the compounds of the invention are the hydroxyalkenes having the ~ormula:
[H2C=c~cH2tdo~cH2~b~mR ~CH2~C VI
in which R4, R5, m, d, b, and c are the same as defined for compounds of Formula I. Included among suitable hydroxyalkenes are allyl alcohol, methallyl alcohol, allyloxyethyl alcohol, 2-allyloxymethylpropanol (from dimethylolethane), and 202-di(al lyloxyme thyl)butanol (from trimethylolpropane).
Polymerization initiators suitable ~or use in the crosslinkable compositions of the invention are compounds which liberate or generate a free-radical on addition of energy~ Such initiators include peroxy, azo, and redox systems each of which are well known and are described frequently in polymerization art, e.g. Chapter II of Photochemistr~, by Calvert and Pitts, John Wiley ~
Sons (1966). Xncluded among free-radical initiators are , : :, the conventional heat activated catalysts such as organic p~roxides and organic hydroperoxides; examples are benzoyl peroxide, tertiary-butyl perbenzoate, cumene hydroperoxide, azobis(isobutyronitrile) and the like. The preferred catalys~s are photopolymerization initiators which facilitate polymerization when the composition is irradia~ed. Included among such initiators are acyloin and derivatives thereof, such as benzoin, benzoin methyl ether, benæoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and a-methylbenzoin; diketones such as benzil and diacetyl, etc.; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, decyl phenyl sulfide, and tetramethylthiuram monosul~ide; S-acyl dithio-carbamates, such as S-benzoyl-N,N-dimethyldithiocarbamate;
phenones such as acetophenone, a,a,a-tribromacetophenone, ~,a-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, o-nitro-~ tribxomace~ophenone benzophenone, and p,p'-tetramethyldiaminobenzophenone;
aromatic iodonium and aromatic sulonium salts; sulfonyl halides such as p-toluenesulfonyl chloride, l-naphthalene~
sulfonyl chloride, 2-naphthalenesulfonyl chloride, 1-3benzenedisulfonyl chloride, 2,4-dinitrobenzenesulonyl bromide and p-acetamidobenzenesulfonyl chloride. Normally the initiator is used in amounts ran~ing from about 0.01 to 5% by weight of khe total polymarizable composition.
When the quantity is less than 0.01% by weight, the poly-merization rate becomes extremely low4 If the initiator is used in excess o~ 5~ by weight, no correspondingly improved eEfect can be expected. Thus, addition of such greater quantity is econ~mically unjustified. Preferably, about 0.25 to 1.0% of initiator is used in the polymerizable compositions.
` The crosslinkable compositions o~ the invention are preferably diluted with an ethylenically unsaturated monomer. Suitable ethylenically unsaturated monomers include methyl methacrylate, e~hyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, 2 chlorostyrene~
J5~3S
2,4-dichlorostyrene, acrylic acid, acrylamide, acryloni-trile, t-butyl acrylate, methyl acrylate, butyl acrylate, 2-(N-butylcarbamyl)ethyl methacrylate and 2-(N-butyl-carbamyl)ethyl methacrylate and 2-(N-ethylcarbamyl) ethyl methacrylate. Other diluting monomers that can be incorporated into the composition of the invention include 1,4-butylene dimethacrylate or acrylate, ethylene dimethacrylate, hexanediol diacrylate or dimethacrylate, glyceryl diacrylate or methacrylate, glyceryl kriacrylate or trimethacrylate, pentaerythritol triacrylate or trimeth-acrylate, pentaerythritol tetraacrylate or tetramethacry-late, diallyl phthalate, dipentaerythritol pentaacrylate, neopentylglycol triacrylate and 1,3,5-tri(2-methacryl-oxyethyl)-s-triazine.
The compositions of the presen~ invention may also contain compounds such as those disclosed in U.S.
Patent No. 3,808,266:
o OH
CH2=C-C-O-CH2-1-CH2` - A
~20 l21 n wherein R20 is hydrogen or methyl, R21 is hydrogen or methyl, n is 2 or 3, and .
A is as defined above for the materials of U.S.
Patent No. 3,821,098, which is X ' -- C ~0 -N N-o wherein X' represents a divalent radical which i8 necessary or the completion of a five-or six-membered, unsubstitued or substituted, he~erocyclic ring.
The radical X' in the N-heterocyclic grouping of ~, . ', .: ' , . . , ;
, formula I can be, e.g. D a radical of the formulae:
l R15 I R C=O l R15 C/R16 N-5 C=O; C ; I R1 ; f - R i ! R ; or O=C
¦ \~Rl 6 1 \Rl 8 i R15 R16 R17 and R18 can each independently represent a hydrogen atom or an alkyl group, preEerably a lower alkyl group having 1-4 carbon atoms, an alkenyl group, preferably a lower alkylene group having 1-4 carbon atoms, a cycloalkyl group (preferably of 3 to 8 carbon atoms), or an unsubstituted or substituted phenyl group.
The valence of the nitrogen atom on the la~t group may be satisfied by hydrogen~ aliphatic, or aromatic groups Rl9, preferably o~ no more than eight carbon atoms. the aliphatic groups may be alkyl groups for example, and the cromatic group may be phenyl or alkylphenyl groups, for example.
The crosslinkable composition can also contain a viscosity modifier or binder. Generally, up to about 50 percent by weight of a compatible polymer is used.
Preferably, the polymer is an acrylic polymer such as poly(acrylic acid), a poly(methacrylic acid), poly~methyl methacrylate), poly(vinyl chloride), poly(vinyl acetate, poly(vinyl butyral) and the like. Other polymers include polye~hers, polyesters, polylactones, polyamides, poly-uret~lanes, cellulose derivatives, polysiloxanes and the like.
The compositions of the invention can al~o include a variety o~ addenda utilized for -their known purpose, such as stabilizers, inhibitors, lubricants, flexibilizers, pigments, carbon black, dyes, reinforcing fillers such as finely divided silica, non~rein~orcing fillers such as diatomaceous earth, metal oxides, ~ . .
~ , ~ . ., - , , ': - ' ' -, ' ~ ' ' ~. ' ' - , . ' ' .' ', '' . ~-.' ' ' ~ .
asbestos, fiberglass, glass bubbles, talc, etc. Fillers can generally be used in proportions up to about 200 percent by weight of the curable components but preferably are used up to about 50 percent by weight. Where the polymerizing energy is radiation, it is desirable that the addenda be transparent to the radiation.
The compositions of the invention are prepared by simply mixing (under "safe light" conditions if the composition is to be sensitized to visible light) the polymerization catalyst and sensitizer twhere used), the poly(ethylenically unsaturated alkoxyalkyl3heterocyclic compound, diluting monomers, binders and addenda. Inert solvents may be employed if desired when effecting this mixture. Examples of suitable solvents are methanol, ethanol, acetone, acetonitrile and includes any solvent which does not react with the components of the mixture.
Utility The crosslinkable compositions of the invention can be used as adhesives, caulking and sealing compositions, casting and molding compositions, potting and encapsulating compositions, impregnating and coating compositions, etc., depending on the particular combination of components. Where the polymerization catalyst is a photoinitiator, the composition can be a composition for in situ curing because of this ins~nsitivity to oxygen.
The photopolymerizable compositions are particularly suitable ~or applications in the field of protective coatings and ~raphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metal~, plastics, rubber~ glass~ paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and thelr capability ~or ~orming high resolution image~. Among such uses are water or water/alcohol developable resi~ts ~or : . . , "
.....
- .. . - ~ .. ., . , ~ , .. . . . . .
- :..... . ~ : . .. .. . .
,f~ 5 chemical milling, gravure images, of~set plates, stencil making, screenless lithography, particulate binders as in microtaggants, relief printing plates, printed circuits, electron beam curing adhesives, radiation and protective coatings ~or glass, metal surfaces and the like and abrasion resistant coatings on a wide range of materials such as opthalmic lenses, light control ~ilms, and organic polymeric resin surfaces in general. Priming layers may be used if desired, and in some cases may be necessary.
The coatings of the present invention find application useful on substantially any solid substrate.
Because the coatings of the present invention can be cured by radiation, even highly temperature sensitive substrates can be coated. The substrates may be in substantially any ~orm, such as sheets, films, fibers, fabrics and shaped solid objects. Amongst the substrates particularly finding advantages with coatings of the present invention are polymeric resins, including both thermopla~tic and thermoset resins (e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls cellulosesters, epoxy resins, polysiloxanes, etc.), ceramic substrates, including glass, Eused ceramic sheetings, and fibers, metals and metallized surEaces, natural cellulosic materials, including wood and paper, natural resins, including rubber and gelatin and other various solid surfaces. The coatings are useful particularly on refractive substrates (e.g., lenses, prisms and the like) as well as reflective substrates (street signs, mirrors, etc.). They are also u3eful on metallized polymeric film which is transparent and used as a light screen on windows.
Where the coating compositions of this invention are not naturally adherent to the particular ~ubstrate selected, primer compositions, comprising single ingredients or blends of materials, may be used to improve the bond of the coating to the substrate. Texturizing, ; chemical, or physical treatment of the surface may also be .
.
': ' , , , used to improve bonding. The coatings of the invention are generally between 0.5 and 500 microns thick, preferably between 1 and 50 microns, and most preferably between 3 and 25 microns.
Particularly useful substrates for application of the coatings of the present invention would be those requiring transparent protective coatings. Finished photographic prints and ilms, paintings, transparencies, car windshields, painted surfaces, instant film (i.e., film which does not require external application of developing chemistry), photothermographic and thermographic paper and film, photoconductive substrates, opthalmic lenses, liquid crystal displays, mo~ion pic~ure film, street and traffic signs, reflective surfaces, lS retroreElective surfaces, traffic ligh~s, and many other substrates are usefully coated according to the practice of the present invention. These coatings are particularly useful on optically functional surfaces or elements, particularly polarizing elements. These include both polymeric film type polarizers and the solvent-coated type polarizers such as are described in U.S. Patnets 2,400,877; 2,481,830; and 2,544,659.
Where the polymerization initiator i5 a photo-initiator, the compo~ition can be a composition for in situ curing because of this insensitivity to oxygen.
The photopolymerizable compositions are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, metal oxides, plastics, rubber, glasst paperr wood, and ceramics; their excellent resistance to most ~olvents and chemicals; their excellent flexibility and weatherabllity;
and ~heir capabili~y for forming high resolution images.
The photopolymerization of the compo~itions of the invention occurs on exposure of the compositions to `!
any source of radiation emitting actinic radiation at a .
, . - ", . . : . .
.. ~
.
- .
, . .
: .
. . , ~16~ 52~35 wavelen~th within the ultraviolet and visible spectral regions. Suitable sources of radiation include mercury, xenon, carbon arc and tungsten filament lamps, sunlight, etc. Exposures may be from less than about 1 second to 10 minutes or more dependin~ upon the amounts of the particular polymerizable materials and photopolymerization catalyst being utilized and depending upon the radiation source, distance from the source, and the thickness of the coating to be cured. The compositions may also be polymerized by exposure to electron beam irradiation.
Generally speaking, the dosage necessary is from less than 1 megarad to 100 megarad or more. One of the major advantages with using electron beam curing is that highly pigmented compositions can be effectively cured at a faster rate than by mere exposure to actinic radiation.
It has been found that at least 15% by weight of the polymer layer should comprise the compounds of the present invention in order to obtain abrasion resistance.
These and other features of the present invention will be shown in the following Examples.
Preparation of 1,3-Bis(3-[2,2 ! 2-(triacryloyloxymet~yl) ethoxy2_hydroxypropyl)-5,5-dimethyl~2,4-imidizolidinedione O O
Il 11 H2C=CH-CO-CH2 CH2-OC-CH=CH2 O OH O OH O
H2C=CH-CO-CH2-( CH O-CH CH CH N'~`N CH CH CH O-CH `-CH2-0C-CH=CH2 H2=CH-CO-CH2 , CH3 Ca2-C-C-CH=CH2 . ,~ . .
.:
. .... ' :
,,: ,: ' .
Com~ound A
Pentaerythritol triacrylate (44.3 g, 0.1 moles, hydroxyl equivalent weight of 443), .OZ5 g 4-methoxy-phenol, and 0.4 9 horontrifluoride e-thera~e were charged into a 250 ml three- necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and a CasO~ drying tube. (It is to be noted that most commercially available pentaerythritol triacrylate is contaminated with acrylated impurities.) The reaction flask was heated to 60C and 13.8 g of 1,3-bis(2,3-epoxypropyl)-5,5-dimethyl 2,4-imidizolidinedione (0.1 m epoxide equivalency~ in 5 ml chloroform was added dropwise over 45 minutes. After the addition, the reaction flask temperature was raised to 85C and stirred for 11.5 hours. After this time, titration of an aliquote for unreacted epoxide indicated that the reaction was greater than 99~ complete. The chloroform was removed by vacuum distillation leaving as residue a viscous liquid that contains predominently compounds of the structure of Compound A. Photocurable impurities introduced with the pentaerythritol triacrylate can be removed by trituration with diethyl ether.
A mixture of the liquid and 2% by weight of the photopolymerization initiator 2,2-dimethoxy-2-phenyl-acetophenone was coated onto 12~m polyester film and driedto provide a 2.5~m layer. The layer was then cured in a UV Processor, Model No. CC 1202 N/A (manuactured by Radiation Polymer Co.) after one pass at 12 m/min. (40 ~eet/min.) under an 80 watts~cm (200 watts/inch) medium pressure mercury lamp. The cured layer exhibited 95-100 cross-hatch adhesion, 2-7% Taber Maze, 13-16~ haze in the Gardner Falling Sand Abrader (i.e., tested according to ASTM Designation D1003-64(Procedure A)) and exc~llent resistance to abrasion by steel wool. The layer was unaffected by treatment with ethanol, acetone, ethyl acetate, toluene, hexane, aqueous sodium hydroxide and 10 aqueous hydrochloric acid.
~ .
.. ., . .. :
.
, ~ :
:
.: :
~~ -18~ ~ ~
Preparation of 1,3-Bis[3-~2-acryloyloxyethoxy)-2-h~drOXy-propyl] -5,5-dime~hyl-2,4-imidizolidinedione Compound B
Distilled hydroxyethyl acrylate ~46.4 g, 0.4 moles), 0.065 g 4-methoxyphenol, and 1 0 g boron~ri-fluoride etherate were charged into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux conden~er, and CaS0~ drying ~ube. The reaction 1ask was heated to 60~C
and 55.2 g 1,3-bis(2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidenedione in 10 ml chloroform was added dropwise over 30 minutes. The reaction flask temperature was raised to 75C for 11 hours. At this time titration of residual epoxide groups indicated tha~ the reaction was 97% com-plete. The volatiles were removed by vacuum distillation leaving as residue a liquid.
A layer o~ th~ compound containing 2~ of 2,2-dimethoxy-2-phenylacetophenone was prepared and cured as in Example 1. The cured layer had chemical resistance similar to that of the layer of Exampie 1.
The analogous dimethacryloyl derivative (Compound C) was prepared in a similar manner utilizing 2-hydroxyethyl methacrylate in place of 2-hydroxyethyl acrylate. Layers prepared and cured with Compound C in the same manner as with Compound B had characteristics silnilar to those layers formed from Compound B.
-Preparation of 1-[3-(2 acryloyloxyethox~ -Z-b~drQ~yRR~ey -3[3-(2-acryloyloxyethoxy)-2-[~3-carboxyacryloyloxy~)propyl~
-5,5-dimethyl-2,4-imidizolidinedione Compound D
:.
Compound B (10.0 g, 0.025 mole~ frorn Example 2) and 2.4 g malqic anhydride were charged into a 100 ml three-necked round bo~tom flask e~uipped with mechanical , ,- : ,. .
', ..
5~35 stirrer, reflux condenser, and CaS04 drying tube. The reaction was heated at 80C for six hours. At this time the reaction was terminated to yield a viscous slightly yellow liquid displaying a strong, broad infrared spectral absorbance centered at 3000 cm~l, characteristic for carboxylic acidsr A layer of this material containing 2% of 2,2-dimethoxy-2-phenylacetophenone was prepared as in Example 1. This layer was cured to insolubility with a Hanovia 3D960 mercury arc lamp in 60 seconds~ The sample was 6 cm from the light source~
EXAMPLES_5-10 Various amounts of Compounds A and B were mixed with trimethylolpropanetriacrylate (TMPTA) and 2% by weight of the photopolymerization initiator of Example 1 added. Each mixture was diluted with an equal weigh~ of acetone and coated onto 12 ~m polyester film and dried.
The dried coating was 2.5 ~m thick. On exposure in air at a distance of 6 cm the radiation from a 100 watt Hanovia 3D690 lamp and the time measured at which each become insoluble in acetone. The data obtained is recorded in Table I.
Tabl e I
Exp. _ Com~os_ ion Cure Time No. Compound t4~ TMPTA (Sec.) 4 None 100 600 A (17) 83 ~
6 A (~8) 72 60 7 A (50) 50 50
The polyglycidyl heterocyclic intermediates useful in the preparation o any and all of the compounds o the present invention are disclosed in U.S. Patents Nos. 3,808,226 and 4,071,477. Preferably, the reaction is performed in solution. However, it also can be performed in the absence of solvent. Generally, a solution of an epoxy-substituted heterocycle can be added incrementally (over a period of time ranging from a few minutes to several hours) to a mixture of 1) an ethylenically unsaturated primary alcohol (or mixtures of ethylenically unsaturated primary alcohols), 2) an inhibitor for ther-mal polymerization, and 3) a Lewis acid while maintaining the temperature of the mixture at 50 to 120C, preferably about 80 to 100C, until the disappearance of the epoxy group, as indicated by chemical titration or nuclear magnetic resonance spectrometric analysis. Heating the mixture for from 2 to 40 hours usually suffices to complete the reaction, after which volatiles are removed by vacuum distillation.
The compounds of Formula II can then be acylated by reaction with an acylating agent, preferably an acyl halide, an acyl anhydride, or an isocyanate that contains polymèrizable ethylenically unsaturated groups. Preferred acylated compounds have the Formula:
- - . ~ ~, .
- : ,. . .
, : . .: . ~ . , "
~, il 6 OC~
~R-O-CH2-C R tnZ III
or o oC-NH-R7 (R-O-CH2-C-R 1nZ IV
R
10 wherein R, Rl, R3, R6, R7, z, m and n are as defined for Formula I.
Exemplary acyla~ing agen~s include acid chlorides such as acetyl chloride, propionyl chloride, valeryl chloride, dodecanyl chloride, acrylolyl chloride, methacryloyl chloride, alpha-chloroacryloyl chloride, crotyl chloride, benzoyl chloride, phenylacetyl chloride, 2,4 dichlorophenylacetyl chloride; and the corresponding carboxylic acids and anhydrides; other anhydrides include the anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, methylenesuccînic anhydride, phthalic anhydride, and 3-chlorophthalic anhydride; and organic isocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, phenyl isocyanate, 4-t-butyl isocyanate, acryloyloxyethyl isocyanate, metbacryloyloxyethyl isocyanate, ~-methacryloyloxybutyl isocyanate, 4-acryloylphenyl isocyanate and 4-vinylphe~yl isocyanate.
The compounds of Formulas III and IV of the invention are prepared by addition of a suitable acylating agent to the compound II, e~g. an organic acid anhydride or halide or an organic isocyanate.
Suitable ethylenically unsaturated primary alcohols ~or use in the preparation o~ the compounds of the invention are the hydroxyalkyl acrylate~ having the formula:
- :. .
~ - -.: . ~ ..... - , :: .. .
... ~ , . ~ , . .
~,5~5 g [ 2C C~4C~CH2~b]mR ~CH2t - coH V
in which R4, R5, m and c are the same as defined Eor compounds of Formula I. Included among suitable hydroxy-alkyl acrylates are the monoacrylate and monomethacrylate esters of aliphatic diols such as ethyleneglycol, propyleneglycol, butyleneglycol, hexamethyleneglycol, diethyleneglycol, and dimethylolcyclohexane; the diacrylates and dlmethacrylates of alipha~ic triols such as trimethylolmethane, l,l,1-trimethylolpropane, 1,2,3-trimethylolpropane; the triacrylates and trimethacrylates of aliphatic tetrols such as pentaerythritol, 1,1,2,2-tetramethylolethane and 1,1,3,3-tetramethylopropanei the tetraacrylates and te~ramethacrylates of polyols such as dipentaerythritol and 1,1~1,2,2~pentamethylolethane; and the pentaacrylates and pentamethacrylates of polyols such as tripentaerythritol and hexamethylolethane.
Other suitable ethylenically unsaturated primary alcohols for use in the preparation of the compounds of the invention are the hydroxyalkenes having the ~ormula:
[H2C=c~cH2tdo~cH2~b~mR ~CH2~C VI
in which R4, R5, m, d, b, and c are the same as defined for compounds of Formula I. Included among suitable hydroxyalkenes are allyl alcohol, methallyl alcohol, allyloxyethyl alcohol, 2-allyloxymethylpropanol (from dimethylolethane), and 202-di(al lyloxyme thyl)butanol (from trimethylolpropane).
Polymerization initiators suitable ~or use in the crosslinkable compositions of the invention are compounds which liberate or generate a free-radical on addition of energy~ Such initiators include peroxy, azo, and redox systems each of which are well known and are described frequently in polymerization art, e.g. Chapter II of Photochemistr~, by Calvert and Pitts, John Wiley ~
Sons (1966). Xncluded among free-radical initiators are , : :, the conventional heat activated catalysts such as organic p~roxides and organic hydroperoxides; examples are benzoyl peroxide, tertiary-butyl perbenzoate, cumene hydroperoxide, azobis(isobutyronitrile) and the like. The preferred catalys~s are photopolymerization initiators which facilitate polymerization when the composition is irradia~ed. Included among such initiators are acyloin and derivatives thereof, such as benzoin, benzoin methyl ether, benæoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and a-methylbenzoin; diketones such as benzil and diacetyl, etc.; organic sulfides such as diphenyl monosulfide, diphenyl disulfide, decyl phenyl sulfide, and tetramethylthiuram monosul~ide; S-acyl dithio-carbamates, such as S-benzoyl-N,N-dimethyldithiocarbamate;
phenones such as acetophenone, a,a,a-tribromacetophenone, ~,a-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, o-nitro-~ tribxomace~ophenone benzophenone, and p,p'-tetramethyldiaminobenzophenone;
aromatic iodonium and aromatic sulonium salts; sulfonyl halides such as p-toluenesulfonyl chloride, l-naphthalene~
sulfonyl chloride, 2-naphthalenesulfonyl chloride, 1-3benzenedisulfonyl chloride, 2,4-dinitrobenzenesulonyl bromide and p-acetamidobenzenesulfonyl chloride. Normally the initiator is used in amounts ran~ing from about 0.01 to 5% by weight of khe total polymarizable composition.
When the quantity is less than 0.01% by weight, the poly-merization rate becomes extremely low4 If the initiator is used in excess o~ 5~ by weight, no correspondingly improved eEfect can be expected. Thus, addition of such greater quantity is econ~mically unjustified. Preferably, about 0.25 to 1.0% of initiator is used in the polymerizable compositions.
` The crosslinkable compositions o~ the invention are preferably diluted with an ethylenically unsaturated monomer. Suitable ethylenically unsaturated monomers include methyl methacrylate, e~hyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, 2 chlorostyrene~
J5~3S
2,4-dichlorostyrene, acrylic acid, acrylamide, acryloni-trile, t-butyl acrylate, methyl acrylate, butyl acrylate, 2-(N-butylcarbamyl)ethyl methacrylate and 2-(N-butyl-carbamyl)ethyl methacrylate and 2-(N-ethylcarbamyl) ethyl methacrylate. Other diluting monomers that can be incorporated into the composition of the invention include 1,4-butylene dimethacrylate or acrylate, ethylene dimethacrylate, hexanediol diacrylate or dimethacrylate, glyceryl diacrylate or methacrylate, glyceryl kriacrylate or trimethacrylate, pentaerythritol triacrylate or trimeth-acrylate, pentaerythritol tetraacrylate or tetramethacry-late, diallyl phthalate, dipentaerythritol pentaacrylate, neopentylglycol triacrylate and 1,3,5-tri(2-methacryl-oxyethyl)-s-triazine.
The compositions of the presen~ invention may also contain compounds such as those disclosed in U.S.
Patent No. 3,808,266:
o OH
CH2=C-C-O-CH2-1-CH2` - A
~20 l21 n wherein R20 is hydrogen or methyl, R21 is hydrogen or methyl, n is 2 or 3, and .
A is as defined above for the materials of U.S.
Patent No. 3,821,098, which is X ' -- C ~0 -N N-o wherein X' represents a divalent radical which i8 necessary or the completion of a five-or six-membered, unsubstitued or substituted, he~erocyclic ring.
The radical X' in the N-heterocyclic grouping of ~, . ', .: ' , . . , ;
, formula I can be, e.g. D a radical of the formulae:
l R15 I R C=O l R15 C/R16 N-5 C=O; C ; I R1 ; f - R i ! R ; or O=C
¦ \~Rl 6 1 \Rl 8 i R15 R16 R17 and R18 can each independently represent a hydrogen atom or an alkyl group, preEerably a lower alkyl group having 1-4 carbon atoms, an alkenyl group, preferably a lower alkylene group having 1-4 carbon atoms, a cycloalkyl group (preferably of 3 to 8 carbon atoms), or an unsubstituted or substituted phenyl group.
The valence of the nitrogen atom on the la~t group may be satisfied by hydrogen~ aliphatic, or aromatic groups Rl9, preferably o~ no more than eight carbon atoms. the aliphatic groups may be alkyl groups for example, and the cromatic group may be phenyl or alkylphenyl groups, for example.
The crosslinkable composition can also contain a viscosity modifier or binder. Generally, up to about 50 percent by weight of a compatible polymer is used.
Preferably, the polymer is an acrylic polymer such as poly(acrylic acid), a poly(methacrylic acid), poly~methyl methacrylate), poly(vinyl chloride), poly(vinyl acetate, poly(vinyl butyral) and the like. Other polymers include polye~hers, polyesters, polylactones, polyamides, poly-uret~lanes, cellulose derivatives, polysiloxanes and the like.
The compositions of the invention can al~o include a variety o~ addenda utilized for -their known purpose, such as stabilizers, inhibitors, lubricants, flexibilizers, pigments, carbon black, dyes, reinforcing fillers such as finely divided silica, non~rein~orcing fillers such as diatomaceous earth, metal oxides, ~ . .
~ , ~ . ., - , , ': - ' ' -, ' ~ ' ' ~. ' ' - , . ' ' .' ', '' . ~-.' ' ' ~ .
asbestos, fiberglass, glass bubbles, talc, etc. Fillers can generally be used in proportions up to about 200 percent by weight of the curable components but preferably are used up to about 50 percent by weight. Where the polymerizing energy is radiation, it is desirable that the addenda be transparent to the radiation.
The compositions of the invention are prepared by simply mixing (under "safe light" conditions if the composition is to be sensitized to visible light) the polymerization catalyst and sensitizer twhere used), the poly(ethylenically unsaturated alkoxyalkyl3heterocyclic compound, diluting monomers, binders and addenda. Inert solvents may be employed if desired when effecting this mixture. Examples of suitable solvents are methanol, ethanol, acetone, acetonitrile and includes any solvent which does not react with the components of the mixture.
Utility The crosslinkable compositions of the invention can be used as adhesives, caulking and sealing compositions, casting and molding compositions, potting and encapsulating compositions, impregnating and coating compositions, etc., depending on the particular combination of components. Where the polymerization catalyst is a photoinitiator, the composition can be a composition for in situ curing because of this ins~nsitivity to oxygen.
The photopolymerizable compositions are particularly suitable ~or applications in the field of protective coatings and ~raphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metal~, plastics, rubber~ glass~ paper, wood, and ceramics; their excellent resistance to most solvents and chemicals; their excellent flexibility and weatherability; and thelr capability ~or ~orming high resolution image~. Among such uses are water or water/alcohol developable resi~ts ~or : . . , "
.....
- .. . - ~ .. ., . , ~ , .. . . . . .
- :..... . ~ : . .. .. . .
,f~ 5 chemical milling, gravure images, of~set plates, stencil making, screenless lithography, particulate binders as in microtaggants, relief printing plates, printed circuits, electron beam curing adhesives, radiation and protective coatings ~or glass, metal surfaces and the like and abrasion resistant coatings on a wide range of materials such as opthalmic lenses, light control ~ilms, and organic polymeric resin surfaces in general. Priming layers may be used if desired, and in some cases may be necessary.
The coatings of the present invention find application useful on substantially any solid substrate.
Because the coatings of the present invention can be cured by radiation, even highly temperature sensitive substrates can be coated. The substrates may be in substantially any ~orm, such as sheets, films, fibers, fabrics and shaped solid objects. Amongst the substrates particularly finding advantages with coatings of the present invention are polymeric resins, including both thermopla~tic and thermoset resins (e.g., polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polyacrylates, polyolefins, polyvinyls cellulosesters, epoxy resins, polysiloxanes, etc.), ceramic substrates, including glass, Eused ceramic sheetings, and fibers, metals and metallized surEaces, natural cellulosic materials, including wood and paper, natural resins, including rubber and gelatin and other various solid surfaces. The coatings are useful particularly on refractive substrates (e.g., lenses, prisms and the like) as well as reflective substrates (street signs, mirrors, etc.). They are also u3eful on metallized polymeric film which is transparent and used as a light screen on windows.
Where the coating compositions of this invention are not naturally adherent to the particular ~ubstrate selected, primer compositions, comprising single ingredients or blends of materials, may be used to improve the bond of the coating to the substrate. Texturizing, ; chemical, or physical treatment of the surface may also be .
.
': ' , , , used to improve bonding. The coatings of the invention are generally between 0.5 and 500 microns thick, preferably between 1 and 50 microns, and most preferably between 3 and 25 microns.
Particularly useful substrates for application of the coatings of the present invention would be those requiring transparent protective coatings. Finished photographic prints and ilms, paintings, transparencies, car windshields, painted surfaces, instant film (i.e., film which does not require external application of developing chemistry), photothermographic and thermographic paper and film, photoconductive substrates, opthalmic lenses, liquid crystal displays, mo~ion pic~ure film, street and traffic signs, reflective surfaces, lS retroreElective surfaces, traffic ligh~s, and many other substrates are usefully coated according to the practice of the present invention. These coatings are particularly useful on optically functional surfaces or elements, particularly polarizing elements. These include both polymeric film type polarizers and the solvent-coated type polarizers such as are described in U.S. Patnets 2,400,877; 2,481,830; and 2,544,659.
Where the polymerization initiator i5 a photo-initiator, the compo~ition can be a composition for in situ curing because of this insensitivity to oxygen.
The photopolymerizable compositions are particularly suitable for applications in the field of protective coatings and graphic arts because of their superior abrasion-resistance and adhesion to many rigid, resilient and flexible substrates such as metals, metal oxides, plastics, rubber, glasst paperr wood, and ceramics; their excellent resistance to most ~olvents and chemicals; their excellent flexibility and weatherabllity;
and ~heir capabili~y for forming high resolution images.
The photopolymerization of the compo~itions of the invention occurs on exposure of the compositions to `!
any source of radiation emitting actinic radiation at a .
, . - ", . . : . .
.. ~
.
- .
, . .
: .
. . , ~16~ 52~35 wavelen~th within the ultraviolet and visible spectral regions. Suitable sources of radiation include mercury, xenon, carbon arc and tungsten filament lamps, sunlight, etc. Exposures may be from less than about 1 second to 10 minutes or more dependin~ upon the amounts of the particular polymerizable materials and photopolymerization catalyst being utilized and depending upon the radiation source, distance from the source, and the thickness of the coating to be cured. The compositions may also be polymerized by exposure to electron beam irradiation.
Generally speaking, the dosage necessary is from less than 1 megarad to 100 megarad or more. One of the major advantages with using electron beam curing is that highly pigmented compositions can be effectively cured at a faster rate than by mere exposure to actinic radiation.
It has been found that at least 15% by weight of the polymer layer should comprise the compounds of the present invention in order to obtain abrasion resistance.
These and other features of the present invention will be shown in the following Examples.
Preparation of 1,3-Bis(3-[2,2 ! 2-(triacryloyloxymet~yl) ethoxy2_hydroxypropyl)-5,5-dimethyl~2,4-imidizolidinedione O O
Il 11 H2C=CH-CO-CH2 CH2-OC-CH=CH2 O OH O OH O
H2C=CH-CO-CH2-( CH O-CH CH CH N'~`N CH CH CH O-CH `-CH2-0C-CH=CH2 H2=CH-CO-CH2 , CH3 Ca2-C-C-CH=CH2 . ,~ . .
.:
. .... ' :
,,: ,: ' .
Com~ound A
Pentaerythritol triacrylate (44.3 g, 0.1 moles, hydroxyl equivalent weight of 443), .OZ5 g 4-methoxy-phenol, and 0.4 9 horontrifluoride e-thera~e were charged into a 250 ml three- necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and a CasO~ drying tube. (It is to be noted that most commercially available pentaerythritol triacrylate is contaminated with acrylated impurities.) The reaction flask was heated to 60C and 13.8 g of 1,3-bis(2,3-epoxypropyl)-5,5-dimethyl 2,4-imidizolidinedione (0.1 m epoxide equivalency~ in 5 ml chloroform was added dropwise over 45 minutes. After the addition, the reaction flask temperature was raised to 85C and stirred for 11.5 hours. After this time, titration of an aliquote for unreacted epoxide indicated that the reaction was greater than 99~ complete. The chloroform was removed by vacuum distillation leaving as residue a viscous liquid that contains predominently compounds of the structure of Compound A. Photocurable impurities introduced with the pentaerythritol triacrylate can be removed by trituration with diethyl ether.
A mixture of the liquid and 2% by weight of the photopolymerization initiator 2,2-dimethoxy-2-phenyl-acetophenone was coated onto 12~m polyester film and driedto provide a 2.5~m layer. The layer was then cured in a UV Processor, Model No. CC 1202 N/A (manuactured by Radiation Polymer Co.) after one pass at 12 m/min. (40 ~eet/min.) under an 80 watts~cm (200 watts/inch) medium pressure mercury lamp. The cured layer exhibited 95-100 cross-hatch adhesion, 2-7% Taber Maze, 13-16~ haze in the Gardner Falling Sand Abrader (i.e., tested according to ASTM Designation D1003-64(Procedure A)) and exc~llent resistance to abrasion by steel wool. The layer was unaffected by treatment with ethanol, acetone, ethyl acetate, toluene, hexane, aqueous sodium hydroxide and 10 aqueous hydrochloric acid.
~ .
.. ., . .. :
.
, ~ :
:
.: :
~~ -18~ ~ ~
Preparation of 1,3-Bis[3-~2-acryloyloxyethoxy)-2-h~drOXy-propyl] -5,5-dime~hyl-2,4-imidizolidinedione Compound B
Distilled hydroxyethyl acrylate ~46.4 g, 0.4 moles), 0.065 g 4-methoxyphenol, and 1 0 g boron~ri-fluoride etherate were charged into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux conden~er, and CaS0~ drying ~ube. The reaction 1ask was heated to 60~C
and 55.2 g 1,3-bis(2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidenedione in 10 ml chloroform was added dropwise over 30 minutes. The reaction flask temperature was raised to 75C for 11 hours. At this time titration of residual epoxide groups indicated tha~ the reaction was 97% com-plete. The volatiles were removed by vacuum distillation leaving as residue a liquid.
A layer o~ th~ compound containing 2~ of 2,2-dimethoxy-2-phenylacetophenone was prepared and cured as in Example 1. The cured layer had chemical resistance similar to that of the layer of Exampie 1.
The analogous dimethacryloyl derivative (Compound C) was prepared in a similar manner utilizing 2-hydroxyethyl methacrylate in place of 2-hydroxyethyl acrylate. Layers prepared and cured with Compound C in the same manner as with Compound B had characteristics silnilar to those layers formed from Compound B.
-Preparation of 1-[3-(2 acryloyloxyethox~ -Z-b~drQ~yRR~ey -3[3-(2-acryloyloxyethoxy)-2-[~3-carboxyacryloyloxy~)propyl~
-5,5-dimethyl-2,4-imidizolidinedione Compound D
:.
Compound B (10.0 g, 0.025 mole~ frorn Example 2) and 2.4 g malqic anhydride were charged into a 100 ml three-necked round bo~tom flask e~uipped with mechanical , ,- : ,. .
', ..
5~35 stirrer, reflux condenser, and CaS04 drying tube. The reaction was heated at 80C for six hours. At this time the reaction was terminated to yield a viscous slightly yellow liquid displaying a strong, broad infrared spectral absorbance centered at 3000 cm~l, characteristic for carboxylic acidsr A layer of this material containing 2% of 2,2-dimethoxy-2-phenylacetophenone was prepared as in Example 1. This layer was cured to insolubility with a Hanovia 3D960 mercury arc lamp in 60 seconds~ The sample was 6 cm from the light source~
EXAMPLES_5-10 Various amounts of Compounds A and B were mixed with trimethylolpropanetriacrylate (TMPTA) and 2% by weight of the photopolymerization initiator of Example 1 added. Each mixture was diluted with an equal weigh~ of acetone and coated onto 12 ~m polyester film and dried.
The dried coating was 2.5 ~m thick. On exposure in air at a distance of 6 cm the radiation from a 100 watt Hanovia 3D690 lamp and the time measured at which each become insoluble in acetone. The data obtained is recorded in Table I.
Tabl e I
Exp. _ Com~os_ ion Cure Time No. Compound t4~ TMPTA (Sec.) 4 None 100 600 A (17) 83 ~
6 A (~8) 72 60 7 A (50) 50 50
8 A (100) 0 10
9 B (100) 0 30 By re~erence to Table I it can be seen that TMPTA requires 10 minute~ to reach insolubility and that with the addition o~ 17% of Compound A (from Example 1) , ' .
` ' ~
.
.
~ ~5~3~
the cure time is reduced to 80 seconds and with increasin~
amounts of A, the composition cures faster until at 100 A, the composition under the stated conditions cures in only 10 seconds. Comparable resul~s can be obtained with Compound B.
A layer, 2.5 m in thickness, of Compound B con-taining 2% of the photopolymerization ca~alys~ o~ Example 1 on 12 m polyester film was prepared as described in Example 1. A patterned template was placed over the layer and exposed in the W Processor ~o one pass at 12 m/min.
of an 30 watts/cm lamp. The exposed sheet was washed with cold water leaving an image having excellent resolution.
One part polyacrylic acid, one part compound A
from Example 1, five parts water, five parts ethanol and 0.02 parts of the photopolymerization catalyst of Example 1 were mixed together to Eorm a ~olution. A layPr 5O0 m in thickness o~ this solution was coated onto 12 m polyester as described in Example 1~ A patterned template was placed over the layer and exposed by a Han~via 3D690 mercury arc lamp at a distance of 6 cm for two minutes.
The exposed sheet was developed with cold water leaving an image having excellent resolution.
PREPARATION OF COMPOUND E
O ' O .' Il U
CH2-CH~ O-CH2-C~CH2 ~ CH2-CH-(:H2-N N-CH2C~ CH~ ~ CH~-C~ c_l;H-cll2 C~H2 O C - C-CH3 I ~
;~ CH2-~H-C-0 C=O ~H3 C=O O-ICl-C~CH2 O ~ NEI O
. , -. .
:. : :~: , . . . . .
,, , ", . , . : .
, , -21~ 5;~
Compound A (20.4 g from ~xample 1) and 10.6 ml dry tetrahydrofuran were dissolved in a 250 ml 3-necked round bottom flask equipped with a ma~netic stirrer, reflux condenser, pressure equalizing dropping funnel and CaS04 drying tube. 5.7 g phenylisocyanate was added dropwise over the course of five minutes. The reaction was terminated a~ter stirring for twenty hours at room temperature. The lack of an isocyanate infrared absorption band indicates the reaction of the isocyanate to be quantitative.
A layer of this material containing 2% of the photopolymerization catalyst of Example 1 was prepared ~s in Example 1. This layer was cured to insolubility with a Hanovia 3D690 mercury arc lamp in 15 seconds. The sample was 6 cm from the light source.
Preparation of 1,3-Bis[3-(2-allyloxyethoxy)-2-hydroxy~ropyl]-5,5-dimethyl-2,4-imidizolidinedione 0~ 0~
CH2=cH-cH2-o-cH2-cH2-o-c~2-~-cl~2-I N-CH2 CH-CH2-0-C 2 2 2 2 COMPOUND F
2-allyloxyethanol (20.43g, 0.lmoles), 0.03g 4-methoxyphenol, and 0.30g borontrifluoride etherate were chargad into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping ~unnel, reflux condenser and CaSO4 drying tube.
The reaction flask temperature was heated to 80C and 13.8g 1,3~bis~2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidinedione in 4.5g chloroform was added dropwise ; over 30 minutes. The reaction was maintained at 80 for 17 hours. At this time titration of residual epoxide groups indicated that the reaction was 99~ complete. The , ~
) , ~ . .
.
, Z~ 5 chloroform was removed by vacuum di3tillation leaving as residue a colorless liquid.
Example 15 Into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and calcium sulfate drying tube were charged 103.0 g pentaerythritol triacrylate (hydroxy equivalent weight of 5153, 23.2 g 2-hydroxyethyl acrylate (0.2 moles), 0.08 g 4-methoxyphenol, and 1.0 g horontrifluoride etheratè. The reaction ~lask was heated to 75C and 55.2 g (0.40 molar epoxy equivalency~ 1,3~bis(2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidinedione in 20 ml chloroform was added dropwise over one hour. After the addition, the reaction ~lask temperature was raised to 88C and stirred for 18.0 hours. At this time, titration of an aliquote ~or unreacted epoxide indicated the reaction was greater than 99% complete. The volatiles were removed by vacuum distillation leaving a viscous liquid which contains a mixture of bis(triacryloyl3-, bis(monoacryloyl)~, and the unsymmetrical monoacryloyl-triacryloyl-imidizolidinedione, and impuritles, introduced with the pentaerythritol triacrylate.
A layer of the reaction product of Example 15, prepared to contain 2% Irgacure 651 and cured as described in Example 1, had abrasion and chemical resistance characteristics similar to those o~ the layer of Example 1.`
.
. . .
, . .
` ' ~
.
.
~ ~5~3~
the cure time is reduced to 80 seconds and with increasin~
amounts of A, the composition cures faster until at 100 A, the composition under the stated conditions cures in only 10 seconds. Comparable resul~s can be obtained with Compound B.
A layer, 2.5 m in thickness, of Compound B con-taining 2% of the photopolymerization ca~alys~ o~ Example 1 on 12 m polyester film was prepared as described in Example 1. A patterned template was placed over the layer and exposed in the W Processor ~o one pass at 12 m/min.
of an 30 watts/cm lamp. The exposed sheet was washed with cold water leaving an image having excellent resolution.
One part polyacrylic acid, one part compound A
from Example 1, five parts water, five parts ethanol and 0.02 parts of the photopolymerization catalyst of Example 1 were mixed together to Eorm a ~olution. A layPr 5O0 m in thickness o~ this solution was coated onto 12 m polyester as described in Example 1~ A patterned template was placed over the layer and exposed by a Han~via 3D690 mercury arc lamp at a distance of 6 cm for two minutes.
The exposed sheet was developed with cold water leaving an image having excellent resolution.
PREPARATION OF COMPOUND E
O ' O .' Il U
CH2-CH~ O-CH2-C~CH2 ~ CH2-CH-(:H2-N N-CH2C~ CH~ ~ CH~-C~ c_l;H-cll2 C~H2 O C - C-CH3 I ~
;~ CH2-~H-C-0 C=O ~H3 C=O O-ICl-C~CH2 O ~ NEI O
. , -. .
:. : :~: , . . . . .
,, , ", . , . : .
, , -21~ 5;~
Compound A (20.4 g from ~xample 1) and 10.6 ml dry tetrahydrofuran were dissolved in a 250 ml 3-necked round bottom flask equipped with a ma~netic stirrer, reflux condenser, pressure equalizing dropping funnel and CaS04 drying tube. 5.7 g phenylisocyanate was added dropwise over the course of five minutes. The reaction was terminated a~ter stirring for twenty hours at room temperature. The lack of an isocyanate infrared absorption band indicates the reaction of the isocyanate to be quantitative.
A layer of this material containing 2% of the photopolymerization catalyst of Example 1 was prepared ~s in Example 1. This layer was cured to insolubility with a Hanovia 3D690 mercury arc lamp in 15 seconds. The sample was 6 cm from the light source.
Preparation of 1,3-Bis[3-(2-allyloxyethoxy)-2-hydroxy~ropyl]-5,5-dimethyl-2,4-imidizolidinedione 0~ 0~
CH2=cH-cH2-o-cH2-cH2-o-c~2-~-cl~2-I N-CH2 CH-CH2-0-C 2 2 2 2 COMPOUND F
2-allyloxyethanol (20.43g, 0.lmoles), 0.03g 4-methoxyphenol, and 0.30g borontrifluoride etherate were chargad into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping ~unnel, reflux condenser and CaSO4 drying tube.
The reaction flask temperature was heated to 80C and 13.8g 1,3~bis~2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidinedione in 4.5g chloroform was added dropwise ; over 30 minutes. The reaction was maintained at 80 for 17 hours. At this time titration of residual epoxide groups indicated that the reaction was 99~ complete. The , ~
) , ~ . .
.
, Z~ 5 chloroform was removed by vacuum di3tillation leaving as residue a colorless liquid.
Example 15 Into a 250 ml three-necked round bottom flask equipped with mechanical stirrer, pressure equalizing dropping funnel, reflux condenser, and calcium sulfate drying tube were charged 103.0 g pentaerythritol triacrylate (hydroxy equivalent weight of 5153, 23.2 g 2-hydroxyethyl acrylate (0.2 moles), 0.08 g 4-methoxyphenol, and 1.0 g horontrifluoride etheratè. The reaction ~lask was heated to 75C and 55.2 g (0.40 molar epoxy equivalency~ 1,3~bis(2,3-epoxypropyl)-5,5-dimethyl-2,4-imidizolidinedione in 20 ml chloroform was added dropwise over one hour. After the addition, the reaction ~lask temperature was raised to 88C and stirred for 18.0 hours. At this time, titration of an aliquote ~or unreacted epoxide indicated the reaction was greater than 99% complete. The volatiles were removed by vacuum distillation leaving a viscous liquid which contains a mixture of bis(triacryloyl3-, bis(monoacryloyl)~, and the unsymmetrical monoacryloyl-triacryloyl-imidizolidinedione, and impuritles, introduced with the pentaerythritol triacrylate.
A layer of the reaction product of Example 15, prepared to contain 2% Irgacure 651 and cured as described in Example 1, had abrasion and chemical resistance characteristics similar to those o~ the layer of Example 1.`
.
. . .
, . .
Claims (11)
The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. Compounds of the forrnula:
wherein A1 and A2 are independently alkoxyalkyl groups having terminal ethylenic unsaturation and the groups having the general formula:
in which R-O- is a monovalent residue of an aliphatic terminally unsaturated primary alcohol, ROH, where R is selected from the formulae:
and [E?CH2?b?mR5?CH2)c wherein E is selected from the formulae and a, and c are independently integers of from 1 to 6, b is zero or an integer of from 1 to 6, R1 and R4 are independently hydrogen or methyl, R5 is an aliphatic group having 1 to 15 carbon atoms which may be interupted with up to two groups selected from the class consisting of ether oxygen groups or groups, E having a valence of m + 1 wherein m is an integer of 1 to 5, R2 is selected from the group of hydrogen, , and wherein R6 is selected from alkyl and alkenyl groups, R is an aliphatic or aromatic group, R3 is an alkylene yroup having 1 to 6 carbon atoms and up to one -O- radical in the group, and Z is a heterocyclic group of the formula:
Wherein X is a divalent group required to complete a 5- or 6-membered heterocyclic ring and is selected rom the group of ,,,,, or wherein R8, R9, R10, and R11 are independently selected from hydrogen, alkyl groups of 1 to 12 carbon atoms, cycloalkyl groups of 3 to 6 carbon atoms, and phenyl groups of 6 to 12 carbon atoms, and A3 is an alkoxyalkyl group as defined above for A1 and A2.
wherein A1 and A2 are independently alkoxyalkyl groups having terminal ethylenic unsaturation and the groups having the general formula:
in which R-O- is a monovalent residue of an aliphatic terminally unsaturated primary alcohol, ROH, where R is selected from the formulae:
and [E?CH2?b?mR5?CH2)c wherein E is selected from the formulae and a, and c are independently integers of from 1 to 6, b is zero or an integer of from 1 to 6, R1 and R4 are independently hydrogen or methyl, R5 is an aliphatic group having 1 to 15 carbon atoms which may be interupted with up to two groups selected from the class consisting of ether oxygen groups or groups, E having a valence of m + 1 wherein m is an integer of 1 to 5, R2 is selected from the group of hydrogen, , and wherein R6 is selected from alkyl and alkenyl groups, R is an aliphatic or aromatic group, R3 is an alkylene yroup having 1 to 6 carbon atoms and up to one -O- radical in the group, and Z is a heterocyclic group of the formula:
Wherein X is a divalent group required to complete a 5- or 6-membered heterocyclic ring and is selected rom the group of ,,,,, or wherein R8, R9, R10, and R11 are independently selected from hydrogen, alkyl groups of 1 to 12 carbon atoms, cycloalkyl groups of 3 to 6 carbon atoms, and phenyl groups of 6 to 12 carbon atoms, and A3 is an alkoxyalkyl group as defined above for A1 and A2.
2. The compound of claim 1 wherein R2 is wherein R7 is selected from alkyl group, phenyl group, acryloyloxyalkyl group, and methacryloyloxyalkyl group.
3. The compound of claim 1 wherein R2 is hydrogen.
4. The compound of claim 1 wherein X is .
5. The compound of claim 4 wherein R8 and R9 are independently selected from hydrogen, alkyl group of 1 to 12 carbon atoms, cycloalkyl of 3 to 6 carbon atoms, and phenyl group of 6 to 12 carbon atoms.
6. The compound of claim 4 wherein E is and m is 2 to 5.
7. The compound of claim 5 wherein E is and m is 2 to 5.
8. The compound of claim 7 wherein X is
9. The compound of claim 6 wherein R2 is selected from hydogen, , and wherein R6 is selected from alkenyl or alkyl radicals of 2 to 5 carbon atoms and R7 is selected from alkyl or phenyl radical of up to eight carbon atoms, acryloyloxyalkyl radical or methacryloyloxyalkyl radical.
10. The compound of claim 7 wherein R2 is selected from hydogen, , and wherein R6 is selected from alkenyl or alkyl radicals of 2 to 5 carbon atoms and R7 is selected from alkyI or phenyl radical of up to eight carbon atoms, acryloyloxyalkyl radical or methacryloyloxyalkyl radical.
11. The compound of claim 8 wherein R2 is selected from hydogen, , and wherein R6 is selected from alkenyl or alkyl radicals of 2 to 5 carbon atoms and R7 is selected from alkyl or phenyl radical of up to eight carbon atoms, acryloyloxyalkyl radical or methacryloyloxyalkyl radical.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/051,876 US4249011A (en) | 1979-06-25 | 1979-06-25 | Poly(ethylenically unsaturated alkoxy) heterocyclic compounds |
| US51,876 | 1979-06-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1125285A true CA1125285A (en) | 1982-06-08 |
Family
ID=21973902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA352,477A Expired CA1125285A (en) | 1979-06-25 | 1980-05-22 | Poly(ethylenically unsaturated alkoxy) heterocyclic compounds |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4249011A (en) |
| BE (1) | BE883999A (en) |
| CA (1) | CA1125285A (en) |
| ZA (1) | ZA803752B (en) |
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| US7678526B2 (en) * | 2005-10-07 | 2010-03-16 | 3M Innovative Properties Company | Radiation curable thermal transfer elements |
| CN101346649B (en) * | 2005-12-23 | 2010-09-01 | 3M创新有限公司 | Films including thermoplastic silicone block copolymers |
| JP5015953B2 (en) * | 2005-12-23 | 2012-09-05 | スリーエム イノベイティブ プロパティズ カンパニー | Multilayer films containing thermoplastic silicone block copolymers |
| US8574666B2 (en) | 2006-12-21 | 2013-11-05 | 3M Innovative Properties Company | Method of imparting corrosion resistance to a multi-layer window film having a metal layer |
| EP2205521A4 (en) * | 2007-09-06 | 2013-09-11 | 3M Innovative Properties Co | Tool for making microstructured articles |
| US9440376B2 (en) * | 2007-09-06 | 2016-09-13 | 3M Innovative Properties Company | Methods of forming molds and methods of forming articles using said molds |
| EP2198332A4 (en) | 2007-09-06 | 2011-11-30 | 3M Innovative Properties Co | Lightguides having light extraction structures providing regional control of light output |
| EP2208100B8 (en) * | 2007-10-11 | 2017-08-16 | 3M Innovative Properties Company | Chromatic confocal sensor |
| CN101821302A (en) * | 2007-10-11 | 2010-09-01 | 3M创新有限公司 | Highly functional multiphoton curable reactive species |
| WO2009075970A1 (en) * | 2007-12-12 | 2009-06-18 | 3M Innovative Properties Company | Method for making structures with improved edge definition |
| US20090169879A1 (en) * | 2007-12-31 | 2009-07-02 | 3M Innovative Properties Company | Corrosion resistant multi-layer window film construction |
| CN101960385B (en) | 2008-02-26 | 2012-11-07 | 3M创新有限公司 | Multi-photon exposure system |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3808226A (en) * | 1971-01-15 | 1974-04-30 | Ciba Geigy Corp | Polyacrylates of n-heterocyclic compounds |
| US3852302A (en) * | 1971-04-16 | 1974-12-03 | Ciba Geigy Corp | Diacrylic acid ester derivatives of hydantoin compounds |
| CH546800A (en) * | 1971-07-09 | 1974-03-15 | Ciba Geigy Ag | PROCESS FOR CURING POLYACRYLATES WITH IONIZING RAYS. |
| CH546798A (en) * | 1971-08-17 | 1974-03-15 | Ciba Geigy Ag | PROCESS FOR CURING ACRYLIC ACID ESTER DERIVATIVES WITH IONIZING RAYS. |
| US4071477A (en) * | 1976-06-10 | 1978-01-31 | Ciba-Geigy Corporation | Hydantoin diglycidyl compounds |
-
1979
- 1979-06-25 US US06/051,876 patent/US4249011A/en not_active Expired - Lifetime
-
1980
- 1980-05-22 CA CA352,477A patent/CA1125285A/en not_active Expired
- 1980-06-24 ZA ZA00803752A patent/ZA803752B/en unknown
- 1980-06-25 BE BE0/201170A patent/BE883999A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ZA803752B (en) | 1981-09-30 |
| US4249011A (en) | 1981-02-03 |
| BE883999A (en) | 1980-12-29 |
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