JPS63159416A - Heat or irradiation light curable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermally or radiation-curable liquid prepolymers, formulations containing said prepolymers, and printing plates, coatings,
The present invention relates to a method of using the prepolymer to make adhesives or sealants. More particularly, the present invention comprises (meth)acrylated commercial molecular hydrocarbon maleates;
itself or with monofunctional or polyfunctional unsaturated monomers, and with either a thermal polymerization initiator or a photopolymerization initiator, and is exposed to heat or ultraviolet light or high-energy ionizing radiation. 1, its purpose is to form a liquid prepolymer that forms a cured material that can be used as a printing plate, coating, adhesive or sealant.

Convention 11 (Photocurable compositions for forming printing plates, coatings, adhesives or sealants are well known in the art.

In particular, in the field of printing plate technology, the compositions are widely used in letterpress, offset lithography and V7 lexo printing. As originally taught in US Pat. No. 2,760,863, photopolymerizable compositions required the use of organic solvents for development.

However, due to the toxicity, high volatility, and low ignition point of commercially available organic solvents, their use often creates harmful conditions and causes pollution problems.

Subsequently, U.S. Pat.
No. 081 disclosed a printing plate in which the unirradiated areas could be removed with a dilute aqueous solution of a detergent. However, the material has a sticky surface, leading to ink filling in the gaps in the paper, which may lead to poor printing quality. A photosensitive composition prepared from a diene polymer having a photopolymerizable unsaturated group, a photopolymerizable vinyl polymer, a photopolymerization initiator, and an optional thermal polymerization inhibitor (
imagewise) teaches a method of polymeric imaging comprising exposing to ultraviolet radiation and removing unexposed portions of the hindlimb composition to form a printing plate. Diene polymers such as polybutanoene can have polymerizable unsaturated bonds and can be chain extended with epichlorohydrin.

One of the objects of the present invention is to provide a liquid heat or radiation curable prepolymer for producing printing plates, coatings, adhesives and sealants. An object of the present invention is to provide a formulation containing the prepolymer. Yet another object of the invention is to provide a method for making printing plates, coatings, adhesives and sealants using the prepolymers and formulations containing the same. A further object of the present invention is to provide a printing plate composition which yields a rapidly curing material which is aqueous developable, has no sticky surface and has good tensile strength.

My duty! The present invention relates to a heat- or radiation-curable liquid prepolymer and a composition containing the prepolymer. The prepolymer has a terminal ya(meth)7 acrylate group and a maleenylic acid group.
It is a high molecular weight hydrocarbon maleate having a (pendant) group. That is, a high molecular weight hydrocarbon is maleated by incorporating maleate groups into the polymer backbone, and the maleated product is reacted with a methacrylate group-containing reactant to give a (meth)acrylate terminated high molecular weight hydrocarbon maleate; The resulting product is maleated to provide pendant maleate groups. Secondary maleation can be done on hydroxyl groups. Therefore, the new polymer has a structure of partially or completely esterified polyhydroxyfulkylene groups, in which the residues of the woven material are monoesterified with (meth)acrylic carboxyl groups, It can also be a liquid hydrocarbon maleate polymer having terminal groups such that the acid portion or all are monoesterified with maleate groups. As shown in the formula below, the polyhydroxyfulkylene is preferably nohydroxyethylene.

Liquid maleated and methacrylated high molecular weight hydrocarbon maleates are 2P (Y)a where P is a homopolymer or copolymer of a hydrocarbon residue, such as butadiene, isoprene or chloroprene, and is a random or block polymer of the diene. and copolymers of the tsene with comonomers such as styrene, imbutylene, propylene, ethylene, acrylonitrile, acrylic acid or neoprene, or wherein the olefinic unsaturation is partially removed by partial hydrogenation. a is 1 or greater, and Y is a pendant or terminal group including (meth)acrylate end groups and maleate groups. Generally a is greater than or equal to 1, preferably having an average value of 1.8 or greater.

The residue Y, which may be truly terminal or pendant to P, preferably has the formula (■): OR.

++ 1 (Cl2)n -QC-C= CH2嘗-X-(C-C=C-C-0-CH2C)I-0)b-
(CC=CC-0)cH(1)III I II
Ill l IIOR, R200
R, R20 However, Ro and R2 each individually represent hydrogen 1. halogen, carboxy, linear or cyclic furkyl having 1-20 carbon atoms, 71J-l, alkaryl and 7ralkyl having 6-20 carbon atoms, R3 is hydrogen or methyl, X is 10-1-8- or -NR-, R is hydrogen or alkyl having 1 to 6 carbon atoms, n is an integer from 1 to 6, and b is an integer from 1 to 10. , and C has an average value of 0.1 to 1.0, ie 10% to 100% of the Y groups on the polymer have pendant malenylic groups.

Prepolymers are generally produced by reacting a functionalized liquid hydrocarbon polymer with a reactant that imparts maleate groups, but are not necessarily used to produce the prepolymers of the present invention. Typical functional liquid hydrocarbon polymers have a polymerized butadiene, isoprene or chloroprene backbone, and include random or block polymers of these dienes, such as styrene, imbutylene, propylene, copolymers with comonomers such as ethylene, acrylonitrile, acrylic acid or neohexene, or corresponding polymers in which the olefinic unsaturation has been partially removed by partial hydrogenation, and amine, hydroxyl or thiol functionalities. This includes polymers containing groups. The types of functional polymers and copolymers useful for making these polymers include rubber
Chemistry and Ticknomy (Rubber)
Chemistry and technology
42, pp. 71-107 (1969) 7
Includes polymers made by free radical polymerization using special catalysts, as described by French, or by anionic polymerization followed by capping of the floating polymer with ethylene oxide or the like. Generally, hydrocarbon polymers containing functional groups are about i
,oo.

It has a molecular weight of 10,000 to 10,000. Polymers having a molecular weight of 3000 or higher are preferred, so a preferred molecular weight range is about 3000 to 10.000.

More specifically, the first step in the preparation of the prepolymer is the preparation of a functional or Letechelic polymer of the type described by Seven Lench in the Rubber Chemistry and Chiknomy paper cited above. It is carried out by reacting a polymer whose terminal and/or pendant functional groups are hydroxyl, thiol, or amino with an unsaturated carboxylic acid anhydride.

As an example of a reaction to introduce maleate groups into a functional polymer, the reaction of hydroxyl-terminated polybutadiene with maleic anhydride is represented as follows: As shown above, approximately 2 moles of maleic anhydride are added to each 1 mole of maleic anhydride. reacts with moles of hydroxyl-terminated polybutanoene.

The maleation reaction is preferably carried out at a temperature range of 60-120°C for a reaction time of 4-12 hours. The reaction is carried out in the presence of a thermal polymerization inhibitor such as di-t-butylcresol.

Although the reaction is preferably carried out in the absence of a solvent, inert solvents such as toluene, benzene, chloroform, methylene chloride, tetrahydroctane, hetacetone and ethyl acetate can be used if necessary.

There is no need for a catalyst, but catalytic amounts of acids such as phosphoric acid and stannous octoate or Lewis acids can be used.Reactants are typically used for reaction times such as maleic anhydride, where there is one hydroxyl group on the polymer. It is added in approximately stoichiometric amounts to allow reaction with acid molecules.

The following general formula, provided that R1 and R2 are hydrogen, halogen, carboxyl,
linear or cyclic alkyl having 1-20 carbon atoms, 6
- Any unsaturated acid anhydride (i.e. maleic acid or maleic acid substituted) of is a member selected from the group consisting of aryl, alkaryl and 7ralkyl having 20 carbon atoms is a hydrocarbon polymer. It can act as a reactant with the above functional groups, such as OH groups, to form the high molecular weight hydrocarbon maleates in the first step of the invention.

In addition, the corresponding unsaturated sea esters and sea acids can also act as reactants, but longer reaction times are usually required.
Includes diphenylmaleic anhydride, dichloromaleic anhydride, 2,3-methylmaleic anhydride, maleic anhydride, promaleic anhydride, citrafun R anhydride, and cis-7conitic anhydride. , but is not limited to this.

In the second step of prepolymer synthesis, the liquid high molecular weight hydrocarbon maleate is reacted with a reactant containing (meth)acrylate groups. While providing the polymer with reactive (meth)acrylate groups, the reaction should yield active hydrogen-containing groups that can undergo maleation. For example, the high molecular weight hydrocarbon maleate produced in the first example above now contains carboxyl groups due to the reaction of hydroxyl-terminated polybutadiene with maleic anhydride;
The C0OH groups on the polymer are methacrylated by reacting with, for example, glycidyl methacrylate (1 mol per equivalent of COOH) and reactive hydroxyl groups are generated: C11° If necessary, excess epoxy compound is added. can be used. Excess epoxide ends up reacting with the hydroxyl groups formed in the initial reaction between the functional terminal olefin addition polymer and the epoxide compound.

Alternatively, reactants containing (meth)acrylate groups and aziridine groups can be used in the (meth)acrylation reaction.

This reaction occurs at temperatures between 25°C and 200°C, but
Temperatures between 60-100'C are preferred.

Acidic or basic catalysts are not required but can be used to shorten the required reaction time and lower the temperature. A few useful catalysts include sodium hydroxide;
These include sodium ethoxide, triethylamine, triethylbenzene chloride, hydrogen chloride, and boron trifluoride ether complexes. Generally 0.001 to 5.0
% catalyst by weight is used.

In the third step of prepolymer synthesis, at least some of the groups containing active hydrogen groups produced in the second step of the reaction are maleated, thus providing pendant maleate groups on the prepolymer. That is, the hydroxyl group produced in the above example upon reaction with glycidyl methacrylate can be reacted with maleic anhydride to provide a pendant maleate group. Maleate side groups are not incorporated into the polymer backbone (
It will be appreciated that fi (in contrast to the results of the initial maleation reaction) is attached to the main chain.

The average number of pendant maleate groups per molecule of prepolymer is about 0.2 to 1.6, preferably about 0.4 to 1.2. This average value is derived from the number of active hydrogen-containing groups generated in the second reaction step and the degree of maleation. (As used herein, the term "degree of maleation" refers to the percentage of active hydrogen-containing groups that are maleated.) For example, prepolymer 1
Formula (11) containing two reactive hydroxyl groups per molecule
), a preferred range of 0.2 to 1.6 is obtained with a degree of maleation of about 10% to 80%. This degree of heptadation is achieved in the third step of prepolymer synthesis by only 0.1 to 0.0.0% per OHI equivalent.
Obtained by using 8 equivalents of maleating agent. Similarly, with respect to formula (I), if a is 2, the above preferred ranges are obtained when C is 0.1 to 0.8 or 0.2 to O, (3), respectively.

By having about 0.2 to 1.6 pendant maleate groups per prepolymer molecule, dispersibility in aqueous detergents is improved compared to corresponding prepolymers that have less or no pendant maleate groups. After curing, an increase in tensile strength and tear strength, a decrease in surface tack and an increase in surface tension (the latter can actually improve the printing properties in ash produced from prepolymers) For macromolecule II (molecular weight greater than about 3,000) prepolymers suitable for use in the present invention, it has been found that the polymers II (molecular weight greater than about 3,000) can achieve a When the average number exceeds about 1.6, the viscosity of the prepolymer, and most useful photosensitive compositions containing the prepolymer, is typically too high for practical use. Generally about 0.00000000000000 per molecule of prepolymer.
Within the more preferred range of 1 to 1.degree. maleate pendant groups, an optimum balance between the above advantages and viscosity is obtained. The cured prepolymer and soprepolymer compositions of the present invention are also used in common printing inks in filtrates, alcohols and alcohol/acetate solvents.
It exhibits resistance to moisture similar to that of cured formulations containing the corresponding prepolymers without pendant maleate functional groups.

Free carboxyl groups are generated with the introduction of maleate side groups. This can in turn be reacted with another glycidyl (meth)7-acrylate molecule.

By repeating this sequence, an optionally large number of (meth)acrylate and maleate functional groups can be developed.

Generally, the prepolymers obtained in the present invention which are olefinically unsaturated in end or pendant groups have Brookfield viscosities between 1.000 and i, ooo, ooo centiboise measured at 25°C. , most preferably a viscous liquid between 20,000 and 10,000 centivoise.

The composition also has a reactivity having the following formula: % formula % where R1 is hydrogen or methyl, and R6 is an organic residue having a valency of n, and n is 1 or greater. It can contain up to 90% by weight of acrylic or methacrylic diluent. The reactive acrylic diluents include, but are not limited to, nitrinochylolepropane triacrylate, hexanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexane. Diol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 200 noacrylate F, tetraethylene glycol-J resin acrylate, triethylene glycol noacrylate, pentaerythritol tetraacrylate,
Triethylene glycol noacrylate, ethoxylated bisphenol-A noacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetra7acrylate, triacrylate of tris(hydroxyethyl)isocyanurate, dipentaerythritol hydroxypentaacrylate, pentaerythritol triacrylate Acrylate, ethoxylated trinotylolpropane triacrylate, triethylene glycol dimethyl acrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol-200 dimethacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol-6
00 dimethacrylate, 1,3-butylene glycol dittaacrylate, ethoxylated bis7E/--A dimethacrylate, trimethylolpropane tritacrylate, diethylene glycol diacrylate, 1,4-
For modifying butanediol diacrylate, diethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, glycerin methacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol diacrylate and cured products. similar substances that can be added to the composition. Cyclohexyl acrylate, isobornyl acrylate,
Mono-7 acrylates such as lauryl acrylate and tetrahydrofurfuryl 7-acrylate and the corresponding methacrylates can also be used as reactive diluents.

Photoinitiators for prepolymers and formulations containing the same include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isopropyl ether and benzoin isobutyl ether alkyl ethers. Other categories of photoinitiators are 2
, 2-dimethoxy-2-phenyl 7cetophenone, i.e. “Irgacure ■651”
(Chipper (Iggy)) and 2,2-jethoxy-2-phenylacetophenone. Yet another class of photoinitiators are aldehyde and ketone carbonyl compounds having at least one aromatic nucleus directly attached to a carboxyl group. These compound initiators include, but are not limited to: benzophenone,
Acetophenone, 0-methoxybenzophenone, acenaphthene-quinone, methyl ethyl ketone, valerophenone, hexanophenone, alpha phenyl-butyrophenone, p-mol 7-olinopropio-7enone, dipenzosuberone, 4-mol 7-olinopenzo-7enone, 4-mol 7-ol Nodeoxybenzophenone, p-noacetylbenzene, 4-7minobenzo7enone, 4'-methoxyacetophenone.

Benzaldehyde, full 7 arterthalon, 9-acetyl 7 enanthrene, 2-7 cetyl 7 enane XI/n, 1
0-f oxanthenone, 3-7 cetyl-7 enanthrene, 3-7 cetiridone, 9-fluorenone, 1-indanone, 1,3,5-triacetylbenzene, thioxanthin-9-one, xanthine-9-one, 7- H-Benz [? 'l-Anthracen-7-one, 1-su7taldehyde, 4.

4′-bis(dimethylamino)-benzophenone, fluoren-9-one, 1′-acetonaphthone, 2′-acetonaphthone, 2,3-butanedione, acetonatene,
Benz [A1 Anthracene 7.12 Tsuen etc. Heptoosphines, such as triphenyl-7osphine and tri-o-)'77osfine, also act as photoinitiators. The photoinitiator or mixture thereof is usually added in an amount ranging from 0.01 to 5% by weight of the total composition.

Classes of actinic light useful for curing include solar or type R3 sunlamps, carbon arc lamps, xenon arc lamps, mercury vapor lamps,
Ultraviolet radiation and other types of actinic radiation commonly found in radiation emitted from artificial light sources such as tungsten halide lamps and the like. Ultraviolet irradiation can be used most effectively if the photocurable composition contains a suitable photoinitiator. The curing period can be adjusted to be extremely short, and therefore it is industrially economical by appropriately selecting the ultraviolet light source, the photopolymerization initiator, and its concentration. Curing times of about 10 seconds are also possible, especially for desired thin film applications, such as coatings. For thicker cured products, preferably 1-5 minutes for up to 100 minutes.
A curing period of 1 minute is typically used.

If UV radiation is used, 0.0004 to 60.0 watts/cJ in the 200-400 nanometer range.
illuminance is commonly used. High energy ionizing radiation can also be used in the curing step in the present invention without the use of photoinitiators. 0.01-1 when using high-energy ionizing radiation, e.g. an electron beam.
07〃Dose in the range of 1.0XIO'''' can to 4
A dose rate of 000 Merad/sec is used. Any radiation having an energy greater than 3.0 electron volts can be used to effect the curing reaction of the present invention.

Thermal polymerization initiators used to cure the prepolymers and formulations containing the same are selected from pinacols, thiurams, organic peroxides, with or without substituents, and mixtures thereof! It is a group starting scrap.

The organic peroxide that can be used has the following general formula: % formula %) R is hydrogen, aryl, alkyl, arylcarbonyl,
alkarylcarbonyl and alkylcarbonyl, and R, is alkyl or aryl, and the alkyl group is 1
It is a peroxide containing from 1 to 10 carbon atoms.

Examples of organic peroxides that can be used include, but are not limited to: 2,5-trimethyl-2
．． 5-D-butylperoxy)-hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, 1
．． 3-bis-(cumylperoxyisopropyl)benzene, 2,4-dichlorobenzoyl peroxide, cabritul peroxide, lauroyl peroxide, t-butyl peroxyisobutyrate, benzoyl peroxide, p''''''chlorobenzoyl peroxydroxyheptyl peroxide , not t-butyldibel 7 tally)
, t-2 tylberacetate, t-butylberbenzoate, dicumyl peroxide, 1. ．． 1. -di(t-butylperoxy)-3,3,5-)limethylcyclohexane and not-t-butylperoxide.

Examples of azo compounds that can be used in Kenpo include, but are not limited to, commercially available compounds such as: 2-t-butylazo 2-thia/propane;
2'-7 zobis(2,4-methyl-4-notoxive-7leronitrile); 2,2'-7 zobis(imbutyronitrile); 2,2°-7zobis(2,4-nomethylvaleronitrile) ) and 1,1′-7zobis(cyclohexanecarbonitrile).

Thiuram, which can be used in the box method as a thermal polymerization initiator, has the following formula: where R, , R2, R1 and VR1 are taken individually, hydrogen, linear or branched alkyl having from about 12 carbon atoms, 2 linear or branched alkenyl having from 3 to about 10 ring carbon atoms, cycloalkyl having 3 to about 10 ring carbon atoms, cycloalkenyl having 3 to about 10 ring carbon atoms, 6 to about 12 can be 7 aryl having ring carbon atoms of R1 and R2, VR co and R1 each represent a divalent fullkylene group having 2 to about 12 carbon atoms (CnHzn-), a divalent fullkylene group having 3 to about 10 carbon atoms (CnH2n-2); , divalent flucanoenylene group having from 5 to about 10 carbon atoms (CnHzn-4), divalent alkali group having about 10 carbon atoms) l) unicine group (-CnH
2n --), a divalent fullkyleneoxyalkylene group (-C,H,) having a total of 4 to about 12 carbon atoms.

0CXH2X ), or a divalent fullkyleneami7alkylene group having a total of 4 to about 12 carbon atoms:
) can be, is later.

Thiurams that can be used include, but are not limited to: tetraethylthiuram disulfide, tetraethylthiuram disulfide, di-N-pentamethylenethiuram thisulfide, tetrabutylthiuram disulfide, diphenyldimethylthiuram disulfide, diphenyl dimethyl. Thiuram disulfide, noethyleneoxythiuram disulfide, etc.

Pinacol with or without a substituent that can be used as a thermal polymerization initiator in Kempo has the following general formula: However, R5 and R3 are the same type or different types, and are aromatic residues with or without a substituent. , R2 and R1 are aliphatic or aromatic residues with or without substituents, and X and Y, which may be the same or different types, are hydroxyl, alkoxy or 7-aryloxy.

Preferred pinacols are those in which R2, R2, R2 and R4 are aromatic residues, especially phenyl groups, and X and Y are hydroxyl groups.

Examples of compounds belonging to this category include, but are not limited to: benzopinacol, 4
．． 4'-dichlorobenzobinafur, 4.4'-dibromobenzobinacol, 4.4°-short benzobinacol, 4.4',4'',4'''-tetrachlorobenzobinacol, 2.4-2 ', 4'-tetrachlorobenzopinacol, 4.4'-dimethylbenzopinacol, 3.
3'-dimethylbenzopinacol, 2,2°-dinothylbenzobinacol, 3.4-3', 4'-tetramethylbenzopinacol, 4.4'-notoxybenzopinacol, 4.4'.

4″14″-tetramethoxybenzobinacol, 4°4
゛-Diphenylbenzopinacol, 4t4'-fuchloro-4''-tumethylbenzopinacol, 4゜4゛-tumethyl-4~-diphenylbenzopinacol, xanthopinacol, fluorenone pinacol, aceto7ene/ampinafur, 4.4' -trimethylacetophenone-binafur, 4,4'-dichloroaceto7e/n-pinacol, 1.1.2-)diphenyl-propane-1,2-nool, 1,2°3,4-tetraphenylbutane-2, 3
-nool, 1,2-diphenylcyclobutane-1,2
-Diol, propiophenone binafur, 4.4'-
trimethylpropiophenone-binacol, 2,2°-ethyl-3,3'-zomethoxyprobiophenone-pinafur, 1,1,1,4.4,4-hexafluoro-2
, 3-diphenylbutane-2,3-nool.

Further thermal polymerization initiators according to the present invention include the following: benzopinacol monomethyl ether, benzopinacol monophenyl ether, benzopinacol monoisobutyl ether, penzopinacol mo/-(jethoxymethyl)ether, etc. .

Thermal polymerization TM initiator or mixture thereof is usually 0.0% of total acid
It is added in amounts ranging from 1 to 10% by weight.

Heat curing is usually carried out at temperatures in the range 80°-150°C. A curing period of up to 30 minutes or more is required for sufficient curing.

Thermal polymerization inhibitors and stabilizers are added to prevent premature crosslinking during heat treatment and storage of prepolymers containing the compositions of the invention. Such stabilizers are well known in the art and include, but are not limited to, the following compounds: di-butyl-p-cresol, hydroxide/methyl ether, pyrogallol, Quinone, hydroquinone, methylene blue, t-butylcatechol, hydroquinone monobennorether, methylhydroquinone, amylhydroquinone, amyloxyhydroquinone, lobethyl 7 ether, phenol, hydroquinone monopropyl ether, phenothiazone and nitrobenzene, and mixtures thereof. When used in amounts ranging from about 0.01 to about 2% by weight of the prepolymer, these stabilizers are highly effective in preventing crosslinking of the prepolymer composition during processing and storage. .

When the prepolymer or composition containing the agent is UV cured, the composition can contain up to about 50% by weight of an inert particulate filler that is substantially transparent to actinic light. The fillers include organophilic silica, bentonite, silica, and glass powders having particle sizes whose largest dimension is less than 0.4 mil. Dimensions are 0
．． Particles of 1 μm or less are preferred. The filler imparts desirable properties to the composition and highlights the advantages of the present invention.

When thermally curing compositions containing the prepolymers of the present invention, equivalent amounts of conventional fillers such as graphite can be used.

The prepolymers of the present invention are used as letterpress printing plates for applications requiring photopolymers that are imagewise exposed (i.e. through a photographic negative) and subsequently developed in an aqueous medium, such as letterpress printing or 7-lexo printing. It is particularly suitable for applications such as

The prepolymer composition of the present invention has a molecular weight of about 200 to about 400
Photographic transparency TTL (
photography
Upon imagewise exposure through y), the composition below the exposed areas becomes insolubilized, while the polymer below the unexposed areas remains dispersible in the aqueous detergent solution. Stop. Subsequent washing of the plate with an aqueous detergent solution removes the dispersing polymer, leaving a replica of the photographic positive in relief. Cleaning is usually carried out with dilute aqueous solutions of anionic or nonionic detergents. Anionic detergents such as alpha olefin sulfonates, alkylaryl sulfonates, lauryl sulfates, alkyl esters of sulfo-succinic acid, or sulfated ethylene oxide condensates of alkylphenols or aliphatic alcohols, and alkyl 7 ethers, aliphatic Nonionic detergents such as ethylene oxide condensates of alcohols or fatty acids can be used. Alpha olefin sulfonates are particularly useful. Generally at temperatures of 25°-60°C, detergent concentrations of about 0.2 to 2% are commonly used. It is often possible to accelerate development by brushing or scrubbing. For large-scale operations, it is advantageous to use aqueous cleaning agents using jet or spray equipment. In some cases it may be useful to use small amounts of organic solvents such as short chain aliphatic alcohols and ketones. Suitable solvents of this type include methanol, ethanol and acetone, which are generally used in amounts of no more than 25-35% of the aqueous detergent developer, preferably less than 1-5%. be done. Following development of the plate, any remaining surface water and any organic solvents that may be present can be removed by flowing warm air over the relief. In some cases, after washing away the uncrosslinked photopolymer composition, by exposure to actinic light at the above wavelengths,
It may be desirable to AIA light or post cure the plate.

The following examples are given to illustrate the invention, but are not intended to limit it.

Unless otherwise specified, all parts and percentages are by weight. The liquid hydrocarbon polymer used in the examples for illustration is hydroxyl-terminated polybutanoene.

500 g of polybutanoene having 1.9 terminal hydroxyl groups per molecule and an average molecular weight of 4750 was added to 0.0 g of polybutanoene having an average molecular weight of 4750.
Reacted with 17 g of maleic anhydride in the presence of 3% 1,6-di-tert-butyl-4-methylphenol at 85° C. for 8 hours.

Further 85% of the intermediate product polybutadiene maleate
°C for 12 h or the acid functionality was determined by titration to 0.05 m
25. until eq/g or less. was reacted with glycitul methacrylate. The resulting methacrylated polybutadiene maleate (790,000 at 25°C
cp) with 2% Irgacure 651 (trade name of Civer Geigy), and a 20 mil thick sample was mixed with Mylar (
Mylar) sheet open for 4 minutes 11 nW/c
It was irradiated with an intensity of d. The cured material exhibited properties of 287 psi modulus, 173 psi tensile stress, 104% elongation, 45 Shore A hardness, and 43% resilience.

250 g of the 7-acrylated polybutanoene maleate described in Example 1 were further mixed with 2I? of maleic anhydride at 85° C. for 8 hours or until infrared analysis showed no consumption of anhydride. Approximately 25% of the available hydroxyl functionality on the intermediate methacrylated polybutadiene maleate is thus maleated and at 25°C 1*612*0
A polymer with a viscosity of 0.00 cp was obtained. The prepolymer was formulated with 2% Iguraki 17651 and irradiated as described in Example 1, resulting in a modulus of 441 psi, a tensile stress of 260 psi, an elongation of 103%, an elongation of 57
A cured material was obtained with a Shore A hardness of 50% and a resilience of 50%.

K1 Life-1 250 g of methacrylate-1-modified polybutadiene maleate described in Example 1 was further added to 41? Maleic anhydride and 111! The reaction was allowed to proceed at 85° C. until no anhydride was consumed or until infrared analysis showed that no anhydride was consumed. Approximately 50% of the available hydroxyl functionality on the intermediate methacrylated polybutanoene maleate is thus maleated and the 2,000.degree.
A polymer with a viscosity greater than 0,000 ep was obtained.

When the prepolymer was formulated with 2% Igracu 7651 and irradiated as described in Example 1, it had a modulus of 537 psi, a tensile stress of 321 psi, an elongation of 90%, a Shore A hardness of 61, and a resilience of 57%. A cured material was obtained.

Seed 1st raw - 3 - The methacrylated polybutadiene maleate ioOg described in Example 1 was added to 431? isobornyl methacrylate), 13. lauryl methacrylate and 0
．． Combined with 8 g of Irgacure 651 and incubated at 25°C for 2 hours.
A composition with a viscosity of 1,000 cp was obtained. When the composition is irradiated once as described in Example 1, 200 ps
modulus of i, 465 psi tensile stress, 22
A cured film was obtained with an elongation of 4%, a Shore A hardness of 42, a resilience of 13% and a tear resistance of 1.91 bs, 7 inches.

100 g of the doubly methacrylated polybutadiene described in Example 2 were mixed with 43 g of isobutyl methacrylate, 13 g of lauryl methacrylate and
．． 89 Irgacure 651, 32,
A composition with a viscosity of 0.000 cp was obtained. When the composition was irradiated as described in Example 1, it had a modulus of 420 psi, a tensile stress of 540 psi, an elongation of 195%, a sit arm hardness of 58, a resilience of 18% and a tear resistance of 4°61 bs, 7 in. A cured film was obtained.

! 2.5. of lauryl methacrylate and 0.8 g of Ircu 7651 to obtain a composition having a viscosity of 29,000 cp at 25°C. When the composition is irradiated as described in Example 1, 310 ps
Modulus of i, 580 psi tensile stress, 192
A cured film was obtained with an elongation of 58%, a sit arm hardness of 58, a resilience of 16% and a tear resistance of 6°51 bs, 7 inches.

Bundle - Turtle fi? -7 To produce a printing plate for lexo printing, the photographic negative was placed on an exposure device of a commercially available type and covered with a polypropylene covering sheet. The polymer formulations described in Examples 4-6 were individually coated to a thickness of 110 mils. Each coated formulation was covered with a 5-mil Mylar-backed sheet. To provide a substrate or floor, the polymer formulation was exposed to a series of UV lamps (2,6 mW/ej) for 40 seconds through a Mylar backing.

This was followed by a 3 minute visual exposure through the negative to a series of UV lamps (3.6 mW/eJ). The exposed plate was stripped of its 11 liters, 1% of a 40% solution of sodium alpha olefin sulfonate (commercially available as Biotergel A S-40 from Stepan Chemicals), and 15% of silicone. A rotary type commercially available mold equipped with a spray of an aqueous detergent solution containing 0.3% defoamer emulsion (Defoamer (commercially available from Dow-Corning as Defoamerl H-10)) Developed in a cleaning device. After cleaning,
The printing plates were post-exposed for 10 minutes under water using a fluorescent lamp.

The printing plates made from the formulations described in Examples 4-6 had comparable resistance to swelling by both water-based and solvent-based inks, but the appearance, surface tackiness and exhibited considerable differences in printing properties.

In particular, compositions containing maleate-functional side groups (as described in Examples 5 and 6) were found to be suitable for aqueous cleaning, as evidenced by the non-sticky surface and matte finish on the printing plate 707. dispersed more easily in the drug solution.

The printing plates made from the compositions containing pendant maleate functional groups (Examples 5 and V6) also had higher surface tensions than the plates made from the material without pendant maleate groups (Example 4). As a result, the former was recognized to have excellent ink transfer performance.

The printing plates thus prepared from the formulation described in Example 6 (in which 50% of the hydroxyl side groups were maleated) had a surface tension of 43 dynes/C leakage and were smooth and free of tack. It showed 7aa.

The formulation described in Example 5 (25 of the hydroxyl side groups)
41% maleated)
It exhibited a smooth floor with a surface tension of dyne/cx and mild surface tack. The formulation described in Example 4 (with maleate pendant groups) had a surface tension of 38 dynes/cm and gave a printing plate characterized by a rough texture and a sticky floor.

Claims (1)

Claims: 1) A liquid heat- or radiation-curable composition comprising a (meth)acrylate-terminated high molecular weight hydrocarbon maleate prepolymer having side maleate groups. 2) Average of 0.2 to 1.6 per molecule of prepolymer
2. A composition according to claim 1, characterized in that it contains 2 pendant maleate groups. 3) Average of 0.4 to 1.2 per molecule of prepolymer
2. A composition according to claim 1, characterized in that it contains 2 pendant maleate groups. 4) The composition of claim 3, wherein said prepolymer has a molecular weight greater than about 3000. 5) Furthermore, there are the following formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼ However, R_4 is hydrogen or methyl, and R_5 is the valence n
Composition according to claim 1, characterized in that it contains up to 90% by weight of reactive monomers of organic residues having n equal to or greater than 1. 6) The composition according to claim 5, further comprising a photopolymerization initiator. 7) The composition according to claim 5, further comprising a thermal polymerization initiator. 8) The prepolymer has the formula P(Y)_a, where P is a hydrocarbon polymer residue, and Y has the following structure ▲ Numerical formula, chemical formula, table, etc. ▼ In the above formula, R_1 and R_2 each individually represent hydrogen, halogen, carboxy, linear or cyclic alkyl with 1-20 carbon atoms, aryl, alkaryl and aralkyl with 6-20 carbon atoms, R_3 is hydrogen or methyl, X is -O- , -S- or -NR-, R is hydrogen or alkyl having 1 to 6 carbon atoms, n is an integer of 1 to 6, b is an integer of 1 to 10, and c is an integer of 1 to 10. has an average value of 0.1 to 1.0, and P
A composition according to claim 1, characterized in that it has: a side group or a terminal group bonded to. 9) a is about 1.8 or greater and c is about 0.1
Claim 8 characterized in that the range is between 0.8 and 0.8.
Compositions as described in Section. 10) The composition according to claim 9, characterized in that c is about 0.2 to 0.6. 11) The hydrocarbon residue is a homopolymer or copolymer of butadiene, isoprene or chloroprene, butadiene,
Claims characterized in that it is a copolymer of isoprene or chloroprene with styrene, isobutylene, propylene, ethylene, acrylonitrile, acrylic acid or neoprene, or the residue of a corresponding partially hydrogenated polymer Composition according to item 8. 12) The composition according to claim 8, wherein X is -O-, n and b are 1, R_1 and R_2 are hydrogen, and R_3 is methyl. 13) a is about 1.8 or greater and c is about 0.
13. A composition according to claim 12, characterized in that it has a molecular weight of 1 to 0.8. 14) A photosensitive polymer material comprising a support and a coating comprising the composition according to claim 1. 15) A photosensitive polymer material comprising a support and a coating comprising the composition according to claim 8. 16) (a) Hydrocarbon polymers containing side groups and/or terminal functional groups selected from the class consisting of amines, hydroxyls and thiols are defined by the following general formula: R_2 is a member of the class consisting of hydrogen, halogen, carboxyl, linear or cyclic alkyl having 1-20 carbon atoms, aryl, alkaryl and aralkyl having 6-20 carbon atoms, respectively; (b) producing a high molecular weight hydrocarbon maleate by reacting it with a member of the class consisting of unsaturated di-esters and di-acids and the corresponding unsaturated di-esters and di-acids for a period sufficient to form the high molecular weight hydrocarbon maleate; A high molecular weight hydrocarbon maleate is treated with at least a stoichiometric amount of a reactant which is reactive with the pendant and/or terminal carboxyl groups of the high molecular weight hydrocarbon maleate and includes a methacrylate group, and at a temperature in the range of 25-200°C. to produce a methacrylated high molecular weight hydrocarbon maleate having active hydrogen-containing groups as pendant groups, and thereafter (c) having maleate pendant groups characterized by reacting an active hydrogen-containing group with the class consisting of unsaturated anhydrides, di-esters, and di-acids (meth)
A method for producing acrylate-terminated high molecular weight hydrocarbon maleate. 17) The hydrocarbon polymer is a homopolymer or copolymer of butadiene, isoprene or chloroprene, a copolymer of butadiene, isoprene or chloroprene with styrene, isobutylene, propylene, ethylene, acrylonitrile, acrylic acid or neoprene, or a partial 17. Process according to claim 16, characterized in that the corresponding polymer is hydrogenated to . 18) A method according to claim 16, characterized in that the hydrocarbon polymer is hydroxy-terminated polybutadiene. 19) The method according to claim 18, wherein the unsaturated anhydride is maleic anhydride. 20) the unsaturated anhydride used in the reaction of step (c),
The amount of di-ester or di-acid is on average 0.2 to 1.
17. The method of claim 16, wherein the amount is sufficient to react with the active hydrogen-containing side groups of 6. 21) the unsaturated anhydride used in the reaction of step (c),
The amount of di-ester or di-acid is on average 0.4 to 1.
17. The method of claim 16, wherein the amount is sufficient to react with the active hydrogen-containing pendant groups of 2. 22) Coating a film of a photopolymerizable composition comprising a (meth)acrylate-terminated high molecular weight hydrocarbon maleate prepolymer having side maleate groups on a substrate, and visually exposing the film to actinic radiation. A process for producing a relief printing plate, characterized in that it comprises the steps of crosslinking the composition in the exposed areas and then removing the composition in the unexposed areas by washing with an aqueous detergent solution. 23) After cleaning with the cleaning solution, the relief printing plate is further exposed to actinic radiation one more time.
The method described in Section 2. 24) The composition further comprises a photoinitiator and up to 90% by weight.
The following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, R_4 is hydrogen or methyl, and R_5 is n
23. The method of claim 22, wherein the reactive monomer is an organic residue having a valency of , and n is 1 or greater. 25) Claim 22, characterized in that the prepolymer contains on average 0.2 to 1.6 pendant maleate groups.
The method described in section. 26) Claim 22, characterized in that the prepolymer contains an average of 0.4 to 1.2 pendant maleate groups.
The method described in section. 27) The prepolymer has the formula P(Y)_a, where P is a hydrocarbon polymer residue, and Y has the following structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the above formula, R_1 and R_2 each individually represent hydrogen, halogen, carboxy, linear or cyclic alkyl with 1-20 carbon atoms, aryl, alkaryl and aralkyl with 6-20 carbon atoms, R_3 is hydrogen or methyl, X is -O- , -S- or -NR-, R is hydrogen or alkyl having 1 to 6 carbon atoms, n is an integer of 1 to 6, b is an integer of 1 to 10, and c is an integer of 1 to 10. has an average value of 0.1 to 1.0, and P
23. A method according to claim 22, characterized in that it is a side group or a terminal group bonded to.