Photosensitive compositions and printing plates containing same

Claim 2

A photosensitive composition, consisting essentially of: (I) a copolymer having a molecular weight of 5,000 to 100,000 and prepared by a process consisting essentially of solution radical copolymerizing (A) 10 to 95 mol % of a conjugated diolefinic hydrocarbon, (B) 5 to 90 mol % of an α,β-ethylenically unsaturated carboxylic acid or anhydride and (C) 0 to 85 mol % of a monoolefinically unsaturated compound and (II) a photosensitizer or a photosensitive crosslinking agent or mixture thereof which is photosensitively effective with said copolymer.

Claim 3

A photosensitive composition, consisting essentially of: (I) a copolymer having a molecular weight of 5,000 to 100,000 and prepared by a process consisting essentially of solution radial copolymerizing (A) 10 to 95 mol % of a conjugated diolefinic hydrocarbon, (B) 5 to 90 mol % of an α,β-ethylenically unsaturated carboxylic acid or anhydride and (C) 0 to 85 mol % of a monoolefinically unsaturated compound; (II) a photosensitizer which is photosensitively effective with said copolymer; and (III) a photo-polymerizable unsaturated monomer.

Claim 4

A photosensitive composition, consisting essentially of: (I) a copolymer having a molecular weight of 5,000 to 100,000 and prepared by a process consisting essentially of solution radial copolymerizing (A) 10 to 95 mol % of a conjugated diolefinic hydrocarbon, (B) 5 to 90 mol % of an α,β-ethylenically unsaturated carboxylic acid or anhydride and (C) 0 to 85 mol % of a monoolefinically unsaturated compound; (II) a photosensitizer which is photosensitively effective with said copolymer; and (III) a photo-polymerizable unsaturated monomer.

Claim 5

The photosenstive composition as claimed in claim 1, wherein at least a part of the carboxyl groups of the α,β-ethylenically unsaturated carboxylic acid or anhydride in the copolymer (I) have been reacted with an inorganic alkali, an alkali salt or an amine compound.

Claim 6

The photosensitive composition as claimed in claim 2, wherein at least a part of the carboxyl groups of the α,β-ethylenically unsaturated carboxylic acid or anhydride in the copolymer (I) have been reacted with an inorganic alkali, an alkali salt or an amine compound.

Claim 7

The photosensitive composition as claimed in claim 1, wherein the copolymer (I) consists of (A) 30 to 70 mol % of a conjugated diolefinic hydrocarbon, (B) 10 to 60 mol % of an α,β-ethylenically unsaturated carboxylic acid or anhydride and (C) 0 to 60 mol % of a monoolefinically unsaturated compound.

Claim 8

The photosensitive composition as claimed in claim 2, wherein the copolymer (I) consists of (A) 30 to 70 mol % of a conjugated diolefinic hydrocarbon, (B) 10 to 60 mol % of an α,β-ethylenically unsaturated carboxylic acid or anhydride and (C) 0 to 60 mol % of a monoolefinically unsaturated compound.

Claim 9

The photosensitive composition as claimed in claim 4, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride in the copolymer (I) has been reacted with an inorganic alkali, an alkali salt or an amine compound in a proportion of 0.05 to 1.0 equivalent per equivalent of the carboxyl group.

Claim 10

The photosensitive composition as claimed in claim 4, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride in the copolymer (I) has been reacted with an inorganic alkali, an alkali salt or an amine compound in a proportion of 0.2 to 1.0 equivalent per equivalent of the carboxyl group.

Claim 11

The photosensitive composition as claimed in claim 4, wherein the inorganic alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammonia, the alkali salt is lithium carbonate, sodium carbonate, potassium carbonate or ammonium carbonate, and the amine compound is a primary amine, a secondary amine, a tertiary amine, an alcohol amine or a cyclic amine.

Claim 12

The photosensitive composition as claimed in claim 9, wherein the amine compound is ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine or morpholine.

Claim 13

The photosensitive composition as claimed in claim 2, wherein the conjugated diolefinic hydrocarbon (A) is a compound represented by the formula, ##STR10## wherein R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, Cl, Br, or I; R 2 is hydrogen, methyl or Cl; and R 3 is hydrogen or methyl.

Claim 14

The photosensitive composition as claimed in one of claims 1 to 10, wherein the conjugated diolefinic hydrocarbon (A) is 1,3-butadiene, isoprene, chloroprene or dimethylbutadiene.

Claim 15

The photosensitive composition as claimed in claim 1, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride (B) is a monocarboxylic acid represented by the formula, ##STR11## wherein R 4 is hydrogen or methyl and R 5 is hydrogen, methyl, ethyl or Cl, a dicarboxylic acid having 4 to 5 carbon atoms, an anhydride thereof or a monoester of a dicarboxylic acid.

Claim 16

The photosensitive composition as claimed in claim 13, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride (B) is selected from the group consisting of acrylic, methacrylic, crotonic, maleic, fumaric, and itaconic acids; maleic and itaconic anhydrides, monomethyl, monoethyl, mono-n-propyl and mono-n-butyl maleates; monomethyl, monoethyl, mono-n-propyl, and mono-n-butyl fumarates, and monomethyl, monoethyl, mono-n-propyl and mono-n-butyl itaconates.

Claim 17

The photosensitive composition as claimed in claim 2, wherein the monoolefinically unsaturated compound (C) is styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, an acrylic or methacrylic ester expressed by the following formula: ##STR12## where R 6 represents hydrogen or a methyl group and R 7 represents an alkyl group with 1 to 18 carbon atoms, a diester of a dicarboxylic acid, an acrylate or methacrylate having a cyclic side chain, an alkoxyalkyl acrylate or methacrylate or alkoxy polyalkyleneglycol acrylate or methacrylate represented by the following formula: ##STR13## where R 8 and R 9 represent hydrogen or a methyl group, R 10 represents an alkyl group with 1 to 12 carbon atoms, and n represents an integer of 1 to 23, or hydroxyalkyl acrylate or methacrylate.

Claim 18

The photosensitive composition as claimed in claim 15, wherein the acrylic or methacrylic ester is methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, tert-butyl acrylate or methacrylate, n-pentyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decyl acrylate or methacrylate, lauryl acrylate or methacrylate, or n-octadecyl acrylate or methacrylate; the diester of a dicarboxylic acid is dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate or dioctyl itaconate; the acrylate or methacrylate having a cyclic side chain is benzyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, tetrahydrofurfuryl acrylate or methacrylate, or glycidyl acrylate or methacrylate; the alkoxyalkyl acrylate or methacrylate or alkoxypolyalkyleneglycol acrylate or methacrylate is methoxyethyl acrylate or methacrylate, ethoxyethyl acrylate or methacrylate, propoxyethyl acrylate or methacrylate, butoxyethyl acrylate or methacrylate, methoxy-i-propyl acrylate or methacrylate, ethoxy-i-propyl acrylate or methacrylate, propoxy-i-propyl acrylate or methacrylate, butoxy-i-propyl acrylate or methacrylate, methoxydiethyleneglycol acrylate or methacrylate, ethoxydiethyleneglycol acrylate or methacrylate, propoxydiethyleneglycol acrylate or methacrylate, butoxydiethyleneglycol acrylate or methacrylate, methoxydipropyleneglycol acrylate or methacrylate, ethoxydipropyleneglycol acrylate or methacrylate, propoxydipropyleneglycol acrylate or methacrylate, butoxydipropyleneglycol acrylate or methacrylate, methoxytetraethyleneglycol acrylate or methacrylate, methoxynonaethyleneglycol acrylate or methacrylate, methoxytetrapropyleneglycol acrylate or methacrylate, or methoxynonapropyleneglycol acrylate or methacrylate; and the hydroxyalkyl acrylate or methacrylate is 2-hydroxyethyl acrylate or methacrylate, or 2-hydroxypropyl acrylate or methacrylate.

Claim 19

The photosensitive composition as claimed in claim 2, wherein the photosensitizer is an α-diketone compound, an acyloin, an acyloin ether, a polynuclear quinone, a peroxide or an azo compound.

Claim 20

The photosensitive composition as claimed in claim 17, wherein the photosensitizer is diacetyl, benzil, benzoin, pivaloin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, anthraquinone, 1,4-napthoquinone, benzoyl peroxide, methyl ethyl ketoneperoxide, or 2,2'-azobisisobutyronitrile.

Claim 21

The photosensitive composition as claimed in claim 1, wherein the photosensitive crosslinking agent is diazidochalcone, 4,4'-diazidostilbene, 4,4'-diazidostilbene-2,2'-disulfonic acid or 2,6-bis-(p-azidobenzal) cyclohexanone.

Claim 22

The photosensitive composition as claimed in claim 2, wherein the amount of the photosensitizer added is 0.1 to 10 weight % based on the weight of the copolymer (I).

Claim 23

The photosensitive composition as claimed in claim 20, wherein the amount of the photosensitizer added is 1 to 5 weight % based on the weight of the copolymer (I).

Claim 24

The photosensitive composition as claimed in claim 1, wherein the amount of the photosensitive crosslinking agent is 0.1 to 10 weight % based on the weight of the copolymer (I).

Claim 25

The photosensitive composition as claimed in claim 1, wherein the amount of the photosensitive crosslinking agent is 1 to 5 weight % based on the weight of the copolymer (I).

Claim 26

The photosensitive composition as claimed in claim 2, wherein the photopolymerizable unsaturated monomer (III) is an unsaturated aromatic compound, an unsaturated nitrile compound, an alkyl acrylate or methacrylate, a hydroxyalkyl acrylate or methacrylate, an acrylate or methacrylate having a cyclic side chain, an α,β-ethylenically unsaturated carboxylic acid, a monoester of an unsaturated polycarboxylic acid, a diester of an unsaturated polycarboxylic acid, acrylamide, methacrylamide, ethyleneglycol diacrylate or dimethacrylate, a polyalkylene glycol diacrylate or dimethacrylate, a diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate or tetramethacrylate of polyhydric alcohol, oligoacrylate or oligomethacrylate represented by the formula, ##STR14## wherein R' is hydrogen or methyl; R" is a C 2-10 glycol residue; R'" is a C 4-8 dicarboxylic acid residue; R"" is a C 3-5 triol residue; and m is an integer of 1 to 10, diallylidenepentaerythritol, 2,2'-bis(4-methacryloxydiethoxyphenyl)propane, 2,2'-bis(4-acryloxydiethoxyphenyl)-propane, or 2,2'-bis(4-acryloxypropyloxyphenyl)propane.

Claim 27

The photosensitive composition as claimed in claim 24, wherein the photopolymerizable unsaturated monomer is styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, diisopropylenylbenzene, divinylbenzene, acrylonitrile, methacrylonitrile, methyl acrylate or methacrylate, ethyl acrylate or methacrylate, propyl acrylate or methacrylate, n-butyl acrylate or methacrylate, isobutyl acrylate or methacrylate, tert-butyl acrylate or methacrylate, n-pentyl acrylate or methacrylate, n-hexyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, n-octyl acrylate or methacrylate, n-decyl acrylate or methacrylate, lauryl acrylate or methacrylate, n-octadecyl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, benzyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, tetrahydrofurfuryl acrylate or methacrylate, maleic acid, fumaric acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, monoethyl maleate, monoethyl fumarate, monoethyl itaconate, dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, dioctyl itaconate, acrylamide, methacrylamide, N,N'-methylenebisacrylamide, N,N'-hexamethylenebisacrylamide, ethyleneglycol diacrylate or dimethacrylate, polyalkyleneglycol diacrylate or dimethacrylate (2 to 23 alkyleneglycol units), diacrylate, triacrylate, tetraacrylate, dimethacrylate, trimethacrylate or tetramethacrylate of glycerin, pentaerythritol, trimethylolalkane or tetramethylolalkane (alkane is methane, ethane or propane), diallylidenepentaerythritol, 2,2'-bis(4-methacryloxydiethoxyphenyl)propane, 2,2'-bis(4-acryloxydiethoxyphenyl)propane, 2,2'-bis(4-acryloxypropyloxyphenyl)propane, monoacryloxyethyl maleate, monomethacryloxyethyl maleate, monoacryloyloxyisopropyl maleate, monomethacryloyloxyisopropyl maleate, monoacryloyloxyethyl succinate, monoacryloyloxyethyl phthalate, monoacryloyloxyethyl tetrahydrophthalate, monoacryloyloxyethyl hexahydrophthalate, monoacrylate or monomethacrylate of polyesterdiol of phthalic acid with ethyleneglycol, monoacrylate or monomethacrylate of polyesterdiol of phthalic acid with propyleneglycol, monoacrylate or monomethacrylate of polyesterdiol of hexahydrophthalic acid with ethyleneglycol, monoacrylate or monomethacrylate of polyesterdiol of hexahydrophthalic acid with propyleneglycol, ester of 2-hydroxyethyl acrylate with phthalic anhydride (2:1 molar ratio), ester of 2-hydroxyethyl methacrylate with phthalic anhydride (2:1 molar ratio), or polyesteracrylate consisting of adipic acid, glycerine and acrylic acid (0.5/1/2 molar ratio).

Claim 28

The photosensitive composition as claimed in claim 2, wherein the photopolymerizable unsaturated monomer is present in an amount of 5 to 200 weight % based on the weight of the copolymer (I).

Claim 29

The photosensitive composition as claimed in claim 26 wherein the photopolymerizable unsaturated monomer is present in an amount of 10 to 100 weight % based on the weight of the copolymer (I).

Claim 30

The photosensitive composition as claimed in claim 2, wherein a part of the photopolymerizable unsaturated monomer component is constituted by an alkoxyalkyl acrylate or methacrylate or alkoxypolyalkyleneglycol acrylate or methacrylate represented by the following formula: ##STR15## where R 11 and R 12 represent hydrogen or a methyl group, R 13 represents an alkyl group with 1 to 12 carbon atoms, and n represents an integer of 1 to 23.

Claim 31

The photosensitive composition as claimed in claim 28, wherein the alkoxyalkyl acrylate or methacrylate, or alkoxypolyalkyleneglycol acrylate or methacrylate is methoxyethyl acrylate or methacrylate, ethoxyethyl acrylate or methacrylate, propoxyethyl acrylate or methacrylate, butoxyethyl acrylate or methacrylate, methoxy-i-propyl acrylate or methacrylate, ethoxy-i-propyl acrylate or methacrylate, propoxy-i-propyl acrylate or methacrylate, butoxy-i-propyl acrylate or methacrylate, methoxydiethyleneglycol acrylate or methacrylate, ethoxydiethyleneglycol acrylate or methacrylate, propoxydiethyleneglycol acrylate or methacrylate, butoxydiethyleneglycol acrylate or methacrylate, methoxydipropyleneglycol acrylate or methacrylate, ethoxydipropyleneglycol acrylate or methacrylate, propoxydipropyleneglycol acrylate or methacrylate, butoxydipropyleneglycol acrylate or methacrylate, methoxytetraethyleneglycol acrylate or methacrylate, methoxynonaethyleneglycol acrylate or methacrylate, methoxytetrapropyleneglycol acrylate or methacrylate, or methoxynonapropyleneglycol acrylate or methacrylate.

Claim 32

The photosensitive composition as claimed in claim 28, wherein the amount of the photopolymerizable unsaturated monomer added is 5 to 200 weight % based on the weight of the copolymer (I) and the amount of alkoxyalkyl acrylate or methacrylate or alkoxypolyalkyleneglycol acrylate or methacrylate is 5 to 95 weight % based on the weight of the photopolymerizable unsaturated monomer.

Claim 33

The photosensitive composition as claimed in claim 30, wherein the amount of the photopolymerizable unsaturated monomer added is 5 to 200 weight % based on the weight of the copolymer (I) and the amount of alkoxyalkyl acrylate or methacrylate or alkoxypolyalkyleneglycol acrylate or methacrylate is 10 to 80 weight % based on the weight of the photopolymerizable unsaturated monomer.

Claim 34

The photosensitive composition as claimed in claim 30, wherein the amount of the photopolymerizable unsaturated monomer is 10 to 100 weight % based on the weight of the copolymer (I).

Claim 35

The photosensitive composition as claimed in claim 2, including a storage stabilizer as an additional component.

Claim 36

The photosensitive composition as claimed in claim 33, wherein the storage stabilizer is nitrosophenylhydroxylamine, a metal salt of dithiocarbamic acid, or thiuram.

Claim 37

The photosensitive composition as claimed in claim 34, wherein the storage stabilizer is aluminum-N-nitrosophenylhydroxylamine, ammonium-N-nitrosophenylhydroxylamine, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc dibutyldithiocarbamate, nickel dibutyldithiocarbamate, tellurium diethyldithiocarbamate, tetramethylthiuram monosulfide, or tetramethylthiuram disulfide.

Claim 38

The photosensitive composition as claimed in claim 33, wherein the amount of the storage stabilizer added is 0.01 to 2 weight % based on the weight of the copolymer (I).

Claim 39

The photosensitive composition as claimed in claim 3, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride in the copolymer (I) has been reacted with an inorganic alkali, an alkali salt or an amine compound in a proportion of 0.05 to 1.0 equivalent per equivalent of the carboxyl group.

Claim 40

The photosensitive composition as claimed in claim 1, wherein the conjugated diolefinic hydrocarbon (A) is a compound represented by the formula, ##STR16## wherein R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, phenyl, Cl, Br, or I; R 2 is hydrogen, methyl or Cl; and R 3 is hydrogen or methyl.

Claim 41

The photosensitive composition as claimed in claim 2, wherein the α,β-ethylenically unsaturated carboxylic acid or anhydride (B) is a monocarboxylic acid represented by the formula, ##STR17## wherein R 4 is hydrogen or methyl and R 5 is hydrogen, methyl, ethyl or Cl; a dicarboxylic acid having 4 to 5 carbon atoms; an anhydride thereof, or a monoester of a dicarboxylic acid.

Claim 42

The photosensitive composition as claimed in claim 1, wherein the monoolefinically unsaturated compound (C) is styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, an acrylic or methacrylic ester expressed by the following formula: ##STR18## wherein R 6 represents hydrogen or methyl and R 7 represents an alkyl group having 1 to 18 carbon atoms, a diester of a dicarboxylic acid, an acrylate or methacrylate having a cyclic side chain, an alkoxyalkyl acrylate or methacrylate or alkoxy polyalkyleneglycol acrylate or methacrylate represented by the following formula: ##STR19## wherein R 8 and R 9 represent hydrogen or methyl, R 10 represents an alkyl group having 1 to 12 carbon atoms, and n represents an integer of 1 to 23, or a hydroxyalkyl acrylate or methacrylate.

Claim 43

The photosensitive composition of claim 1 or 2 wherein said copolymer (I) further comprises from 14 to 85 mol % of said monoolefinically unsaturated compound (C).

Claim 44

A photosensitive resin plate, comprising the photosensitive composition of claim 1 on a support.

Claim 45

A photosensitive resin plate useful in the production of a flexographic printing plate, comprising: the photosensitive resin composition of claim 2 on a support.

Claim 46

The photosensitive resin plate of claim 43, wherein said support is manufactured from a flexible material.