JPH03100552A - Photosensitive resin composition for printing plate - Google Patents

Abstract

PURPOSE:To obtain a flexographic printing plate superior in developability and good in image reproducibility by incorporating a polyamide specified in molecular weight and a salt of a tertiary amine compd. and an organic acid as a part of an ethylenically unsaturated compound and/or a plasticizer component each specified in the content. CONSTITUTION:The photosensitive resin composition is composed essentially of the ethylenically unsaturated compound, the plasticizer component, a photopolymerization initiator, and the polyamide soluble in these mixture and having a number average molecular weight of 5X10<3> - 1X10<5> and a content of 5 - 30wt.% of the total photosensitive resin composition. The salt of the tertiary amine and the organic acid is used as at least one part of the ethylenic compound and/or the plasticizer component, and contained in an amount of 5 - 70wt.% of the total photosensitive resin component, and it functions as a strong solvent of the polyamide, thus permitting the obtained photosensitive resin composition to provide the flexographic printing plate developable with water and more improved in image reproducibility.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive resin composition for printing plates, and in particular, as a flexible printing plate or flexo printing plate, it has good flexibility, ink resistance, developability, etc. The present invention relates to a photosensitive resin composition that provides an improved solid printing plate material with improved moldability.

[Prior art] Chlorinated rubber, styrene-butadiene block copolymer,
Using an elastomer such as polyurethane as a carrier resin component,
A photosensitive resin composition containing an ethylenically unsaturated compound and a photopolymerization initiator is useful as a flexographic printing plate material by taking advantage of the characteristics of an elastomer.
No. 48611, Specification No. 3024180, Special Publication No. 1973-
Many proposals have been made, such as in Publication No. 43374.

However, since such photosensitive resin solid plate materials require halogenated hydrocarbon development, they have problems such as health problems and environmental pollution.

On the other hand, water- or alcohol-developable photosensitive resin solid printing plate materials are known, for example, Japanese Patent Publication No. 46-26125,
As shown in Japanese Patent Publication No. 50-32645, Japanese Patent Publication No. 57-28485, etc., printing plate materials whose photosensitive layer is a photosensitive resin composition containing a polyamide soluble in water or alcohol as a carrier resin component are widely known. However, although printing plates obtained from such water- or alcohol-developable solid printing plate materials are resistant to oil-based inks, they are resistant to inks containing polar solvents such as aqueous or alcohol-based, especially Not resistant to flexo printing inks.

In order to solve the above-mentioned problems, the present inventors have developed a photosensitive resin composition for a water- or alcohol-developable solid printing plate material that can be used in flexographic printing, including a small amount of alcohol-soluble polyamide and, if necessary, It was discovered and proposed that a photosensitive resin composition in which a large amount of ethylenically unsaturated compound containing a photopolymerization initiator is solidified using an organic solvent gelling agent as a gelling agent component is useful (Japanese Patent Application Laid-Open No. 1983-1982). 27
Publication No. 8053).

The flexographic printing plate material obtained from the photosensitive resin composition shown in this proposal provided a practical level flexographic printing plate, but the developability, image reproducibility,
Further improvements in properties such as printing durability have been desired, and improvements in processability during the production of printing plate materials have also been desired.

``Problems to be Solved by the Invention'' The object of the present invention is to provide a photosensitive resin that can be developed with water or alcohol, particularly water developability, and which provides a flexographic printing plate with further improved characteristics such as image reproducibility and printing durability. Another object of the present invention is to provide a photosensitive resin composition that has improved processability during the production of printing plate materials.

[Means for Solving the Problems] The object of the present invention is to provide a polyamide with a number average molecular weight of 5.000 to 1oo, ooo, which is soluble in an ethylenically unsaturated compound, a plasticizer component, a photopolymerization initiator, and a mixture thereof. In a photosensitive resin composition mainly consisting of
and as at least a part of the ethylenically unsaturated compound and/or plasticizer component, a salt formed from a tertiary amine compound and an organic acid is added in an amount of 5 to 70% by weight based on the total photosensitive resin composition. This is achieved by a photosensitive resin composition for printing plates characterized by containing %. The present inventors used a small amount of polyamide to function as a gelling agent for a large amount of liquid or brittle photosensitive resin composition even in solid form as shown in JP-A No. 63-278053. In the method of making a solid or tougher photosensitive resin printing plate material, the photosensitive resin composition to be solidified or toughened contains a salt formed from a tertiary amine compound and an organic acid. , and a number average molecular weight of 5,000 to 100 as a polyamide that functions as a gel agent.
．． The present invention was achieved by discovering that by selecting polyamide No. 000, a photosensitive resin composition that meets the purpose of the present invention can be obtained.

In other words, the salt formed from the above-mentioned tertiary amine compound and organic acid functions as a strong solubilizing agent for polyamide, so it has a useful property that was previously impossible to use due to solubility or processability during manufacturing. In addition to making it possible to use polyamides such as
The present invention was also achieved based on the discovery that by selecting the composition components, a printing plate material having good polar solvent resistance, that is, flexographic ink solvent resistance, can be obtained.

Here, it is preferable that at least a part of the tertiary amine compound or the organic acid have a photoreactive ethylene double bond, as this results in an increase in the photocurable component in the photosensitive resin composition. Considering the function, it is not necessarily essential to have a photoreactive group, but it should be selected depending on the required characteristics of the intended printing plate material.

The tertiary amine compound used in the present invention is not particularly limited, and is selected depending on the combination with the organic acid and the required characteristics of the intended printing plate material. Alternatively, aromatic tertiary amines and aliphatic or aromatic group-substituted products thereof can be widely used, but in accordance with the purpose of the present invention,
A tertiary amine compound having one or more hydroxyl groups in the molecule and having a molecular weight of 300 or more, preferably 500 or more, more preferably 700 or more is used.

When the molecular weight is less than 300, the intended printing plate tends to have insufficient ink resistance.

A tertiary amine compound having one or more hydroxyl groups in the molecule and having a molecular weight of 300 or more has one or more hydroxyl groups and a tertiary amino group or tertiary amine bond in the molecule and has a molecular weight of 300 or more. All compounds can be used, and are not particularly limited, but preferably the first
Addition reaction between a compound having a primary or secondary amino group and a compound having an α, β unsaturated carbonyl group, a compound having a hydroxyl group, a compound having a primary or secondary amino group, and an epoxy compound body etc. are used. The first of the specific raw material components forming the tertiary amine compound
Examples of class amines include alkylamines having 2 to 18 carbon atoms, cyclohexylamines, monoalkanolamines, alkylene diamines, polyalkylene polyamines, 1.3
-diaminocyclohexane, metaxylylenediamine,
Isophorone diamine, 1,4-bis(3-aminopropyl)piperazine, 2.4.8.10-tetraoxaspiro[5,5]undecane, polyamide polyamine, etc. are used.

Examples of secondary amines include dialkyl or dialkenylamines having an alkyl or alkenyl group having 1 to 38 carbon atoms, dialkanolamines, and N-alkyl of the above-mentioned primary amines; N
Reaction of secondary amines or primary amines with alkenyl or N-alkanol substitution with alkyl glycidyl ethers having 1 to 20 carbon atoms or glycidyl methacrylate, 3.4 epoxycyclohexylmethyl methacrylate, and various acrylates. The raw material component primary amines include alkylamines having 2 to 18 carbon atoms, cyclohexylamine, monoalkanolamines, alkylene diamines, polyalkylene polyamines, and 1,3-diaminocyclohexane. , metaxylylene diamine, isophorone diamine, 1,4-bis(3-aminopropyl)piperazine, 2.4.8.10-tetraoxaspiro[5
, 5] Undecane, polyamide polyamine, etc. are used.

As the compound having an α,β unsaturated carbonyl group, a compound having an acryloyl group is mainly used, and monoacrylates and polyacrylates are preferably used, but there are no particular limitations, and known compounds may be used. All can be used. For example, in addition to various alkyl monoacrylates, mono- or polyacrylates synthesized by reaction products of alkylene glycol and acrylic acid, unsaturated epoxy compounds and carboxylic acids, unsaturated carboxylic acids, and amines, Furthermore, mono- or polyvalent acrylamide or mono- or polyvalent urethane acrylate is used, but particularly preferably used compounds have one or more hydroxyl groups in the molecule and have a hydroxyl equivalent of 50 to 500. Examples of such compounds include epichlorohydrin-modified bisphenol A diacrylate, epichlorohydrin-modified butyl acrylate,
Ethylene oxide modified phthalic acid acrylate such as epichlorohydrin modified diethylene glycol diacrylate, epichlorohydrin modified phenyl acrylate, β-hydroxyethyl β-acryloyloxyethyl phthalate, caprolactone or polycaprolactone modified acrylate, polyethylene oxide modified phthalate ethyl acrylate, polypropylene oxide modified phthalate Examples include acid ethyl acrylate, polypropylene glycol acrylate, polyethylene glycol acrylate, etc. In addition, compounds having one acrylic group and one or more methacrylic groups can also be preferably used.

The epoxy compound has 1 to 2 carbon atoms as described above.
0 alkyl glycidyl ether or glycidyl methacrylate, 3.4 epoxycyclohexylmethyl methacrylate-1, etc. are used.

Among the above addition reactants, tertiary amine compounds having a molecular Ji of 300 or more and having one or more hydroxyl groups in the molecule are preferably used, and among these compounds, tertiary amine compounds are more preferably used.
A photopolymerizable unsaturated compound having a class amine bond and a hydroxyl group is selectively used.
No. 079, Special Publication No. 51-2113, Special Publication No. 51-41
Compounds described in No. 612, JP-A No. 63-162660, etc. and having a molecular weight of 300 or more can be preferably used.

The organic acids used in the present invention include mono- or polyvalent aliphatic or aromatic carboxylic acids, or carboxylic acids as aliphatic or aromatic substitutes thereof;
Similarly, many organic acids may be used, including, but not limited to, aliphatic or aromatic sulfonic acids, aliphatic or aromatic phosphoric acids, or monoesters of aliphatic or aromatic phosphoric acids. Organic acids that are preferably used in accordance with the purpose include organic acids having ethylenically unsaturated groups, and examples of such compounds include compounds represented by the following general formula (1).

CTl 2 = C-C-0-X -Y1 (wherein, R is 11 or Cl-13, X has 1 carbon atom
~24 divalent hydrocarbon groups or 10--CO in the molecule
A divalent hydrocarbon group having 1 to 24 carbon atoms having O-1-NHCO-, Y is -COOH.

SO, T-1, OI (OH -P-OII, -P-OR', R+ represents 100 alkyl group or phenyl group having 1 to 10 carbon atoms) represented by this general formula Specific examples of the compound include, for example, the compounds described on the following pages. Here, R in the formula is -■ (or -CFI3). These compounds can be used alone or in combination of two or more.

○ O Q=OU=OQ=OQ=O ni 10 wards-〇 Nee〇 Nee〇II
II II
II1 11 1 1 111 = S= 工の工, U==O1, l u=.

Engineering 1 Engineering 0-QQ-t) 111 = Engineering OQ Organic acids preferably used as compounds having an ethylene double bond include those having a number average molecular weight of 500 or more and having one or more ethylene double bonds in the molecule; Examples of such compounds include oligomers and polymer acids having a number average molecular weight of preferably 1.000 or more, more preferably 2.000 or more and 30°000 or less. Examples include isoprene and acrylic acid or methacrylic acid copolymers. Various oligomers modified with maleic acid that utilize the reactivity of maleic acid double bonds can also be used.

In the photosensitive resin composition of the present invention, the salt formed from the above-mentioned tertiary amine compound and organic acid functions as an ethylene compound or at least a part of the plasticizer component, and provides a photosensitive function that meets the purpose of the present invention. The amount used is 5 to 70% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total photosensitive resin composition. If it is less than 5% by weight, the effect of salt inclusion cannot be expected;
If it is more than 0% by weight, the green plate material absorbs more moisture, resulting in poor stability over time, which is not preferable.

The polyamide used in the present invention includes a mixture of an ethylenically unsaturated compound, a plasticizer component, and a photopolymerization initiator used as components of the photosensitive resin composition.
All polyamides which are soluble at a temperature of 0°C can be used. The polyamide used in the present invention is
As shown in Publication No. 3-278053, it functions as a polymer gelling agent, and as a solidifying or toughening agent for a mixture consisting of an ethylenically unsaturated compound, a plasticizer component, and a photopolymerization initiator. From the viewpoint of a gelling agent, the number average molecular weight of the resin composition is 5.0.
00 to 100,000, and the amount thereof used is preferably 5 to 30% by weight in the total photosensitive resin composition. That is, if the number average molecular weight is less than 5,000, or if the amount used is less than 5% by weight, the practical strength as a solid printing plate material will be insufficient, and if the number average molecular weight is less than 1.
If it is larger than 00.000, or if the amount used is larger than 30% by weight, problems will arise in the manufacturing processability of the solid printing plate material, which is not preferable.

In the present invention, a wide variety of polyamides that meet the above conditions can be used, and there are no particular limitations. , polyesteramide copolymerized with dicarboxylic acid is widely used, but at least a part of the polyamide component is a polyalkyleneoxy segment having an alkylene bond having 3 or more carbon atoms in the polyamide, or a polyesteramide having 10 carbon atoms.
Polyetheramides or polyetheresteramides having the above alkylene bonds are preferably used to obtain a photosensitive resin composition that provides a water-developable flexographic printing plate material, which is the main objective of the present invention. Printing plates obtained from photosensitive resin compositions containing such polyamides are useful as flexographic printing plates, but they have not been generally used in the past due to manufacturing processability or water developability. However, in the present invention, these problems have been solved.

Such polyamides are produced by polycondensation using α·ω-diaminopropyl polyoxyalkylenes such as α·ω-diaminopropylpolyoxybutylene and α·ω-diaminopropylpolyoxypropylene and salts of dicarboxylic acids as raw materials. or a polyamide obtained by copolycondensation, and examples of dicarboxylic acids include succinic acid, adipic acid, dodecanedicarboxylic acid, 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, terephthalic acid, Isophthalic acid, phthalic acid, diphenic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, etc., and as a copolymerization component, a lactam having 5 to 13 ring atoms, and/or these salts of the aminocarboxylic acid and/or diamine/dicarboxylic acid type that constitute the lactam, where the dicarboxylic acid can be the same as above;
Examples of diamines include pentamethylene diamine, hexamethylene diamine, pentamethylene diamine,
Octamethylene diamine, or these C- and N
-substituted derivatives such as N-methylhexamethylenediamine, N-ethylhexamethylenediamine, 1,6-cyamitsu-3methylhexane, and also alicyclic diamines such as 1,4-diaminocyclohexane, p-p -bis(4aminocyclohexyl)methane, aromatic diamine,
Examples include 4,4-diaminodiphenylmethane, m-xylylenediamine, m-phenylenediamine, and other bis(aminopropyl)piperidines, and examples of lactams include caprolactam, enantholactam, capryllactam, and laurilolactam. It will be done.

The polyether ester amide is a polyether ester amide obtained by polycondensing a polyalkylene glycol/dicarboxylic acid and a lactam or a ring-opened product of these lactams, and/or a salt of a diamine/dicarboxylic acid, or a copolymer thereof. Here, the polyalkylene glycols include, for example, polybutylene glycol, poly(1,2 and 1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol,
Block or random copolymers of ethylene oxide and propylene oxide are used.

As the lactam or ring-opened product of these lactams and/or diamine/dicarboxylic acid, compounds similar to those of polyetheramide can be used.

As these polyetheramides and polyetheresteramides, polycondensates having a number average molecular weight of ff11O,000 or more are particularly preferably used, and these polycondensates can be produced by known melt polymerization methods.

A salt formed from a tertiary amine compound and an organic acid is used as at least a part of the ethylenically unsaturated compound and/or plasticizer component used in the present invention. It may be present, and known ethylenically unsaturated compounds or plasticizer components may be used in combination. The ethylenically unsaturated compound component is a photopolymerizable compound having at least one ethylenic double bond in the molecule and a boiling point of 100°C or higher, and all known compounds meeting this condition are used. Possible, for example, various alkyl monoacrylates and alkyl monomethacrylates, reaction products of alkylene glycol and acrylic acid, methacrylic acid, etc., unsaturated epoxy compounds and carboxylic acids, unsaturated carboxylic acids, and amines. Mono- or poly-acrylates, mono- or poly-methacrylates, mono- or poly-valent acrylamides or methacrylamides, mono- or polyvalent urethane acrylates or methacrylates, and liquid polybutadiene synthesized by reactions such as Polyene oligomers such as polyester are used, but are not limited to these, and can be used as appropriate depending on the required characteristics of the desired molded product or in combination with polyamide that functions as a polymer gelling agent. It is selected.

Ethylenically unsaturated compounds preferably used to obtain a water-developable printing plate material, which is the main objective of the present invention, have one or more hydroxyl groups in the molecule and have a hydroxyl equivalent of 50 to 50. ethylenically unsaturated compounds in the range of 500, such as epichlorohydrin-modified bisphenol A diacrylate,
or epichlorohydrin-modified bisphenol A di(meth)acrylate (hereinafter, both are collectively abbreviated as epichlorohydrin-modified bisphenol A di(meth)acrylate. In addition, in the following explanation, all descriptions of (meth)acrylate are abbreviated to both acrylate and methacrylate. ), caprolactone-modified 2-hydroxyethyl (meth)acrylate, epichlorohydrin-modified propylene glycol di(meth)acrylate-1-,
Ethylene such as propylene oxide-epichlorohydrin-modified (meth)acrylate, epichlorohydrin-modified butyl (meth)acrylate, epichlorohydrin-modified diethylene glycol di(meth)acrylate, epichlorohydrin-modified phenyl (meth)acrylate, β-hydroxyethyl β′-acryloyloxyethyl phthalate. Oxide-modified phthalic acid (meth)acrylate, polycaprolactone-modified 2-hydroxyethyl (
Examples include, but are not limited to, meth)acrylate, polyethylene oxide-modified ethyl phthalate (meth)acrylate, polypropylene oxide-modified ethyl phthalate (meth)acrylate, polypropylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, etc. Other ethylenically unsaturated compounds with hydroxyl equivalents in the range of 50 to 500 can be widely used, and it is also possible to use two or more types together, and it is also possible to use them in combination with other ethylenically unsaturated compounds. It is.

Furthermore, in order to obtain a flexographic printing plate material, which is the object of the present invention, a compound preferably used as a part of the ethylenically unsaturated compound component has a number average molecular weight of 300 to 20.
,000 polyenes or modified products thereof, specifically, liquid polyisoprene, polybutadiene, etc., or modified products utilizing the reactivity of the main chain, side chain, and terminal group of these polyenes.

As the plasticizer component, compounds known as plasticizer components for polyamide photosensitive resin compositions such as alkylbenzenesulfonamides, polyalkylene glycols, and lactams can be widely used.

As the photopolymerization initiator for rapidly photopolymerizing the composition of the present invention, all conventionally known compounds can be used. Examples include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls. These photopolymerization initiators can be used in an amount of 0.01 to 10% by weight based on the ethylenically unsaturated compound in the entire composition.

Further, in order to increase the thermal stability of the photosensitive resin composition of the present invention, conventionally known polymerization inhibitors can be used. Preferred polymerization inhibitors include phenols, hydroquinones, catechols, and phenothiazine. These heat stabilizers are 0.00% of the total composition.
It can be used in a range of 1 to 5% by weight. Other additives that can be added include dyes, pigments, surfactants, antifoaming agents, ultraviolet absorbers, fragrances, and plasticizers.

Since the photosensitive resin composition of the present invention uses a small amount of polyamide, which is a resin component that functions as a polymer gelling agent,
Although it is characterized by a wide range of composition selection from the viewpoint of compatibility, in order to further improve the compatibility, shape retention, etc. of the printing plate material obtained from the photosensitive resin composition of the present invention,
The present composition includes N-acylamino acid derivatives, i.e., N-acylamino acid amine salts, N-acylamino acid amides, N-acylamino acid derivatives,
At least one of acyl amino acid esters, carboxylated polyoxyethylene alkyl ethers or salts thereof, 12-hydroxystearic acid or salts thereof, metal soaps, alkylidene sorbitols, condensates of benzaldehyde and polyhydric alcohols, and polysaccharide acylated products. It is preferable to add seeds, and these compounds are preferably used in an amount of 0.1 to 10 parts by weight based on the total amount of the composition.

As a method for producing the photosensitive resin composition of the present invention, first, a resin component such as polyamide is added to a heat stabilizer, an ethylenically unsaturated compound, and if necessary a plasticizer component, and the mixture is heated to a temperature of 70 to 200% while stirring. C., preferably 100 to 180.degree. C. to dissolve the resin component, and then mix and dissolve the photopolymerization initiator and other additive components to produce a substantially solvent-free solution. Here, the salt consisting of the tertiary amine compound and the organic acid component is used as at least a part of the ethylenically unsaturated compound and/or the plasticizer component, but the tertiary amine compound and the organic acid are usually added sequentially to form a composition. Salts are formed during the preparation process. The order of addition is not particularly limited; for example, a tertiary amine compound may be added at the time of dissolving the resin component, or a primary amine,
A method of adding a secondary amine to form a tertiary amine in the stock solution preparation step can also be effectively employed.

This solution can be cast or cast and cooled to directly obtain a molded product.

The photosensitive resin composition of the present invention is characterized by being substantially a thermoreversible gel, and is a solid with practical strength at room temperature, but becomes a relatively low viscosity liquid when heated. Therefore, an easy molding method that takes advantage of this property can be applied.

The photosensitive resin composition of the present invention can be designed to be a liquid having a poise of 1°000 or less at 150°C, and further, a liquid having a poise of 1°000 or less at 100°C.

In order to form a printing plate material using the photosensitive resin composition of the present invention, for example, a solution of the present composition can be directly cast onto a support and molded.

If necessary, dry film forming may be performed if a solvent is used, but since molding is usually done without a solvent, photosensitive resin sheets can be produced by cooling only, and thick films can be formed. It is also easy to mold.

As a support, a metal plate made of steel, stainless steel, aluminum, copper, etc., which has an adhesive layer if necessary, a plastic sheet such as a polyester film, a synthetic rubber sheet, etc. is used, and the photosensitive layer is usually 0.1 to 10 mm thick.
formed to a thickness of

In order to form a relief image for printing using the photosensitive resin composition of the present invention, a negative or positive original film is closely adhered to the photosensitive layer prepared as described above, and a wavelength of 300 to 450 mμ is usually centered on the photosensitive layer. UV light from a high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, xenon lamp, chemical lamp, carbonark lamp, etc. is irradiated to cause curing through a photoreaction. A relief is then formed on the support by dissolving or dispersing the uncured portion in a solvent using a spray-type developing device or a brush-type developing device.

The photosensitive resin composition of the present invention has the characteristic of solidifying a conventional liquid or near-liquid composition at room temperature, and therefore is useful as a solid printing plate material for flexible printing plates, flexographic printing plates, etc. It is most effective when used as a letterpress printing plate material, but it is especially the best water-developable flexo printing plate material, and has unprecedented water-developability and flexographic ink solvent resistance. It becomes the plate material.

Hereinafter, the present invention will be explained in detail with reference to Examples. The number average molecular weight used in the present invention is based on the number average molecular weight in terms of nylon 6.6 and terminal group determination by GPC (gel permeation chromatography), and is described in each case.

Further, the quantitative determination of the salt formed from the tertiary amine and the organic acid was determined based on the measurement results of the tertiary amino group concentration and carboxyl group concentration by separation and quantitative analysis of the prepared stock solution.

Note that the numbers used in the following examples are parts by weight.

Synthesis Example 1 A copolyamide consisting of the following components was synthesized based on a known recipe (for example, the one described in JP-A-55-79437).

ε-caprolactam / Equimolar salt of hexamethylene diamine and adipic acid / Equimolar salt of α, ω-diaminopropyl polyoxyethylene (number average molecular weight 1,000) and adipic acid = 20/20/60 Number based on terminal group determination method The average molecular weight was approximately 33°000.

Synthesis Example 2 Known formulation (e.g. JP-A-58-117537)
Based on this, a polyether ester amide consisting of the following components was synthesized.

ε caprolactam/number average molecule ff1l, 000 polyethylene glycol and equimolar terephthalic acid mixture=
40/70 The polyether nisulamide obtained here had a GPC number average molecular weight of 8,000.

Synthesis Example 3 A polyether ester amide consisting of the following components was similarly synthesized.

Laurolactam/number average molecular weight ff1,000 polytetramethylene glycol and equimolar terephthalic acid mixture = 60/40 The GPC method number average molecular weight of the polyether ester amide obtained here was 25,000.

Synthesis Example 4 1 mol of metaxylylenediamine and 2-
2 molar adduct of ethylhexyl acrylate (60°C, 3
After synthesizing (time reaction), 2 mol of 2-ethylhexyl glycidyl ether was further added (reaction at 70°C for 2 hours)
The resulting compound was synthesized.

Synthesis Example 5 An adduct of 1 mol of isophorone diamine and 1 mol of 2-ethylhexyl glycidyl ether (70°C
, 3 hour reaction) was synthesized.

Example 1 5 parts of the polyetheramide obtained in Synthesis Example 1 and 15 parts of the polyetheresteramide obtained in Synthesis Example 3,
Heat stabilizer hydroquinone 0.05 parts, caprolactone modified 2-hydroxyethyl methacrylate 15 parts, β-
25 parts of hydroxyethyl β-acryloyloxyethyl phthalate, 10 parts of 2-acryloyloxyethyl hexahydrophthalic acid, and 20 parts of maleic anhydride-modified polybutadiene "M2O0O-20" (manufactured by Nippon Petrochemical Co., Ltd.) were mixed and heated. After raising the temperature and stirring at 105°C for 1 hour to open the ring of "M2O0O-20", 10 parts of the additive shown in Synthesis Example 5 was added, and the mixture was stirred at 140°C for 1 hour to form a tertiary amine. After 30 minutes, 1.5 parts of benzyl dimethyl ketal was added as a photopolymerization initiator, 3 parts of carboxylated penta(oxyethylene) lauryl ether, 3 parts of dibenzylidene sorbitol, and N-lauroyl were added as other additive components. -Shi-Glutamic acid-α・γ
-2 parts of di-n-butylamide were added and dissolved. The solution obtained in this way was cast and coated on a 100μ thick polyester substrate on which a polyester adhesive had been applied and cured in advance so that the photosensitive layer would have a thickness of 1,500μ, and then coated at room temperature. A solid photosensitive resin printing plate material was obtained by standing. The concentration of tertiary amine salt in the photosensitive layer of the woodblock material was approximately 55% by weight.

On the photosensitive layer of this printing plate material, a gray scale negative film for sensitivity measurement (manufactured by Stouffer, 21 Steps) was applied.
5sensitivity Guide) and negative film for image reproducibility evaluation (150 line 3%, 5%, 1
0% halftone dot, diameter 200μ, and 300μ independent dot, width 5
0μ and 70μ thin wires) are vacuum-adhered and 2KW
Exposure was performed for 3 minutes from a distance of 1 m using an ultra-high pressure mercury lamp.

After exposure, development was carried out using a brush type washing machine (liquid temperature: 25°C) containing neutral water. Depth 1.0 in 5 minutes development time
A relief image of 00μ was formed.

As a result of evaluating this relief image, the gray scale part was 1
Up to 4 steps remain, and the print area is 5% halftone dot, 300
It was found that μ independent points, 50μ thin lines, etc. were almost completely reproduced. The hardness of the printing plate is Shore A after post-exposure.
The hardness was 55. This printing plate uses water-based ink,
A flexographic printing test was conducted on 50,000 sheets each using alcohol-based ink, and good printed matter was obtained.

Comparative Example 1 In Example 1, 10 parts of 2-acryloyloxyethyl hexahydrophthalic acid, 20 parts of maleic anhydride-modified polybutadiene, and 3 parts of carboxylated pentaoxyethylene lauryl ether were not used, and β-hydroxyethyl β' - A photosensitive resin printing plate material was similarly obtained using 55 parts of acryloyloxyethyl phthalate, but this printing plate material had almost no water developability, and the development depth in 5 minutes was was 10μ.

Comparative Example 2 A photosensitive resin printing plate material was obtained in the same manner as in Example 1 except that the amount of β-hydroxyethyl β'-acryloyloxyethyl phthalate used was 35 parts, and in the system shown in Synthesis Example 5 without using the additive. However, this printing plate material had almost no water developability, and the development depth in 5 minutes was 15μ.

Comparative Example 3 A photosensitive resin printing plate was prepared in the same manner as in Example 1 except that 10 parts of 2-acryloyloxyethylhexahydrophthalic acid was not used and the amount of β-hydroxyethyl β'-acryloyloxyethyl phthalate was changed to 35 parts. However, compared to the printing plate material obtained in Example 1, the water development rate of this printing plate material was reduced to about 115.

Comparative Example 4 A photosensitive resin printing plate material was obtained in the same manner as in Example 1 except that 20 parts of maleic anhydride-modified polybutadiene was not used and the amount of β-hydroxyethyl β'-acryloyloxyethyl phthalate was 55 parts. However, compared to the printing plate material obtained in Example 1, the water development rate of this printing plate material was 30% lower.

Comparative Example 5 A photosensitive resin printing plate material was obtained in the same manner as in Example 1 without using carboxylated pentaoxyethylene lauryl ether, but this printing plate material was compared with the printing plate material obtained in Example 1. Therefore, the water development speed is about 1. , /2.

Example 2 21 parts of the polyether ester amide obtained in Synthesis Example 2 was mixed with 55 parts of β-hydroxyethyl β'-acryloyloxyethyl phthalate and liquid rubber "Nisseki Polybutadiene" B2000-20 (manufactured by Nippon Petrochemical Co., Ltd., liquid The mixture was added to a mixture of 10 parts of polybutadiene), 14 parts of 2-acryloyloxyethyl phthalic acid, 0.005 parts of hydroquinone, and 8.5 parts of the additive obtained in Synthesis Example 5, heated with stirring, and heated to 150°C. The additive component obtained in Synthesis Example 5 was reacted with the acrylate component by stirring for 1 hour, and 3
After forming the grade amine, 1.5 parts of benzyl dimethyl ketal as a photopolymerization initiator, 2 parts of N-lauroyl-glutamic acid-α number γ-n-butylamide and 3 parts of dibenzylidene sorbitol were added as additives. Dissolved. The solution obtained in this manner was cast and coated on a 100 μm thick polyester substrate, which had been coated with a polyester adhesive and cured in advance, so that the photosensitive layer had a thickness of 1,500 μm, and was coated at room temperature. A solid photosensitive resin printing plate material was obtained by standing. The concentration of tertiary amine salt in the photosensitive layer of the woodblock material was about 50% by weight. Example 1 from this printing plate material
A printing plate was obtained using the same method.

The Shore A hardness of this printing plate is 61, and water-based ink,
This resulted in an excellent flexographic printing plate that is suitable for alcohol-based inks.

Example 3 In Example 1, the polyether ester amide obtained in Synthesis Example 2 was used instead of polyether amide,
A printing plate material was similarly obtained by using the amine component obtained in Synthesis Example 4 instead of the amine component in Synthesis Example 5 and setting the preparation temperature to 150°C. The tertiary amine salt concentration in the photosensitive layer of this plate material was approximately 35% by weight.

A printing plate was produced from this printing plate material in the same manner as in Example 1.

This printing plate was even more suitable for printing using flexo ink than the printing plate obtained in Example 1, and gave good prints in 1oo and oooo printing tests using water-based ink. .

Example 4 In Example 1, 2-acryloyloxyethyl acid phosphate was used in place of 2-acryloyloxyethyltetrahydrophthalic acid, and similar results were obtained.

Example 5 In Example 1, 2-methacryloyloxyethyl phthalic acid was used in place of 2-acryloyloxyethyltetrahydrophthalic acid, and results similar to those obtained were obtained.

[Effects of the Invention] Since the present invention is constructed as described above, it is possible to provide a photosensitive resin composition that provides a flexographic printing plate that is excellent in moldability and developability, and has good image reproducibility and ink resistance. be.

Claims (1)

[Claims] 1. A number average molecular weight 5 that is soluble in ethylenically unsaturated compounds, plasticizer components, photopolymerization initiators, and mixtures thereof.
,000 to 100,000, the polyamide is in the range of 5 to 30% by weight based on the total photosensitive resin composition, and the ethylenically unsaturated compound and/or As at least a part of the plasticizer component, a salt formed from a tertiary amine compound and an organic acid is added in an amount of 5 to 70% based on the total photosensitive resin composition.
A photosensitive resin composition for printing plates, characterized in that it contains % by weight. 2. The photosensitive resin composition for printing plates according to claim 1, wherein the tertiary amine compound is a compound having a molecular weight of 300 or more and having one or more hydroxyl groups in the molecule. 3. The photosensitive resin composition for printing plates according to claim 1, wherein the organic acid is a compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is H or CH_3, X is the number of carbon atoms 1 to 2
-O-, -COO in the divalent hydrocarbon group or molecule of 4
-, -NHCO-, a divalent hydrocarbon group having 1 to 24 carbon atoms, Y is -COOH, -SO_3H) ▲Mathematical formulas, chemical formulas, tables, etc.
There are tables, etc. ▼ indicates, and R^1 indicates an alkyl group having 1 to 10 carbon atoms or a phenyl group. ) 4. The photosensitive resin composition for printing plates according to claim 1, wherein the organic acid is an oligomer or polymeric acid having one or more ethylene double bonds in the molecule and having a number average molecular weight of 500 or more. 5. The printing according to claim 1, wherein at least a part of the polyamide component is a polyalkyleneoxy segment having an alkylene bond having 3 or more carbon atoms or a polyamide or polyester amide having an alkylene bond having 10 or more carbon atoms in the polyamide. Photosensitive resin composition for plates.