JP2842035B2 - Photosensitive resin composition, production method thereof and flexographic printing plate precursor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-developable photocurable resin composition, and more particularly, to a rubber composition having rubber elasticity,
The present invention also relates to a photosensitive resin composition containing a photosensitive microgel having a carbon-carbon double bond on the surface of gel particles, and a flexographic printing plate precursor obtained using the same.

[0002]

2. Description of the Related Art In recent years, flexographic printing has come into the spotlight with the modernization of packaging. However, in the conventional method of manufacturing a flexographic plate, (a) production of a metal plate,
(B) Molding, (c) Vulcanization of raw rubber requires at least three steps, and requires a skilled technique and a long time, so that the cost cannot be avoided. For this reason, a solvent development type photosensitive resin plate has appeared, and a flexographic plate can be easily made. However, since these plates are based on a diene rubber such as polybutadiene, a halogen-based solvent such as trichlene or perchrene must be used as a developing solution during development. However, recently, halogen solvents have been regulated due to environmental problems and toxicity of the halogen solvents to the human body.

[0003] Then, it can be developed with non-toxic water to the human body,
There has been a long-awaited need for a flexographic printing plate having resistance to water-based inks used for flexographic printing. However, it has been difficult for the prior art to satisfy the conflicting requirements of water developability, water resistance and alcohol resistance. The inventor of the present invention has invented a novel method for synthesizing a reactive microgel (Japanese Patent Application Laid-Open No. 02-263805), and has been studying the application to a flexographic plate. However, a satisfactory one can be obtained in terms of rubber elasticity. It was difficult.

Further, the present inventors have proposed a method of (a) repeating cast → dry → cast using an aqueous dispersion of a photosensitive microgel, and (a) gradually drying a thick film at about room temperature. Have produced thick resin plates for flexographic printing plates, but all of the methods have problems that not only takes much time and labor, but also that other components and initiators used are limited to aqueous ones.

[0005]

The inventors of the present invention have conducted intensive studies to develop a photosensitive resin composition which is water-developable and has the characteristics required for a flexographic printing plate. When a compound having at least one carbon-carbon double bond per molecule is added as a second component to the photosensitive microgel having Urethane compounds having one carbon-carbon double bond and / or polydienes having a carbon-carbon double bond at the terminal or in the side chain (hereinafter abbreviated as polydienes having a carbon-carbon double bond); Urethanation using a mixture with another compound having a heavy bond and further having at least one carbon-carbon double bond in one molecule as a second component When added goods and polydienes, it found that rich rubber elasticity, leading to the present invention.

Further, a photosensitive resin composition obtained by drying a mixture of a photosensitive microgel (1) and a compound (2) having a carbon-carbon double bond as a second component not limited to an aqueous system, or a photosensitive resin The microgel (1) is dried, and then a photosensitive resin composition obtained by adding and mixing a compound (2) having a carbon-carbon double bond, which is a second component not limited to an aqueous system, is subjected to pressure molding. As a result, it has been found that a sheet having a predetermined thickness can be quickly and easily formed, and the characteristics as a flexographic printing plate can be dramatically improved.

[0007] Initially, it was thought that it would be impossible to obtain a continuous film (sheet) in the subsequent processing by drying the microgel micronized once to form a discontinuous film. It was possible to form a sheet, and a more tough continuous film (sheet) could be obtained by mixing the second component. By adding the second component (2) to the photosensitive microgel (1), the gap between the fine particles of the photosensitive microgel (1) is filled with the second component, and the fine particles can be efficiently cured and cross-linked. It is considered that the strength, elongation, and the like were improved due to the fact that it became possible.

[0008]

According to the present invention, a compound (a) having a carbon-carbon double bond is used as a tertiary ammonium salt-containing compound (b) and, if necessary, a low molecular surfactant as an emulsifier. Microgel microparticles (A) synthesized by emulsion polymerization using a compound (B) having an epoxy group and at least one carbon-carbon double bond that react with a tertiary ammonium salt in one molecule. , A photosensitive microgel having a carbon-carbon double bond on its surface (1), and a compound having a carbon-carbon double bond (2)
And a flexographic printing plate precursor obtained by using the photosensitive resin composition.

Among the compounds (a) having a carbon-carbon double bond used for synthesizing the microgel fine particles (A), monofunctional ones are (1) (meth) acrylic compounds are (meth) acrylic Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid alkyl esters of C ₁ -C ₁₈ (meth) acrylic acid lauryl like: glycidyl (meth) acrylate: allyl (meth) acrylate of (meth) alkenyl esters of C ₂ -C ₈ acrylic acid: hydroxyethyl (meth ) acrylates, C ₂ -C ₈ hydroxyalkylene of (meth) acrylic acid such as hydroxyethyl (meth) acrylate Glycol ester: such alkenyloxyl alkyl ester :( meth) acrylic acid C ₃ -C ₁₉ (meth) acrylic acid such as allyl (meth) acrylate, (2) styrene as a vinyl aromatic compound, alpha-methyl styrene (3) Other acrylonitrile, methacrylonitrile, methyl isopropenyl ketone: vinyl acetate, vinyl propionate, vinyl pivalate and the like.

Further, polyfunctional monomers and oligomers having two or more carbon-carbon double bonds for three-dimensionally cross-linking the inside of the microgel fine particles (A) include (1) (meth) acrylate-based monomers. (2) polyolefin compounds such as tri (meth) acrylate of trimethylolpropane, di (meth) acrylate of glycols, poly (meth) acrylate of polyol, and di (meth) acrylate of polyester Butadiene, isoprene, chloroprene, divinylbenzene, diallyl phthalate, etc.
Oligomers having one or more polymerizable unsaturated double bonds.

The urethane compound having a carbon-carbon double bond can be produced from a diol compound, a diisocyanate compound, or a compound having a hydroxyl group and a carbon-carbon double bond. Examples of the diol compound include various lactones, for example, β-propiolactone and a substituted product thereof, δ-valerolactone and a substituted product thereof, ε-caprolactone, etc.
Ring-opening polymerization of a membered ring or a higher lactone in the presence of ethylene glycol or the like in the presence or absence of a catalyst, or in the presence of an excess of a glycol component, in which the glycol component is condensed with a dibasic acid or the like, for example, Examples thereof include those having a hydroxyl group at a terminal such as polyethylene adipate, polypropylene adipate, polyethylene succinate, and polyhexamethylene adipate, and polyethylene glycol, polypropylene glycol, and polyepichlorohydrin. Examples of the diisocyanate compound include toluylene diisocyanate, diphenylmethane-4,4 diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the compound having a hydroxyl group and a carbon-carbon double bond include hydroxyethyl (meth) arylate, hydroxypropyl (meth) acrylate, and allyl alcohol.

Polydienes having a carbon-carbon double bond include, for example, polybutadiene or polyisoprene having an epoxy group or an acid anhydride group at a terminal or a side chain thereof, and a functional group capable of reacting with such a group. A compound having a heavy bond, such as hydroxyethyl (meth) acrylate,
C ₂ -C such as hydroxypropyl (meth) acrylate
It is obtained by reacting ₂₀ hydroxyalkyl esters, allyl alcohol, allylamine and the like. Alternatively, it can be obtained by reacting an excessive amount of a diisocyanate group with a terminal or side chain hydroxyl group and reacting the remaining isocyanate group with a hydroxyalkyl ester or allyl alcohol.

These compounds having a carbon-carbon double bond are appropriately selected according to the desired physical properties, and can be used alone or in combination of two or more. In order to satisfy various resistances and characteristics required for a flexographic printing plate, it is desirable that the inside (core) of the microgel fine particles (A) is three-dimensionally crosslinked. It is desirable to use one or more of those having a double bond, that is, a polyfunctional monomer or oligomer.

The tertiary ammonium salt-containing compound (b) used for emulsifying the compound (a) having a carbon-carbon double bond is effective as an emulsifier, and is usually a compound having a tertiary amino group. Is neutralized with an acid and tertiary salified. As those of low molecular weight of such emulsifiers, dimethyl lauryl amine, dimethyl myristyl amine, dimethyl palmityl amine, dimethyl stearyl amine, diethyl laurylamine, diethyl myristylamine, diethyl palmitylamine, C ₆ such as diethyl stearylamine alkyl and alkenyl tertiary amines -C _20, 2,2-dimethylaminoethyl (meth)
Hydrochloric acid, nitric acid, sulfuric acid, acetic acid, propionic acid, butyric acid, and tertiary amine, which is a reactive monomer having an amino group such as acrylate and 2,2-diethylaminoethyl (meth) acrylate,
There is a reaction product with an acid such as (meth) acrylic acid.

As the polymer emulsifier, a reactive monomer having an amino group such as 2,2-dimethylaminoethyl (meth) acrylate and 2,2-diethylaminoethyl (meth) acrylate and another reactive monomer, for example, Methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
C ₁ -C of (meth) acrylic acid such as propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and lauryl (meth) acrylate ₁₈ alkyl esters of allyl (meth) acrylate of (meth) alkenyl esters of C ₂ -C ₈ acrylic acid: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, C of (meth) acrylic acid etc. ₂ -C ₈ hydroxyalkyl esters: allyl oxyl ethyl (meth) acrylate of (meth) alkenyloxyl alkyl esters of C ₃ -C ₁₉ acrylic acid:
Examples thereof include those obtained by copolymerizing one or more vinyl monomers selected from (meth) acrylic acid and the like, followed by neutralization with an acid. Further, a polymer obtained by neutralizing a polymer containing an amino group, such as a natural polymer such as chitosan or a synthetic polymer such as polyethyleneimine, with an acid can also be used.

The above polymer emulsifier can be used as it is or
By reacting a part of the quaternary ammonium salt with a compound containing an epoxy group and a carbon-carbon double bond such as glycidyl (meth) acrylate, a carbon-carbon double bond can be introduced and used as a reactive emulsifier. By using the reactive emulsifier, the emulsifier itself can be fixed to the inside (core) when the inside (core) of the microgel fine particles (A) is three-dimensionally crosslinked. By fixing an emulsifier (shell) inside (core) of microgel fine particles (A), various resistances such as strength, elongation, hardness, water resistance and abrasion resistance of a flexographic printing plate using a photosensitive microgel. Can be improved. The polymer emulsifier is used in an amount of 0.1 to 80% by weight, preferably 3 to 50% by weight, based on the compound (a) having a carbon-carbon double bond. When used in combination with the following low molecular surfactants, it is used in an amount of 0.1 to 50% by weight, preferably 3 to 20% by weight.

The low molecular surfactant used in combination with the above-mentioned high molecular emulsifier includes a nonionic surfactant and a cationic surfactant. As nonionic surfactants, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan monolaurate, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan trioleate, and glycerin fatty acid esters And polyoxyethylene fatty acid esters.

Examples of the cationic surfactant include hydrochlorides of primary amines such as monomethylamine, monoethylamine and monostearylamine, hydrochlorides of secondary amines such as dimethylamine, diethylamine and distearylamine, trimethylamine, triethylamine, and the like. Hydrochlorides of tertiary amines such as stearyl dimethylamine, hydrochlorides of ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, hydrochlorides of polyethylene polyamines such as ethylenediamine and diethylenetriamine, amines such as pyridine, morpholine and hydrazine And the like.

The low molecular surfactant is used in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, based on the compound (a) having a carbon-carbon double bond. Emulsion polymerization temperature is 50 ~ 95
° C, preferably 65-80 ° C. Emulsion polymerization is carried out at a solid content of the compound (a) having a carbon-carbon double bond and the emulsifier of 10 to 50% by weight, preferably 15 to 30% by weight.
In the present invention, the particle size of the microgel formed by emulsion polymerization is usually 10 to 500 nm as measured by a light scattering method.

The tertiary ammonium salt present on the surface of the microgel particles (A) thus formed and the compound (B) having an epoxy group and at least one carbon-carbon double bond in one molecule The reaction is performed to introduce a carbon-carbon double bond into the surface of the microgel fine particles. As the compound (B), glycidyl (meth) acrylate, N-
Epoxy compounds having a polymerizable unsaturated double bond such as glycidyl (meth) acrylamide, glycidyl allyl ether, and 1,2-epoxy-5-hexene are exemplified. These compounds (B) are appropriately selected according to desired physical properties,
They can be used alone or in combination of two or more. Compound (B) is the third compound on the surface of the microgel particles.
The reaction can be carried out at a free ratio of 1 to 100 mol% with respect to the quaternary ammonium base. The reaction is completed only by mixing the compound (B) with the microgel emulsion and stirring the mixture at a temperature of 30 to 90 ° C, preferably 60 to 80 ° C for about 2 hours.

As the compound (2) having a carbon-carbon double bond, one or more of monomers, oligomers and prepolymers can be used. As this example, the same as the compound (a) having a carbon-carbon double bond, which is the material of the core of the photosensitive microgel, can be mentioned. Among them, compounds having flexibility, flexibility, toughness, rubber elasticity and the like in a state after crosslinking / curing are preferable, for example, a urethane compound having a carbon-carbon double bond, a carbon-carbon double bond at a terminal or a side chain. Polydienes.

As a method for adding the compound (2) having a carbon-carbon double bond, the following method can be considered. (I) Addition / Mixing → Drying Compound (2) is added to the aqueous solution of the photosensitive microgel and dried. When the compound (2) is uniformly dispersed or dissolved in the aqueous photosensitive microgel dispersion, the dried product can be immediately subjected to pressure molding. On the other hand, if it is not so uniform, it is needless to say that after drying, it is necessary to sufficiently disperse and mix the mixture prior to pressure molding.

(II) Drying → Mixing After the aqueous dispersion of the photosensitive microgel is dried, the compound (2) is added, and the mixture is dispersed (dispersed, milled) with a two-roll, three-roll, kneader, plastmill or the like, and then uniformly mixed. Disperse. Of course, the dispersion / mixing step and the step of forming a sheet by pressure molding may be a series of steps.
Rather, a series is more desirable in the working process. The method for drying the photosensitive microgel or the photosensitive resin composition containing the photosensitive microgel is not particularly limited, such as vacuum drying, freeze drying, and spray drying. Of course, thin films and thick films formed by the conventional casting method are also applicable.

If necessary, an initiator, a sensitizer, a filler, a hydrophilic monomer, a resin, and the like can be added to the photosensitive resin composition. As a method of adding these initiators, sensitizers, etc., any of (I) addition / mixing → drying (II) drying → addition / mixing may be used as in the case of adding the second component. Crosslinking by radiation occurs even without a photopolymerization initiator, but in the case of ultraviolet irradiation, the addition of an appropriate photopolymerization initiator increases the crosslinking efficiency. Benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy
2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] 2-morpholinopropanone-1, and the like. The photopolymerization initiator is used in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition.

The hydrophilic monomer is used for improving water developability, for example, N, N-methylenebis (meth) acrylamide, 1,2-di (meth) acrylamide ethylene glycol, N, N-oxymethylenebisacrylamide, Examples include (meth) acrylamide, vinylpyrrolidone, 2-hydroxyethyl (meth) acrylate, polyoxyethylene (meth) acrylate, and polyoxyethylene di (meth) acrylate. Further, in order to impart various functions to the resin of the present invention, a coloring agent, an extender, a lubricant, a plasticizer, a stabilizer, a flame retardant, an antifoaming agent, an antioxidant, a bactericide, and a conductive agent are provided as necessary. Additives such as materials and magnetic materials can also be included.

The photosensitive resin composition containing the photosensitive microgel (1) produced as described above and the compound (2) having at least one carbon-carbon double bond in one molecule is extruded by a molding machine, a press or the like. A film (sheet) for the original plate is formed using a machine or the like. By irradiating the original plate with radiation such as ultraviolet rays and electron beams, the irradiated portions are crosslinked and cured, and the uncured portions are washed away with water to obtain a desired plate.

[0027]

EXAMPLES The present invention will be described in more detail with reference to Examples. In the examples, first, a method for producing a photosensitive microgel, which is one of the main components of the photosensitive resin composition, will be described. Next, an example of mixing this and the second component will be described. Finally, the photosensitive resin composition will be used. The water resistance, IPA resistance, rubber hardness, rupture strength, rupture elongation, etc. of the sheet after photocuring were evaluated. In the examples, "parts" and "%" indicate parts by weight and% by weight.

A. Synthesis of Cationic Polymer Emulsifier 140 parts of lauryl methacrylate, 60 parts of 2-dimethylaminoethyl methacrylate and 200 parts of 2-propanol were heated to 80 ° C. in a 2 liter reaction vessel with stirring in a nitrogen atmosphere. Azobisisobutyronitrile (hereinafter referred to as AIBN)
1.6 parts were added and maintained for 2 hours, then 0.4 parts of AIBN was added, and then the reaction mixture was maintained at 80 ° C. for 4 hours to complete the polymerization.
After cooling to room temperature, a mixture of 38.2 parts of acetic acid and 1000 parts of ion-exchanged water was added, and the mixture was heated to remove 2-propanol and water by azeotropic distillation. Thereafter, 9.0 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere and maintained for 2 hours to obtain a methacryl group-pending cationic polymer emulsifier.

B. Synthesis of urethane dimethacrylate Molecular weight of about 1000 consisting of butanediol and adipic acid
100 g of polyester diol, 75 g of diphenylmethane diisocyanate, and 0.1 g of dibutyltin laurate, and reacted at 50 ° C. for 30 minutes and 90 ° C. for 2 hours, cooled to 70 ° C., and added 26 g of 2-hydroxyethyl methacrylate to further add 3 g. The reaction was continued for an hour to obtain urethane dimethacrylate.

(Synthesis example 1 of photosensitive microgel) 40 parts of urethane dimethacrylate synthesized in b, 100 parts of an aqueous solution of a reactive cationic polymer emulsifier synthesized in a (solid content: 20%),
160 parts of deionized water were heated to 80 ° C. in a 500 ml reaction vessel with stirring and in a nitrogen atmosphere. 3% azobis amidino propane
8 parts of an aqueous solution of dihydrochloride (hereinafter referred to as AAPD) was added, and the mixture was maintained for 2 hours. Then, 2 parts of a 3% aqueous solution of AAPD was added. After completion of the addition, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and a microgel aqueous dispersion was obtained. The measurement result of the particle size by the light scattering method was about 200 nm. After leaving the aqueous microgel dispersion overnight, 2.7 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere and maintained for 2 hours to complete the reaction.

(Synthesis example 2 of photosensitive microgel) 30 parts of urethane dimethacrylate synthesized in b, 10 parts of polypropylene glycol monomethacrylate, 100 parts of an aqueous solution of a reactive cationic polymer emulsifier synthesized in a (solid content: 20%), 160 parts of deionized water were heated to 80 ° C. in a 500 ml reaction vessel with stirring and in a nitrogen atmosphere. 8 parts of a 3% AAPD aqueous solution was added, and the mixture was maintained for 2 hours. Then, 2 parts of a 3% AAPD aqueous solution was added. After completion of the addition, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and a microgel aqueous dispersion was obtained. The measurement result of the particle size by the light scattering method was about 50 nm. After leaving the aqueous microgel dispersion overnight, 2.7 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere and maintained for 2 hours to complete the reaction.

(Synthesis example 3 of photosensitive microgel) M-1000-8
0 (Acrylate of polybutadiene manufactured by Nippon Oil Co., Ltd.) 40 parts, reactive cationic polymer emulsifier aqueous solution synthesized in a (100% solid content) 100 parts, Emulgen 420 (Kao Corporation)
2.5 parts of polyoxyethylene oleyl ether) and 160 parts of ion-exchanged water were heated to 80 ° C. in a nitrogen atmosphere with stirring in a 500 ml reaction vessel. Eight parts of a 3% AAPD aqueous solution was added and maintained for 2 hours, and then 2 parts of a 3% AAPD aqueous solution was added. After completion of the addition, the reaction mixture was kept at 80 ° C. for 4 hours to complete the polymerization, and a microgel aqueous dispersion was obtained. The measurement result of the particle size by the light scattering method was about 100 nm. After leaving the aqueous microgel dispersion overnight, 2.1 parts of glycidyl methacrylate was added, and the mixture was heated to 70 ° C. in an air atmosphere and maintained for 2 hours to complete the reaction.

(Examples 1, 2, and 3) The photosensitive microgel aqueous dispersions obtained in Synthesis Examples 1, 2, and 3 (solid content: 25%)
Water was distilled off until the fluidity disappeared with an evaporator, and then transferred to a vat and further dried in a vacuum drier.
A seed powder was obtained. During this time, the time required to obtain a powder from the dispersion was about 3 hours. To 7 parts of the obtained three kinds of powder, 3 parts of a bifunctional acrylate monomer and 0.5 part of Darocure 2959 (manufactured by Merck) were added and dispersed by a three-roll mill.

(Examples 4, 5, and 6) To 7 parts of the three kinds of powders obtained in Example 1, 3 parts of urethane dimethacrylate synthesized in b and 0.5 parts of Darocure 2959 (manufactured by Merck) were added. Dispersed with two rolls. (Examples 7, 8, 9) Three parts of M-1000-80 (acrylated product of polybutadiene manufactured by Nippon Oil Co., Ltd.) and 7 parts of Darocur 2959 (Merck Co., Ltd.) were added to 7 parts of the three kinds of powder obtained in Example 1. Was added and dispersed with two rolls.

(Comparative Examples 1, 2, and 3) The photosensitive microgel aqueous dispersions obtained in Synthesis Examples 1, 2, and 3 (solid content: 25%)
2.5 parts of Darocure 2959 (manufactured by Merck) were added to the mixture, and water was distilled off using an evaporator until the fluidity disappeared. Thereafter, the mixture was transferred to a vat and further dried in a vacuum dryer to obtain a powder. During this time, the time required to obtain powder from the dispersion is about 3
It was time.

(Formation of film) About 10 parts of the photosensitive resin composition obtained in Examples 1 to 9 and the powder obtained in Comparative Examples 1 to 3 were respectively pressed by a press machine to form a uniform film of about 3 mm. did. Pressing conditions are 50 ° C, 100 kg / cm ² , and 15 minutes.

(Evaluation of Physical Properties) The film formed as described above was irradiated with ultraviolet rays at 4000 mJ / cm ² to obtain a cured film. The rupture strength, rupture elongation, rubber hardness, water resistance, alkali resistance, and IPA resistance of the cured film were measured at room temperature (25 ° C.). water resistant,
Alkali resistance and IPA resistance are measured with ion-exchanged water, sodium carbonate aqueous solution (pH = 9), and isopropyl alcohol (IPA).
It was evaluated by soaking for 24 hours and measuring the swelling rate. Table 1 shows the results. Breaking strength: Measured by a tensile tester Breaking elongation Sample size: 10 * 20 * 3 (mm) Test conditions: Tensile speed 50 mm / min Rubber hardness: According to JIS-K6301. Swelling rate: ((weight after immersion for 24 hours / weight before immersion) -1) *
100 resolution: A mask film having patterns of various line widths was superposed on the film, and the film was irradiated with ultraviolet rays, and the finest line width obtained by developing with water was defined as the resolution.

[0038]

[Table 1]

[0039]

The cured film formed by using the photosensitive resin composition of the present invention has a higher breaking strength than a film formed by a conventional casting method using a photosensitive microgel aqueous dispersion.
The breaking elongation and the rubber hardness have been dramatically improved, and an excellent flexographic plate which can be developed with water can be manufactured. In addition,
Various characteristics required for the flexographic plate such as resolution, water resistance, alkali resistance, and IPA (isopropyl alcohol) resistance were comparable to those of the conventional photosensitive microgel alone.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 289/00 C08F 289/00 290/04 290/04 290/06 290/06 290/12 290/12 299/00 299/00 299/06 299/06 G03F 7/027 G03F 7/027 7/033 7/033 7/035 7/035 (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 1/00-101/14 C08F 290/00-290/14 C08F 299/00-299/08 C08F 2/00-2/60 C08F 8/00-8/50 C08F 289/00 G03F 7/00-7/14 B41N 1/00-1 /twenty four

Claims (8)

(57) [Claims] 1. Compound (a) having a carbon-carbon double bond
Is obtained by emulsion polymerization using a tertiary ammonium salt-containing compound (b) as an emulsifier, microgel fine particles (A), an epoxy group which reacts with a tertiary ammonium salt in one molecule, and at least one carbon atom. A photosensitive resin composition comprising a photosensitive microgel (1) obtained by reacting with a compound (B) having a double bond, and a compound (2) having a carbon-carbon double bond. 2. Compound (a) having a carbon-carbon double bond
Is a urethane compound having a carbon-carbon double bond and / or a polydiene having a carbon-carbon double bond at a terminal or a side chain, or a mixture of the urethane compound and / or the polydiene with another compound having a carbon-carbon double bond. The photosensitive resin composition according to claim 1, which is a mixture. 3. A tertiary ammonium salt-containing compound (b)
Contains a carbon-carbon double bond. The photosensitive resin composition according to claim 1 or 2, wherein 4. The photosensitive resin composition according to claim 1, wherein a low molecular surfactant is used in combination when producing the microgel fine particles (A) by emulsion polymerization. 5. The photosensitive resin composition according to claim 4, wherein the low molecular surfactant is a nonionic surfactant or a cationic surfactant. 6. Compound (2) having a carbon-carbon double bond
Is a urethane compound having a carbon-carbon double bond and / or a polydiene having a carbon-carbon double bond in a terminal or a side chain, or another compound having a carbon-carbon double bond with the urethane compound and / or the polydiene. The photosensitive resin composition according to any one of claims 1 to 5, wherein the photosensitive resin composition is a mixture of: 7. The photosensitive composition according to claim 1, wherein the aqueous dispersion of the photosensitive microgel (1) is dried, and the compound (2) having a carbon-carbon double bond is mixed. A method for producing a resin composition. 8. A flexographic printing plate precursor comprising the photosensitive resin composition according to claim 1. Description: [0001]