JP6977615B2 - Photosensitive resin composition, photosensitive resin laminate, and photosensitive resin printing plate original plate - Google Patents

Description

The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, and a photosensitive resin printing plate original plate.

A photosensitive resin printing plate original plate using a photosensitive resin laminate having a layer formed of a photosensitive resin composition generally has a soluble polymer, a photopolymerizable unsaturated group-containing monomer, and photopolymerization initiation in the photosensitive resin layer. By containing the agent as an essential component and irradiating the photosensitive resin layer with ultraviolet light via a negative or positive original image film, a portion that dissolves in the solvent and a portion that does not dissolve in the solvent are formed in the photosensitive resin layer. , A relief image is formed and used as a printing plate.

For pad printing, use a concave printing plate, place ink on the plate surface and scrape it off with a metal doctor blade, or in a ring-shaped ceramic or special metal edged ink cup that acts as a doctor blade. By putting ink and scraping the surface of the plate with an ink cup, the recesses of the concave printing plate are filled with ink, the ink is transferred to a flexible pad surface such as silicone rubber, and the ink-adhered surface of the pad is printed. It is a type of offset printing that prints by crimping to the body. Since the intaglio printing plate used for pad printing scrapes the ink on the plate surface with a doctor blade or an ink cup due to the printing method, the plate surface is required to have abrasion resistance and no uneven ink scraping. On the other hand, the photosensitive resin printing plate original plate is also required to be able to develop the photosensitive resin layer exposed to an image with water from the viewpoint of reducing the environmental load and the ease of plate making.

So far, as a photosensitive resin composition used for printing applications requiring abrasion resistance, a photosensitive resin composition containing inorganic fine particles which are abrasive particles as shown in Patent Document 1 or 2 has been proposed. ing. As a photosensitive resin composition that can be developed with water, a photosensitive resin composition containing a water-soluble or water-swellable polymer as a soluble polymer as shown in Patent Documents 2 or 3 has been proposed.

Japanese Unexamined Patent Publication No. 58-18635 JP 2016-139130 Japanese Patent Application Laid-Open No. 2000-162770

In the technique described in Patent Document 1, although the abrasion resistance is improved by the blended inorganic fine particles, the surface roughness of the intaglio printing plate becomes rough, the ink scraping property is insufficient, and the developing solution is prepared. There was a problem in being an organic solvent. The techniques described in Patent Documents 2 and 3 are excellent in ink scraping property and can be developed in water, but have a problem in wear resistance.

The present invention has been made in view of the above circumstances, and is capable of water development, has excellent wear resistance, and has excellent photosensitivity for scraping ink on the plate surface when squeezed with a blade of a pad printing machine. It is an object of the present invention to provide a resin composition, a photosensitive resin laminate, and a photosensitive resin printing plate original plate.

The photosensitive resin composition of the present invention that solves the above problems has (A1) a polyamide having a hydrophilic group, (B) an average particle size of 0.5 μm or more and 4 μm or less, and a sphericity of 0.9 or more. A photosensitive resin composition comprising (C) a compound having an ethylenic double bond and (D) a photopolymerization initiator , wherein the (A1) hydrophilic group is contained. It is a photosensitive resin composition characterized in that the polyamide having it has a piperazine ring.

The photosensitive resin composition, the photosensitive resin laminate, and the photosensitive resin printing plate original plate of the present invention are water-developable, have excellent wear resistance, and are inks on the plate surface when squeezed by a blade of a pad printing machine. Excellent in scraping property.

Hereinafter, embodiments of the present invention will be described.

Copolymerization in which it is easy to introduce a hydrophilic group for imparting water developability into the polyamide having a hydrophilic group (A1) which is a component (A1) constituting the photosensitive resin composition of the present invention. Polyamide is preferably used.

(A1) The polyamide having a hydrophilic group has a function as a carrier resin for making the photosensitive resin composition into a solid state and retaining its morphology, and also for imparting developability with water to the photosensitive resin layer. used. Examples of such polyamides include water-soluble or water-dispersible polyamides containing 6-nylon as a constituent, and copolymerized polyamides containing 6-nylon and a hydrophilic component and 6-nylon are chemically modified. Examples include modified polyamides. Further, the polyamide of the present invention may contain an ester bond or a urethane bond in addition to the amide bond.

Specific examples of the copolymerized polyamide include a polyamide having a sulfonic acid group or a sulfonate group in the side chain described in JP-A-48-72250, and a polyamide containing a polyether segment described in JP-A-55-74537. Examples thereof include polyamides having basic nitrogen described in JP-A-50-7605.

Among the above-mentioned polyamides, a polyamide containing basic nitrogen and / or a polyamide containing a polyether segment is preferably used. The polyamide having basic nitrogen is a polymer containing basic nitrogen in a part of the main chain or the side chain. Basic nitrogen is a nitrogen atom that constitutes an amino group that is not an amide group. As such a polyamide, a polyamide having a tertiary amino group in the main chain is preferable. The polyamide having basic nitrogen can be obtained by subjecting a monomer having basic nitrogen alone or using another monomer to polycondensation, a polyaddition reaction, or the like.

As the basic nitrogen, piperazine and N, N-dialkylamino groups are preferable, and piperazine is more preferable. Specific examples of the monomer having basic nitrogen for providing the polyamide used in the present invention are N, N'-bis (aminomethyl) -piperazine and N, N'-bis (β-). Aminoethyl) -piperazine, N, N'-bis (γ-aminobenzyl) -piperazine, N- (β-aminoethyl) piperazine, N- (β-aminopropyl) piperazine, N- (ω-aminohexyl) piperazine , N- (β-aminoethyl) -2,5-dimethylpiperazine, N, N-bis (β-aminoethyl) -benzylamine, N, N-bis (γ-aminopropyl) -amine, N, N' Diamines such as -dimethyl-N, N'-bis (γ-aminopropyl) -ethylenediamine, N, N'-dimethyl-N, N'-bis (γ-aminopropyl) -tetramethylenediamine, N, N' -Bis (carboxymethyl) -piperazine, N, N'-bis (carboxymethyl) -methylpiperazine, N, N'-bis (carboxymethyl) -2,6-dimethylpiperazine, N, N'-bis (β-) Carboxyethyl) -piperazine, N, N-bis (carboxymethyl) -methylamine, N, N-bis (β-carboxyethyl) -ethylamine, N, N-bis (β-carboxyethyl) -methylamine, N, N-di (β-carboxyethyl) -isopropylamine, N, N'-dimethyl-N, N'-bis- (carboxymethyl) -ethylenediamine, N, N'-dimethyl-N, N'-bis- (β) -Carboxyethyl) -Dicarboxylic acids such as ethylenediamine or their lower alkyl esters, acid halides, N- (aminomethyl) -N'-(carboxymethyl) -piperazine, N- (aminomethyl) -N'-(β) -Carboxyethyl) -piperazine, N- (β-aminoethyl) -N'-(β-carboxyethyl) -piperazine, N-carboxymethylpiperazine, N- (β-carboxyethyl) piperazine, N- (γ-carboxyl) Hexil) piperazine, N- (ω-carboxyhexyl) piperazine, N- (aminomethyl) -N- (carboxymethyl) -methylamine, N- (β-aminoethyl) -N- (β-carboxyethyl) -methyl Amine, N- (aminomethyl) -N- (β-carboxyethyl) -isopropylamine, N, N'-dimethyl-N- (aminomethyl) -N'-(carboxymethyl) -ethylenediamine and other ω-amino acids, etc. There is. In addition to these monomers, those polymerized in combination with diamines, dicarboxylic acids, ω-amino acids, lactams, etc. can also be used. These basic nitrogen-containing monomer components are 10 to 100 mol% with respect to the sum of all polyamide components, that is, aminocarboxylic acid units (including the case of lactam as a raw material), dicarboxylic acid units and diamine units. It is preferably present, and more preferably 10 to 80 mol%. When it is 10 mol% or more, the water solubility becomes high and the compatibility with the component (C) becomes high, which is preferable.

Further, among the above-mentioned polyamides, a polyamide containing an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue is preferable. By having an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue, the glass transition point of the polyamide can be increased and the abrasion resistance can be improved. The alicyclic group referred to here is a cyclic structure containing carbon or nitrogen.

Examples of the alicyclic diamine residue include isophorone diamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, and 1,4-bis (aminomethyl) cyclohexane. , 1-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-amino) Examples thereof include cyclohexyl) propane, 1,4-bis (3-aminopropyl) piperazine, N- (2-aminoethyl) piperazine, methylcyclohexanediamine, norbornandiamine, and tricyclodecanediamine.

Examples of the alicyclic dicarboxylic acid residue include isophorone dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-norbornandicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 2-methyl-1,4-cyclohexane. Dicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, 2-propyl-1,4-cyclohexanedicarboxylic acid, 2-butyl-1,4-cyclohexanedicarboxylic acid, 2-t-butyl-1,4-cyclohexane Dicarboxylic acid, 2,3-dimethyl-1,4-cyclohexanedicarboxylic acid, 2,3-diethyl-1,4-cyclohexanedicarboxylic acid, 2,3-dipropyl-1,4-cyclohexanedicarboxylic acid, 2,3-dibutyl -1,4-Cyclohexanedicarboxylic acid, 2-methyl-3-ethyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-propyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-butyl-1 , 4-Cyclohexanedicarboxylic acid, 2-ethyl-3-propyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-3-butyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-t-butyl-1 , 4-Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,6-decalindicarboxylic acid, 3-methyl-2,6-decalindicarboxylic acid, 3-ethyl-2,6-decalindicarboxylic acid, 3-propyl -2,6-decalindicarboxylic acid, 3-butyl-2,6-decalindicarboxylic acid, 3,4-dimethyl-2,6-decalindicarboxylic acid, 3,4-diethyl-2,6-decalindicarboxylic acid, 3 , 4-Dipropyl-2,6-decalindicarboxylic acid, 3,4-dibutyl-2,6-decalindicarboxylic acid, 3,8-dimethyl-2,6-decalindicarboxylic acid, 3,8-diethyl-2,6 -Decalindicarboxylic acid, 3,8-dipropyl-2,6-decalindicarboxylic acid, 3,8-dibutyl-2,6-decalindicarboxylic acid, 3-methyl-4-ethyl-2,6-decalindicarboxylic acid, 3 Examples thereof include −methyl-4-propyl-2,6-decalindicarboxylic acid, 3-methyl-4-butyl-2,6-decalindicarboxylic acid and 3-ethyl-4-butyl-2,6-decalindicarboxylic acid.

The polyamide used in the present invention is a polyamide containing 30 to 90 mol% of an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue and 20 mol% or more of an alicyclic dicarboxylic acid residue. Is preferable. By containing 30 mol% or more of the alicyclic diamine residue and / or the alicyclic dicarboxylic acid residue, the glass transition point of the polyamide can be improved and the abrasion resistance of the printing plate precursor can be improved. On the other hand, by containing 90 mol% or less of the alicyclic diamine residue and / or the alicyclic dicarboxylic acid residue, the elastic modulus of the polyamide can be controlled and cracking of the printing plate original plate can be prevented. Further, by containing 20 mol% or more of the alicyclic dicarboxylic acid residue, the glass transition point of the polyamide can be improved and the abrasion resistance of the printing plate precursor can be improved.

The mol% of alicyclic diamine residue and / or alicyclic dicarboxylic acid residue contained in polyamide is the number of moles of alicyclic residue with respect to the total number of moles obtained from aminocarboxylic acid, diamine, and dicarboxylic acid. It shows the ratio of. The mol% of the alicyclic residue can be calculated from the number of moles in the raw material charging stage or ^{the measurement result of 1 H-NMR. 1 1} H-NMR analysis is a commonly used analysis method, in which the mol% of each structural unit is calculated from the integrated value.

Further, as another embodiment of the photosensitive resin composition of the present invention, a modified partially saponified polyvinyl acetate having a functional group that can be crosslinked by a radical reaction, which is a component (A2), in a side chain is included. Generally, as a functional group that can be crosslinked by such a radical reaction, a non-aromatic unsaturated carbon-carbon bond, particularly an ethylenic double bond is often used, and a vinyl group or a (meth) acryloyl group is used. Can be mentioned. By using a modified partially saponified polyvinyl acetate having a functional group that can be crosslinked by such a radical reaction in the side chain, the polymer polymerizes with the monomer component, so that the abrasion resistance is improved.

As a method for introducing a functional group that can be crosslinked by such a radical reaction into the side chain of partially saponified polyvinyl acetate, for example, the methods described in JP-A-3-274558 and JP-A-4-283479 are used. Examples thereof include the methods described in JP-A-2007-79494.

In the methods described in JP-A-3-274558 and JP-A-4-283479, a partially saponified polyvinyl acetate is reacted with an acid anhydride, and a carboxyl group is generated starting from the hydroxyl group of the partially saponified polyvinyl acetate. A functional group that can be introduced into the polymer side chain and can be crosslinked by a radical reaction by reacting the carboxyl group with an unsaturated epoxy compound is introduced, or vinyl acetate is copolymerized with an unsaturated carboxylic acid or a salt thereof. A functional group that can be crosslinked by a radical reaction by partially saponifying the obtained polymer and reacting the carboxyl group contained in the obtained anion-modified polyvinyl alcohol having a saponification degree of 60 to 90 mol% with an unsaturated epoxy compound. Is a method of introducing. Among them, the partially saponified polyvinyl acetate obtained by the former method is preferably used because the effect of the present invention is remarkably exhibited.

The functional group that can be crosslinked by such a radical reaction is preferably present in compound (A2) at 0.08 to 0.72 mol / kg, more preferably 0.12 to 0.36 mol / kg. Is. When it is 0.72 mol / kg or less, excellent water developability can be obtained, which is preferable, and when it is 0.08 mol / kg or more, a functional group that can be crosslinked by a radical reaction reacts. It is preferable because it is possible to obtain an effect such as suppressing relief chipping during development, which is improved. The modified partially saponified polyvinyl acetate having a functional group that can be crosslinked by the (A2) radical reaction thus obtained has at least the following structural units (I), (II), and (III). It is preferable to have.

(In (II), R represents a hydrocarbon group having 1 to 20 carbon atoms, and in (III), X represents a functional group having an unsaturated carbon-carbon bond at the terminal.)
(A2) Since partially saponified polyvinyl acetate having a functional group that can be crosslinked by a radical reaction requires water developability, the unit of the structure (I) is preferably 60 to 99 mol%, more preferably 70. ~ 95 mol%. When the structural unit of (I) is 60 mol% or more, sufficient water developability can be obtained, and when it is 99 mol% or less, the solubility in water at room temperature can be maintained. The average degree of polymerization of the component (A2) is preferably in the range of 300 to 2000, more preferably 500 to 1000. When the average degree of polymerization is 300 or more, sufficient water resistance can be obtained. When the average degree of polymerization is 2000 or less, water solubility sufficient to obtain sufficient water developability can be obtained.

On the other hand, the method described in JP-A-2007-79494 is a reaction between a partially saponified polyvinyl acetate and an acrylic compound having an N-methylol group, and crosslinks the side chains of the partially saponified polyvinyl acetate by a radical reaction. It is a method of introducing a functional group that can be used. The blending amount of the acrylic compound having an N-methylol group is preferably 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of polyvinyl acetate. When the blending amount of the acrylic compound having an N-methylol group is 40 parts by weight or less, excellent water developability can be obtained. Further, when the amount is 2 parts by weight or more, an effect such as relief chipping at the time of development, which is improved by the reaction of functional groups that can be crosslinked by a radical reaction, is exhibited.

Examples of the acrylic compound having an N-methylol group include N-methylolacrylamide, N-methylolmethacrylamide, N-methyl-N-methylolacrylamide, N-methyl-N-methylolmethacrylamide, and N-ethyl-N. -Methylolacrylamide, N-ethyl-N-methylolmethacrylamide and the like can be mentioned, but N-methylolacrylamide and N-methylolmethacrylamide are particularly preferable. These may be used alone or in combination of two or more.

Further, the photosensitive resin composition of the present invention can also contain both the component (A1) and the component (A2).

The photosensitive resin composition of the present invention contains inorganic fine particles having an average particle diameter of 0.5 μm or more and 4 μm or less and a sphericity of 0.9 or more as the component (B) (hereinafter, “inorganic”). Fine particles (B) "). By using such inorganic fine particles (B), it is possible to provide a photosensitive resin composition having excellent wear resistance and excellent scraping property of ink on the plate surface when squeezed by a blade of a pad printing machine.

The inorganic fine particles (B) have an average particle size of 0.5 μm or more to improve wear resistance when the pad printing machine is bladed, and 4 μm or less to be squeezed by the pad printing machine blade. The ink scraping property on the plate surface is improved. The average particle size of the inorganic fine particles (B) is preferably 0.5 μm or more, more preferably 1.0 μm or more. The average particle size is preferably 4.0 μm or less, more preferably 3.0 μm or less. Further, since the sphericity of the inorganic fine particles (B) is 0.9 or more, preferably 0.90 or more, more preferably 0.90 to 1.0, the surface roughness of the printing plate becomes small. The ink scraping property is further improved. In the present invention, the average particle diameter of the inorganic fine particles (B) is the median diameter measured by the laser diffraction / scattering method. The sphericity is defined as the arithmetic mean value of 50 inorganic fine particles (B) obtained by observing the shape of 50 inorganic fine particles (B) with a scanning electron microscope and determining the ratio of the shortest diameter / longest diameter of each inorganic fine particle. It is a thing.

Examples of such inorganic fine particles (B) include single metal fine particles, inorganic oxide particles, inorganic salt fine particles, fine particles composed of organic components and inorganic components, and the like. Of these, a polyamide having a hydrophilic group (A1), which is an organic component contained in the photosensitive resin composition, from the viewpoint of suppressing scattering of ultraviolet light when the photosensitive resin composition is irradiated with light and light-cured. , (A2) Modified partially saponified polyvinylacetate having a functional group that can be crosslinked by a radical reaction in the side chain, (C) Compound having an ethylenic double bond, and (D) Refractive rate with a photopolymerization initiator. Silica particles that are relatively close to each other are preferable. Further, amorphous silica is more preferable from the viewpoint of safe handling.

The method for producing such amorphous silica is not particularly limited, but as shown in JP-A-58-145613, a method for melting silica particles in a flame, JP-A-2006-36915. As shown in Japanese Patent Publication No., a method of producing by burning silicon powder by a VMC (Amorphized Metal Particle) method is known.

Further, the specific surface area of the inorganic fine particles (B) is preferably 10 m ² / g or less. When it is 10 m ² / g or less, the fluidity of the resin solution in which the photosensitive resin composition is dissolved in a solvent is good, and it is easy to form a smooth film surface. The specific surface area of the inorganic fine particles (B) is more preferably 9 m ² / g or less, still more preferably 8 m ² / g or less. In the present specification, the specific surface area of the inorganic fine particles (B) can be measured based on the method described in JIS Z8830: 2013.

On the other hand, the maximum particle size of the inorganic fine particles (B) is preferably 20 μm or less, more preferably 20.0 μm or less. When the maximum particle size is 20 μm or less, the ink scraping property when squeezed by the blade of the pad printing machine is good. The maximum particle size of the inorganic fine particles (B) is more preferably 10 μm or less. The maximum particle size was set by passing the inorganic fine particles through a sieve of the corresponding size.

Further, the inorganic fine particles (B) preferably contain the pH of the extracted water in the range of 5.5 to 8.5. Within this range, the dispersibility in other components used in the present invention is improved, and the aggregation of the inorganic fine particles (B) is suppressed. It is more preferable that the pH of the extracted water is in the range of 6.0 to 8.0. In the present specification, the pH of the extracted water of the inorganic fine particles (B) can be measured with a pH meter after the powder of the inorganic fine particles is dispersed in distilled water in an amount of 10% by mass and stirred for 30 minutes. The pH of the inorganic fine particles can be adjusted by allowing an activity inhibitor to act on the active hydroxyl group of the inorganic fine particles. As an example of the activity inhibitor, one or more selected from an organic phosphine compound, a sulfide compound, a mercaptan compound, a ketone compound, and an amide compound may be used, but the present invention is not limited to this. These activity inhibitors can be mixed with the inorganic fine particles (B) and heated at a temperature of 90 to 180 ° C. for 4 to 24 hours before use.

When such inorganic fine particles (B) are used, the inorganic fine particles (B) are aggregated and reaggregated when blended with the component (A1), the component (A2), or (C) a compound having an ethylenic double bond. Is suppressed, and the ink scraping property on the plate surface is improved by the blade of the pad printing machine.

The inorganic fine particles (B) are preferably contained in an amount of 3% by mass or more in 100% by mass of the photosensitive resin composition in order to impart abrasion resistance, and 70% by mass or less in order to enable the formation of a layer. Is preferable. The content of the inorganic fine particles (B) is more preferably 8% by mass or more, and more preferably 60% by mass or less.

It is also possible to introduce an ethylenic double bond onto the surface of the inorganic fine particles (B) using a surface modifier. Examples of such modifiers include (3-acroylpropyl) trimethoxysilane, metachloropropyltrimethoxysilane, metachloropropyltriethoxysilane, metachlorooxymethyltriethoxysilane, and metachlorooxymethyltrimethoxysilane. However, this is not the case. By surface-modifying the inorganic fine particles (B) with an ethylenic double bond, the inorganic fine particles (B) become uniform and aggregate when mixed with the component (A1), the component (A2), or the compound having the (C) ethylenic double bond. Reaggregation can be suppressed.

The photosensitive resin composition of the present invention contains (C) a compound having an ethylenic double bond.

Specific examples of the (C) ethylenically double bond-containing compound preferably used include, but are not limited to, the following.

For example, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acryloy. Loxyethyl phthalic acid, neopentyl glycol- (meth) acrylic acid-benzoic acid ester, (meth) acryloylmorpholine, styrene and its derivatives, vinylpyridine, N-vinyl-2-pyrrolidone, β- (meth) acryloyloxyethyl Hydrogen phthalate, N-phenylmaleimide and its derivatives, N- (meth) acrylic oxysuccinimide, (meth) -2-naphthyl acrylate, N-phenyl (meth) acrylamide, divinylethylene urea, divinylpropylene urea, vinyl caprolactam , Vinyl carbazole, bicyclopentenyl (meth) acrylate, 1-vinyl imidazole, 2-methyl-1-vinyl imidazole, (2-methyl-ethyldioxolan-4-yl) methyl acrylate, imide acrylate, (2-oxy-1) , 3-Dioxolan-4-yl) methyl (meth) acrylate, 2- (oxydiimidazolidine-1-yl) ethyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, methyl (Meta) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, chloroethyl (Meta) acrylate, chloropropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy Dipropylene glycol (meth) acrylate, (meth) acrylamide, diacetone (meth) acrylamide, N, N'-methylenebis (meth) acrylamide, 2,2-dimethylaminoethyl (meth) acrylate, 2,2-diethylaminoethyl (meth) ) Acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylic ami Do, compounds having only one ethylenic double bond such as 2-hydroxyethyl (meth) acrylate, di (meth) acrylate of polyethylene glycol such as diethylene glycol di (meth) acrylate, trimethyl propantri (meth) acrylate. , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol diglycidyl ether with ethylenic double bonds such as unsaturated carboxylic acids and unsaturated alcohols and active hydrogen. Multivalent (meth) obtained by addition reaction of unsaturated epoxy compounds such as polyvalent (meth) acrylate and glycidyl (meth) acrylate obtained by addition reaction of compounds with compounds having active hydrogen such as carboxylic acid and amine. ) Polyvalent (meth) acrylamide such as acrylate, methylenebis (meth) acrylamide, polyvalent vinyl compound such as divinylbenzene, and compounds having two or more ethylenic double bonds.

Among these (C) ethylenic double bond-containing compounds, those having one or more hydroxyl groups in the molecule have good compatibility with the components (A1) and (A2), and the extracted water is also good. The dispersibility of the inorganic fine particles (B) in the pH range of 5.5 to 8.5 is also good, and a uniform composition can be produced when blended in the photosensitive resin composition. Examples of such (C) ethylenic double bond-containing compound include 2-hydroxy-3-phenoxypropyl (meth) acrylate, [4- (hydroxymethyl) cyclohexyl] methyl (meth) acrylate, and 2-hydroxyethyl (meth). ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, β-hydroxy-β'-(meth) acryloyloxyethyl phthalate, 3 -Chloro-2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate and the like can be mentioned.

Further, the (C) ethylenic double bond-containing compound having two or more hydroxyl groups in the molecule can suppress the swelling of the intaglio printing plate due to the organic solvent of the ink used for pad printing due to the hydrogen bond of the hydroxyl groups. Examples of such a compound include, but are not limited to, glycerin mono (meth) acrylate and pentaerythritol mono (meth) acrylate.

The content of these (C) ethylenic double bond-containing compounds is preferably 5 to 200 parts by mass with respect to 100 parts by mass in total of the components (A1) and (A2). When the amount is 5 parts by mass or more, the printing plate can be used without swelling when printing with ink, and when the amount is 200 parts by mass or less, the photosensitive resin composition can be easily molded, which is preferable. .. The ethylenic double bond-containing compound (C) is more preferably contained in an amount of 10 parts by mass or more, more preferably 20 parts by mass or more, based on 100 parts by mass of the total of the components (A1) and (A2). The content of the (C) ethylenic double bond-containing compound is more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less.

The (C) ethylenic double bond-containing compound preferably contains both an acryloyl group and a meta-acryloyl group, and (C) the number of meta-acryloyl groups in the (C) ethylenic double bond-containing compound is larger than the number of acryloyl groups. Is preferable. In general, metaacryloyl groups have a slower reaction rate than acryloyl groups. Therefore, when ultraviolet rays are irradiated through the positive film, the recesses of the relief become deep due to the large number of meta-acryloyl groups. The screen stitch makes it easy to adjust the depth of the recess.

Further, the photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. (D) As the photopolymerization initiator, any one that can polymerize a polymerizable carbon-carbon unsaturated group by light can be used. Among them, those having a function of generating radicals by autolysis or hydrogen extraction by light absorption are preferably used. (D) Examples of the photopolymerization initiator include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, diacetyls and the like.

The blending amount of the photopolymerization initiator (D) is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the components (A1) and (A2). When it is 0.1 part by mass or more, the formability of the relief image is improved, and when it is 20 parts by mass or less, the precipitation of the photopolymerization initiator can be suppressed. The blending amount of the (D) photopolymerization initiator is more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more. Further, the blending amount of the (D) photopolymerization initiator is more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less.

The photosensitive resin composition of the present invention contains ethylene glycol, diethylene glycol, triethylene glycol, glycerin and its derivatives, trimethylolpropane and its derivatives, trimethylolethane and trimethylolethane as compatibility aids for enhancing compatibility and flexibility. It is also possible to optionally add polyhydric alcohols such as the derivative, pentaerythritol and the derivative thereof. It is preferable to add 30% by mass or less of these polyhydric alcohols to the entire photosensitive resin composition. In particular, by improving the compatibility, it is possible to suppress turbidity of the resin composition and bleed-out of low molecular weight components.

Further, in an intaglio printing plate formed from a photosensitive resin printing plate original plate using the photosensitive resin composition of the present invention, light scattering in the photosensitive resin layer is caused in order to form recesses having a good shape. An ultraviolet absorber may be added for the purpose of suppressing. Preferred ultraviolet absorbers include benzotriazole-based, triazine-based, and benzophenone-based compounds, and one or more of these can be used. The amount of the ultraviolet absorber to be blended is preferably in the range of 0.001 to 5% by mass with respect to the total photosensitive resin composition.

Further, in order to increase the thermal stability of the photosensitive resin composition of the present invention, a conventionally known polymerization inhibitor can be arbitrarily added. Preferred polymerization inhibitors include phenols, hydroquinones, catechols, N-nitrosamine derivatives and the like. The blending amount of these is preferably in the range of 0.001 to 5% by mass with respect to the total photosensitive resin composition.

In addition, dyes, pigments, surfactants, defoamers, fragrances and the like can be arbitrarily added to the photosensitive resin composition of the present invention as other components.

The photosensitive resin laminate of the present invention includes an adhesive layer (G), a photosensitive resin layer (F) formed from the photosensitive resin composition of the present invention, and a protective layer on at least the support (E). They are stacked in order. The photosensitive resin printing plate original plate of the present invention is formed by using the photosensitive resin laminate.

As the support (E), a plastic sheet such as polyester, a synthetic rubber sheet such as styrene-butadiene rubber, or a metal plate such as steel, stainless steel, or aluminum can be used. To put the ink on and scrape it off with a metal doctor blade, or to put ink in a ring-shaped ceramic or special metal edged ink cup that acts as a doctor blade and scrape off the plate surface with an ink cup. It is preferable to use a metal plate so that the support is not deformed by the force of scraping.

The thickness of the support is not particularly limited, but is preferably in the range of 100 to 500 μm from the viewpoint of handleability. If it is 100 μm or more, the support is suppressed from being deformed, and if it is 500 μm or less, the handleability is improved.

The support (E) is preferably easily adhered for the purpose of improving the adhesiveness with the photosensitive resin layer (F). Examples of the easy-adhesion treatment method include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment by coating, etc., but providing an adhesive layer (G) by coating is a viewpoint of adhesiveness. It is preferable from.

The adhesive layer (G) is not particularly limited as long as it improves the adhesiveness of the support (E) and the photosensitive resin layer (F). The adhesive layer (G) preferably contains at least a part of the structural units contained in the photosensitive resin layer (F), so that the adhesiveness is further improved. As such a common structural unit, a polymer compound having solubility in a solution containing a lower alcohol is exemplified. Further, as the soluble polymer compound, a polyamide resin containing a unit of ε-caprolactam can be preferably mentioned.

The photosensitive resin layer (F) is formed from the photosensitive resin composition of the present invention. The thickness of the photosensitive resin layer (F) is preferably 0.01 mm or more, more preferably 0.02 mm or more, from the viewpoint of having a sufficient relief depth and improving printability. On the other hand, the thickness of the photosensitive resin layer (F) is preferably 1 mm or less, more preferably 0.7 mm or less, from the viewpoint of cost and resource saving.

The photosensitive resin printing plate original plate of the present invention preferably has a cover film (H) as a protective layer on the photosensitive resin layer (F) from the viewpoint of surface protection and prevention of adhesion of foreign substances and the like. The photosensitive resin layer (F) may be in direct contact with the cover film (H), or may have one or more layers between the photosensitive resin layer (F) and the cover film (H). good. Examples of the layer between the photosensitive resin layer (F) and the cover film (H) include a peeling auxiliary layer (I) provided for the purpose of preventing adhesion on the surface of the photosensitive resin layer.

The material of the cover film (H) is not particularly limited, but a plastic sheet such as polyester or polyethylene is preferably used. The thickness of the cover film (H) is not particularly limited, but a range of 10 to 150 μm is preferable from the viewpoint of handleability and cost. Further, the surface of the cover film may be roughened for the purpose of improving the adhesion of the original film.

Next, the photosensitive resin composition of the present invention and a method for producing a photosensitive resin printing original plate using the same will be described. For example, after the component (A1) and / or the component (A2) is heated and dissolved in a mixed solvent containing water as a main component, (C) an ethylenic double bond-containing compound, (D) a photopolymerization initiator and necessary Add plasticizers and other additives accordingly, stir and mix well. Then, the inorganic fine particles (B) are added, mixed and dispersed to obtain a photosensitive resin composition solution.

Examples of the method for dispersing the inorganic fine particles include a mechanical stirring method, an ultrasonic dispersion method, a high-pressure dispersion method, and a media dispersion method. Among these, a media dispersion method capable of highly dispersing inorganic fine particles is preferable.

In the photosensitive resin layer (F) made of the photosensitive resin composition, the photosensitive resin composition solution obtained by the above method is cast on a support (E) having an adhesive layer (G) and dried. Can be obtained by After that, the photosensitive resin printing plate original plate can be obtained by bringing the cover film (H) coated with the peeling auxiliary layer (I) into close contact with the photosensitive resin layer (F). Further, a photosensitive resin printing plate original plate can also be obtained by producing a photosensitive resin sheet by dry film formation and laminating the photosensitive resin sheet so as to sandwich the photosensitive resin sheet between the support (E) and the cover film (H). Further, it is also possible to provide a photosensitive resin composition containing no inorganic fine particles (B) between the adhesive layer (G) and the photosensitive resin layer (F).

When the photosensitive resin printing plate original plate has the peeling auxiliary layer (I), the method for forming the peeling auxiliary layer (I) is not particularly limited, but the peeling auxiliary layer (I) component is dissolved in a solvent for the convenience of forming a thin film. A method of applying the prepared solution on the cover film (H) to remove the solvent is particularly preferable. Examples of the method for removing the solvent include hot air drying, far infrared drying, and natural drying. The solvent for dissolving the peeling auxiliary layer (I) component is not particularly limited, but water or alcohol, or a mixture of water and alcohol is preferably used.

Next, a printing plate formed by using the photosensitive resin printing plate original plate of the present invention will be described. The printing plate of the present invention can be obtained by exposing and developing the above-mentioned photosensitive printing plate original plate of the present invention.

When the photosensitive resin printing plate original plate has a cover film (H), the cover film (H) is peeled off, a positive original image film is brought into close contact with the photosensitive resin layer (F), and the photosensitive resin layer (F) is irradiated with ultraviolet rays. F) is photocured. Ultraviolet irradiation can be carried out using a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like, which can usually irradiate a wavelength of 300 to 400 nm.

Next, a halftone dot screen film of 300 lines and 90% is brought into close contact with the screen and irradiated with ultraviolet rays to form screen stitches in the recesses and adjust the depth of the recesses to be appropriate.

Next, the photosensitive printing plate original plate is immersed in a developing solution, and a relief image is formed on the substrate by a brush-type developing device that scrubs and removes the uncured portion with a brush. It is also possible to use a spray-type developing device in addition to the brush-type developing device. As the developing solution, water or water to which a surfactant is added can be used.

The liquid temperature during development is preferably 15 to 40 ° C. After forming the relief image, it is dried at 50 to 70 ° C. for about 10 minutes, and if necessary, further treated with active light in the atmosphere or vacuum to obtain an intaglio printing plate.

The photosensitive resin composition of the present invention is most suitable for use in a photosensitive resin printing plate original plate for intaglio printing or pad printing, but is used for lithographic printing, letterpress printing, stencil printing, and photoresist. It can also be used as.

[Examples 2 to 11]
Hereinafter, the present invention will be described in detail with reference to Examples. However, Examples 1 to 7 and 9 to 14 shall be read as reference examples.

<Synthesis of polyamide (A1) having a hydrophilic group>
Synthesis example 1:
10 parts by weight of ε-caprolactam, 90 parts by weight of nylon salt of N- (2-aminoethyl) piperazine and adipic acid and 100 parts by weight of water were placed in a stainless steel autoclave, and the internal air was replaced with nitrogen gas at 180 ° C. After heating for 1 hour, water was removed to obtain polyamide 1 having a hydrophilic group as a component (A1) and basic nitrogen in the main chain. The content of alicyclic diamine residues was 39 mol%.

Synthesis example 2:
60 parts by weight of an equimolar salt of α, ω-diaminopolyoxyethylene and adipic acid obtained by adding acrylonitrile to both ends of polyethylene glycol having a number average molecular weight of 600 and hydrogen reducing it, and 20 parts by weight of ε-caprolactam. And 20 parts by weight of an equimolar salt of hexamethylenediamine and adipic acid was melt-polymerized, and then water was removed to obtain a polyamide 2 having a hydrophilic group as a component (A1) and a polyether segment in the main chain. ..

Synthesis example 3:
10 parts by mass (30 mol%) of ε-caprolactam, 8 parts by mass (20 mol%) of N- (2-aminoethyl) piperazine, 6 parts by mass (15.4 mol%) of 1,3-bis (aminomethyl) cyclohexane , 1,4-Cyclohexanedicarboxylic acid 18 parts by mass (34.6 mol%) was placed in a stainless steel autoclave, the internal air was replaced with nitrogen gas, and then heated at 180 ° C. for 1 hour to remove water (34.6 mol%). A1) Polyamide 3 having a hydrophilic group as a component and basic nitrogen in the main chain was obtained. The content of the alicyclic diamine residue was 35.4 mol%, and the content of the alicyclic dicarboxylic acid was 34.6 mol%.

<Synthesis of modified partially saponified polyvinyl acetate (A2) having a functional group that can be crosslinked by a radical reaction in the side chain>
Synthesis example 4:
Partially saponified polyvinyl acetate "Gosenol" (registered trademark) KL-05 (polymerization degree about 500, saponification degree 78-82 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. is swollen in acetone and succinic anhydride. 1.0 mol% was added, and the mixture was stirred at 60 ° C. for 6 hours to add a carboxyl group to the molecular chain. The polymer was washed with acetone to remove unreacted succinic anhydride and dried. The acid value was measured and found to be 10.0 mgKOH / g. 100 parts by weight of this polymer was dissolved in 200 parts by weight of a mixed solvent of ethanol / water = 30/70 (weight ratio) at 80 ° C. To this, 6 parts by weight of glycidyl methacrylate was added to introduce a functional group capable of cross-linking into partially saponified polyvinyl acetate by a radical reaction. From the analysis results by the potential difference drip method, it was confirmed that the carboxyl group in the polymer reacted with the epoxy group of glycidyl methacrylate and the methacryloyl group was introduced into the side chain of the polymer, and it was possible to crosslink by the radical reaction which is the component (A2). A modified partially saponified polyvinyl acetate 1 having a capable functional group in the side chain was obtained. The obtained modified partially saponified polyvinyl acetate contained 79 mol% of the structure (I), 20 mol% of the structure (II), and 1 mol% of the structure (III).

Synthesis example 5:
A polymer containing 1 mol% of methacrylic acid as a copolymerization unit in vinyl acetate was saponified to obtain an anion-modified polyvinyl acetate having an average polymerization degree of 650 and a saponification degree of 75 mol%. 100 parts by weight of this polymer was dissolved in 200 parts by weight of a mixed solvent of ethanol / water = 30/70 (weight ratio) at 80 ° C. To this, 6 parts by weight of glycidyl methacrylate was added to introduce a functional group capable of cross-linking into partially saponified polyvinyl acetate by a radical reaction. From the analysis results by the potential difference drip method, it was confirmed that the carboxyl group in the polymer reacted with the epoxy group of glycidyl methacrylate and the metachloro group was introduced into the side chain of the polymer, and it was possible to crosslink by the radical reaction which is the component (A2). A modified partially saponified polyvinyl acetate 2 having a capable functional group in the side chain was obtained. The obtained modified partially saponified polyvinyl acetate contained 79 mol% of the structure (I), 20 mol% of the structure (II), and 1 mol% of the structure (III).

Synthesis example 6:
Partially cross-linked polyvinyl acetate "Gosenol" (registered trademark) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. KL-05 (polymerization degree about 500, saponification degree 78-82 mol%) 100 parts by weight into 100 parts by weight of water Dissolve, add 15 parts by weight of N-methylol acrylamide, add 1 part by weight of phosphoric acid as an acid catalyst, adjust by stirring at 100 ° C. for 4 hours, then remove water to remove water, acrylic based with N-methylol group. A modified partially saponified polyvinyl acetate 3 having a functional group in the side chain which can be crosslinked by a radical reaction which is a component (A2) obtained by the reaction with the compound was obtained. The obtained modified partially saponified polyvinyl acetate contained 79 mol% of the structure (I), 20 mol% of the structure (II), and 1 mol% of the structure (III).

Inorganic fine particles (B):
The powder of the inorganic fine particles shown in Table 1 was used. Of these, the inorganic fine particles of Nos. 1 to 7 are amorphous silica. The average particle size was measured using LA-500 manufactured by HORIBA, Ltd. with water as the dispersion medium and a refractive index set to 1.1. The maximum particle size was set to 20.0 μm by passing through a sieve of 20.0 μm mesh. The specific surface area was measured by the BET method using Tristar 3000 manufactured by Shimadzu Corporation.

The pH of the water extraction of the inorganic fine particles (B) was measured by dispersing 10% by mass of the powder of the inorganic fine particles in distilled water, stirring for 30 minutes, and then measuring the supernatant water with D-71LAB manufactured by Horiba Seisakusho Co., Ltd.

(C) Ethylene double bond-containing compound (indicated as "component (C)" in Table 2)
Glycerol dimethacrylate, a compound having an ethylenic double bond with one hydroxyl group (Light Ester G101P manufactured by Kyoeisha Chemical Co., Ltd.)
-2-Hydroxypropyl methacrylate (light ester HOP manufactured by Kyoeisha Chemical Co., Ltd.)
Glycerol monomethacrylate, a compound having an ethylenic double bond with two hydroxyl groups (Blemmer GLM manufactured by NOF CORPORATION)
Isobutylmethacrylate, a compound having an ethylenic double bond that does not have a hydroxyl group (Light Ester IB manufactured by Kyoeisha Chemical Co., Ltd.)
-Trietierenglucol dimethacrylate (Light Ester 3EG manufactured by Kyoeisha Chemical Co., Ltd.).

(D) Photopolymerization Initiator (Indicated as "(D) component" in Table 2)
2,2-dimethoxy-1,1-diphenylethane-1-one (IRGACURE651 manufactured by BASF)
-Polymerization inhibitor: N- (ammonium oxy) -N-nitrosophenylamine (Kuperon manufactured by Kanto Chemical Co., Inc.)
-Ultraviolet absorber: 2,4-di-tert-butyl-6- (5-chloro-2H-1,2,3-benzotriazole-2-yl) phenol (TINUVIN326, manufactured by BASF).

<Preparation of support (E) having adhesive layer (G)>
66 parts by mass of "Vinitol" (registered trademark) # 284 (manufactured by Nagoya Yuka Co., Ltd.) and 2 parts by mass of hexamethylenetetramine (manufactured by Kanto Chemical Co., Ltd.) were mixed with 16 parts by mass of dimethylformamide and 16 parts by mass of xylene. A solution prepared by mixing 90 parts by mass of bisphenol A "jER" (registered trademark) 834 (manufactured by Mitsubishi Chemical Corporation) with a solvent of 30 parts by mass of dimethylformamide and 30 parts by mass of xylene was added to the solution for the adhesive layer (G). Coating liquid 1 was obtained.

20 parts by mass of "Amilan" (registered trademark) CM833 (manufactured by Toray Co., Ltd.), 50 parts by mass of ethanol, 10 parts by mass of water, 10 parts by mass of dimethylformamide, and 50 parts of benzyl alcohol of "CJPARL" (manufactured by Automotive & Industrial Systems). It was mixed in a mixed solvent by mass at 70 ° C. for 2 hours and dissolved. Then, at 25 ° C., 5 parts by mass of bisphenol A "jER" (registered trademark) 834 (manufactured by Mitsubishi Chemical Corporation) and 0.3 parts by mass of dicyanodiamide (manufactured by Kanto Chemical Co., Inc.) were added for the adhesive layer (G). Coating liquid 2 was obtained.

The coating liquid 1 for the adhesive layer (G) is applied on an iron plate (manufactured by Nippon Steel & Sumitomo Metal Corporation) having a thickness of 250 μm, which is the support (E), with a bar coater so that the film thickness becomes 10 μm after drying. After removing the solvent by heating in an oven at 180 ° C. for 3 minutes, the coating liquid 2 for the adhesive layer (G) is applied on it with a bar coater so that the dry film thickness is 10 μm, and the oven at 160 ° C. After heating for 3 minutes, a support (E) having an adhesive layer (G) was obtained.

<Cover film (H)>
A 100 μm-thick “Lumirror” (registered trademark) S10 (polyester film, manufactured by Toray Industries, Inc.) was used as the cover film (H).

[Evaluation method]
The evaluation in each Example and Comparative Example was performed by the following method.

(1) Abrasion resistance Only the polyester film of the cover film (H) is peeled off from the 7 cm × 14 cm photosensitive printing original plate (the outermost surface of the photosensitive printing original plate after peeling is a peeling auxiliary layer having a dry film thickness of 1 μm), and positive. The film was brought into close contact with vacuum and exposed with a chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Oslam Co., Ltd.) under the condition that the gray scale sensitivity was 13 ± 1 step (main exposure), and the photosensitive resin plate of 7 cm × 14 cm. The entire surface was photocured. After that, it was developed with water at a liquid temperature of 25 ° C. for 1 minute with a brush-type developing device, dried at 60 ° C. for 10 minutes, and then further exposed with a chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Osram Co., Ltd.) as the main exposure. After exposure under the conditions, a printing plate for evaluation of wear resistance was obtained.

The printed plate thus obtained was attached to hermetic 6-12 universal (manufactured by TAMPORINT) and squeezed 50,000 times using PAD-PLV-1 ink white (manufactured by Navitas) as the ink, and the printing plate was worn. The depth was measured. When the worn depth is 10 μm or more, the recesses filled with ink become shallow during printing, which causes printing defects. It is preferable that the wear depth is less than 10 μm, more preferably 8 μm or less, and further preferably 6 μm or less.

(2) Scraping property of ink by blade The cover film (H) is peeled off from the 7 cm × 14 cm photosensitive printing original plate, the positive film is vacuum-adhered, and the chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Oslam Co., Ltd.) ) Was exposed under the condition that the gray scale sensitivity was 13 ± 1 step (main exposure), and the entire surface of the 7 cm × 14 cm photosensitive resin plate was photocured. After that, it was developed with water at a liquid temperature of 25 ° C. for 1 minute with a brush-type developing device, dried at 60 ° C. for 10 minutes, and then further exposed with a chemical lamp FL20SBL-360 20 watts (manufactured by Mitsubishi Electric Oslam Co., Ltd.) as the main exposure. After exposure under the conditions, a printing plate for evaluating the scratchability of the ink was obtained.

The printed plate thus obtained was mounted on a hermetic 6-12 average (manufactured by TAMPORINT), squeezed once using PAD-PLV-1 ink white (manufactured by Navitas) as the ink, and remained on the surface of the printing plate. The thickness of the ink was measured at 10 points, and the average value was obtained. If the ink residue is 1 μm or more on the entire surface of the squeegee portion, printing defects occur because the ink is transferred to other than the printed image portion. If there is no above, it is marked as ○.

Example 1
<Preparation of composition solution 1 for photosensitive resin composition 1>
In a three-necked flask equipped with a stirring spatula and a cooling tube, the component (A1) shown in the column of Example 1 in Table 2 was added, and "Solmix" (registered trademark) H-11 (alcohol mixture, Japan) was added. After mixing 50 parts by mass of a mixed solvent of 50 parts by mass of alcohol (manufactured by Alcohol Co., Ltd.) and 50 parts by mass of water, the mixture was heated at 90 ° C. for 2 hours with stirring to dissolve the component (A1). After cooling to 70 ° C., other components in the column of Example 1 in Table 2 were added thereto, and the mixture was stirred for 30 minutes. After further cooling to 25 ° C., the mixture was dispersed using a continuous media disperser (NANO GRAIN MILL, manufactured by Asada Iron Works Co., Ltd.) to obtain a composition solution 1 for the photosensitive resin composition 1.

<Manufacturing of photosensitive resin printing plate original plate 1>
The obtained composition solution 1 was cast on a support (E) having the adhesive layer (G) and dried at 60 ° C. for 2.5 hours. At this time, the plate thickness (iron plate + photosensitive resin layer) after drying was adjusted to 0.5 mm. A mixed solvent of water / ethanol = 50/50 (weight ratio) is applied onto the photosensitive resin layer (F) thus obtained, and a cover film (H) is pressure-bonded to the surface thereof for photosensitive resin printing. I got the original version 1. Table 2 shows the results of evaluating the characteristics of the printing plate by the above method using the obtained photosensitive printing original plate 1.

Examples 2 to 15
A photosensitive resin sheet and a photosensitive printing original plate were produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as shown in Examples 2 to 15 in Table 2. The evaluation results are shown in Table 2.

Comparative Examples 1 to 4
A photosensitive resin sheet and a photosensitive printing original plate were produced in the same manner as in Example 1 except that the composition of the photosensitive resin composition was changed as shown in Comparative Examples 1 to 4 in Table 2. Comparative Example 5 whose evaluation results are shown in Table 2.
A photosensitive resin composition was prepared as shown in Comparative Example 5 in Table 2 using the polyamide "Amilan" (registered trademark) CM9000 (manufactured by Toray Industries, Inc.) having no hydrophilic group, but it could not be water-developed, so it was evaluated. could not.

Comparative Example 6
Partially saponified polyvinyl acetate "Gosenol" (registered trademark) KL-05 (polymerization degree about 500, saponification degree 78-82 mol%, Japan synthesis) having no functional group that can be crosslinked by radical reaction in the side chain A photosensitive resin composition was prepared as shown in Comparative Example 6 in Table 2 using (manufactured by Chemical Industry Co., Ltd.). The evaluation results are shown in Table 2.

Comparative Example 7
The composition of the photosensitive resin composition was prepared as shown in Comparative Example 7 in Table 2, but could not be evaluated because it could not be formed into a sheet.

Claims (10)

(A1) Polyamide having a hydrophilic group, (B) Inorganic fine particles having an average particle size of 0.5 μm or more and 4 μm or less and a sphericity of 0.9 or more, and (C) having an ethylenic double bond. A photosensitive resin composition containing a compound and (D) a photopolymerization initiator , wherein the (A1) polyamide having a hydrophilic group has a piperazine ring . The photosensitive resin composition according to claim 1, wherein the polyamide having the (A1) hydrophilic group has an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue. The specific surface area of the (B) inorganic fine particles is 10 m. ² The photosensitive resin composition according to claim 1 or 2, which is / g or less. The photosensitive resin composition according to any one of claims 1 to 3, wherein the maximum particle size of the (B) inorganic fine particles is 20 μm or less. The photosensitive resin composition according to any one of claims 1 to 4, wherein the inorganic fine particles (B) are amorphous silica. The photosensitive resin composition according to any one of claims 1 to 5, wherein the pH of the extracted water of (B) is 5.5 to 8.5. The photosensitive resin composition according to any one of claims 1 to 6, wherein the compound having an ethylenic double bond (C) has one or more hydroxyl groups in the molecule. The photosensitive resin composition according to any one of claims 1 to 7, wherein the compound having an ethylenic double bond (C) has two or more hydroxyl groups in the molecule. A photosensitive resin printing plate original plate in which an adhesive layer, a photosensitive resin layer formed from the photosensitive resin composition according to any one of claims 1 to 8, and a protective layer are sequentially laminated on at least a support. The photosensitive resin printing plate original plate according to claim 9, which is used for intaglio printing or pad printing.