JP2018141977A - Photosensitive resin laminate, and photosensitive resin printing plate precursor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin laminate and a photosensitive resin printing plate precursor capable of producing an intaglio printing plate which enables water development and has good adhesion to a support, provides a printed matter having a sharp contour, and is excellent in abrasion resistance and scraping properties of ink on a plate surface.SOLUTION: A photosensitive resin laminate has a photosensitive resin layer provided on a support, where the photosensitive resin layer has a thickness of 50 μm or less and is formed of a double-layer structure, a first photosensitive resin layer on the support side contains no inorganic fine particle, a second photosensitive resin layer provided on the first photosensitive resin layer contains inorganic fine particles having an average particle diameter of 0.5 μm or more and 4 μm or less, a thickness in the second photosensitive resin layer is thicker than a thickness of the first photosensitive resin layer, and the photosensitive resin layer contains a resin enabling water development.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin laminate and a photosensitive resin intaglio printing plate precursor.

  A photosensitive resin printing plate precursor using a photosensitive resin laminate having a layer formed of a photosensitive resin composition is generally composed of a soluble polymer, a photopolymerizable unsaturated group-containing monomer, and photopolymerization in the photosensitive resin layer. It contains an agent as an essential component, and by irradiating the photosensitive resin layer with ultraviolet light through negative and positive original film, it forms a part that dissolves in the solvent and a part that does not dissolve in the photosensitive resin layer. A relief image is formed and used as a printing plate.

  Pad printing using an intaglio printing plate places ink on the plate surface and scrapes it off with a metal doctor blade, or in a ring-shaped ceramic or special metal edge ink cup that acts as a doctor blade. It is a type of offset printing that prints by putting ink and scraping the surface of the plate with an ink cup to transfer the ink filled in the recesses to a flexible pad surface such as silicone rubber and pressing it onto the substrate. . Intaglio printing plates used for pad printing are required to have abrasion resistance on the plate surface because the ink on the plate surface is scraped off with a doctor blade or an ink cup because of the printing method. As a photosensitive resin composition that requires such abrasion resistance, a photosensitive resin composition in which inorganic fine particles that are abrasive particles are blended is proposed as shown in Patent Document 1.

  Moreover, in the pad printing plate, as shown in Patent Document 2, a screen eye is formed in the recess and the amount of ink transferred is adjusted by the depth of the screen eye. Is used for pad printing, the screen eyes are transferred to the printed matter, and the image reproducibility is lowered. Therefore, as shown in Patent Document 3, a photosensitive resin intaglio printing original plate having a photosensitive resin layer that is a thin relief layer that does not form a screen is known.

  By the way, from the viewpoint of facilitating plate making, the photosensitive resin printing plate precursor is required to develop the image-exposed photosensitive resin layer with water. Examples thereof include a photosensitive resin composition containing a water-soluble or water-swellable polymer as a soluble polymer as shown in Patent Document 4 or 5.

Japanese Patent Laid-Open No. 2-6957 JP-A-9-171259 JP-A-5-165200 JP 2016-139130 A JP 2000-162770 A

  However, when a photosensitive resin composition containing inorganic fine particles is directly formed on a support for the purpose of forming a thin relief layer that does not form a screen, a photosensitive resin composition containing the support and inorganic fine particles is formed. There was a problem that the adhesion of objects was poor. In addition, a resin that is soluble only in an organic solvent is preferably selected in order to impart abrasion resistance to the plate surface, but the plate making conditions of the photosensitive resin printing plate material including a step of eluting the undissolved portion using a developer However, using an organic solvent is not preferable from the viewpoint of workability.

  The present invention has been made in view of the above circumstances, and can be developed with water, has good adhesion to a support, and has excellent image reproducibility, a photosensitive resin laminate for photosensitive printing, and a photosensitive resin intaglio. The issue is to provide a printing plate precursor.

  In order to achieve the above object, the photosensitive resin laminate of the present invention has the following constitution. A photosensitive resin laminate in which a photosensitive resin layer is provided on a support, wherein the photosensitive resin layer is at least above the first photosensitive resin layer on the support side and the first photosensitive resin layer. An inorganic fine particle having a multilayer structure including a provided second photosensitive resin layer, wherein the first photosensitive resin layer does not contain inorganic fine particles and the second photosensitive resin layer has an average particle diameter of 0.5 μm or more and 4 μm or less. The thickness of the second photosensitive resin layer is larger than the thickness of the first photosensitive resin layer, and the thickness of the photosensitive resin layer is 20 μm or more and 50 μm or less, and the photosensitive resin layer is water. It contains a developable resin.

  According to the present invention, it is possible to provide a photosensitive resin laminate and a photosensitive resin printing plate precursor capable of producing an intaglio printing plate capable of being developed with water, having good adhesion to a support and having excellent image reproducibility.

  Embodiments of the present invention will be described below.

  The photosensitive resin laminate of the present invention is a photosensitive resin laminate in which a photosensitive resin layer is provided on a support, and the thickness of the photosensitive resin layer is 20 μm or more and 50 μm or less, and includes at least two layers. The first photosensitive resin layer on the support side does not contain inorganic fine particles, and the second photosensitive resin layer provided above the first photosensitive resin layer has an average particle diameter of 0.5 μm or more. Containing inorganic fine particles of 4 μm or less, the thickness of the second photosensitive resin layer is greater than the thickness of the first photosensitive resin layer, and the photosensitive resin layer contains a water-developable resin Has been. The thickness of the photosensitive resin layer, and the thickness of the second photosensitive resin layer containing inorganic fine particles and the thickness of the first photosensitive resin layer not containing inorganic fine particles were observed with an optical microscope or a scanning electron microscope (SEM). It can be measured from a cross-sectional photograph of the photosensitive resin laminate. Specifically, the depth at which the inorganic fine particles are not observed from the surface of the second photosensitive resin layer (the surface away from the support) is measured, and this depth is the thickness of the second photosensitive resin layer. And Further, an interface at which inorganic fine particles of the second photosensitive resin layer are not observed is defined as a boundary between the first photosensitive resin layer and the second photosensitive resin layer, and a depth from the boundary to the support is defined as the first photosensitive resin layer. The thickness of the photosensitive resin layer can be obtained.

  As the support used in the present invention, a plastic sheet such as polyester, a synthetic rubber sheet such as styrene-butadiene rubber, and a metal plate such as steel, stainless steel, and aluminum can be used. Put ink in an ink cup with a ring-shaped ceramic or special metal edge to scrape with a metal doctor blade or with a metal doctor blade, and scrape the plate surface with an ink cup Therefore, it is preferable to use a metal plate support so that the support is not deformed by the force of scraping.

  Although the thickness of a support body is not specifically limited, From the viewpoint of handleability, the range of 100-500 micrometers is preferable. If it is 100 micrometers or more, it will be suppressed that a support body deform | transforms, and if it is 500 micrometers or less, handleability will improve.

  The support is preferably subjected to easy adhesion treatment for the purpose of improving adhesiveness with the photosensitive resin layer. Examples of the easy adhesion treatment method include mechanical treatment such as sandblasting, physical treatment such as corona discharge, and chemical treatment such as coating. However, it is preferable from the viewpoint of adhesiveness to provide an adhesive layer by coating. As such an adhesive layer, those shown in Japanese Patent Application Laid-Open No. 2008-257007 are known. For example, the adhesive layer contains at least a part of structural units included in the photosensitive resin layer. Further, the adhesiveness is improved. As such a common structural unit, a polymer compound having solubility in an aqueous solution is exemplified. Moreover, as a soluble high molecular compound, the polyamide resin containing the unit of (epsilon) -caprolactam can be mentioned preferably.

  In the present invention, the thickness of the photosensitive resin layer provided on the support is 20 μm or more and 50 μm or less. By making the thickness of the photosensitive resin layer 20 μm or more, it is possible to print with sufficient color intensity by pad printing. On the other hand, by making the thickness 50 μm or less, it can be transferred to a flexible pad surface such as silicone rubber. Thus, when the ink adhering surface of the pad is pressure-bonded to the printing medium, a decrease in print quality due to excessive crushing of the ink is suppressed. In addition, by setting this range, it is not necessary to form screen eyes in the recesses and adjust the amount of ink transferred according to the depth of the screen eyes, and the screen eyes formed by exposure and development in the recesses are not transferred to the printed matter. As a result, the outline of the printed material becomes sharp and the print quality is improved. The thickness of the photosensitive resin layer is preferably 23 μm or more, more preferably 25 μm or more. The thickness of the photosensitive resin layer is preferably 40 μm or less, more preferably 35 μm or less.

  The photosensitive resin layer in the present invention has a multilayer structure consisting of at least two layers, and the first photosensitive resin layer on the support side does not contain inorganic fine particles and is provided above the first photosensitive resin layer. The second photosensitive resin layer contains inorganic fine particles having an average particle diameter of 0.5 μm or more and 4 μm or less, and the thickness of the second photosensitive resin layer is larger than the thickness of the first photosensitive resin layer. The photosensitive resin layer has a multilayer structure including two or more layers including a first photosensitive resin layer and a second photosensitive resin layer. The first photosensitive resin layer is disposed on the support side and laminated on the support or the adhesive layer. The second photosensitive resin layer is disposed on the side opposite to the support of the first photosensitive resin layer. Another layer may be interposed between the first photosensitive resin layer and the second photosensitive resin layer, or the first photosensitive resin layer and the second photosensitive resin layer are directly laminated. May be.

  Since the first photosensitive resin layer does not contain inorganic fine particles, the first photosensitive resin layer can be satisfactorily adhered onto a support, particularly a support having an adhesive layer. Moreover, it is preferable that the thickness of the 1st photosensitive resin layer is 1 micrometer or more and 20 micrometers or less. By setting the thickness of the first photosensitive resin layer to 1 μm or more, it is possible to ensure adhesion with the support, and by setting it to 20 μm or less, the second photosensitive resin contains inorganic fine particles having wear resistance. It becomes possible to form the photosensitive resin layer with a sufficient thickness. The thickness of the first photosensitive resin layer is more preferably 3 μm or more and 15 μm or less.

  Next, the second photosensitive resin layer of the present invention comprises (A1) a polyamide having a hydrophilic group, (B) inorganic fine particles having an average particle diameter of 0.5 μm to 4 μm, and (C) an ethylenic double bond. A compound having (D) a photopolymerization initiator, or (A2) a modified partially saponified polyvinyl acetate having a functional group capable of crosslinking by a radical reaction in the side chain, (B) average It is preferable to contain inorganic fine particles having a particle size of 0.5 μm to 4 μm, (C) a compound having an ethylenic double bond, and (D) a photopolymerization initiator. Moreover, it is preferable that a 1st photosensitive resin layer contains the same component as a 2nd photosensitive resin layer except not containing the inorganic fine particle of (B) mentioned above. That is, the first photosensitive resin layer preferably contains (A1) a polyamide having a hydrophilic group, (C) a compound having an ethylenic double bond, and (D) a photopolymerization initiator. (A2) modified partially saponified polyvinyl acetate having a functional group that can be cross-linked by radical reaction in the side chain, (C) a compound having an ethylenic double bond, and (D) a photopolymerization initiator It is preferable to contain.

  Hereinafter, the photosensitive resin composition which comprises a 1st photosensitive resin layer and a 2nd photosensitive resin layer is demonstrated. As described above, the photosensitive resin composition constituting the first photosensitive resin layer is the same as the photosensitive resin composition constituting the second photosensitive resin layer except that it does not contain the inorganic fine particles (B). It contains the components, and the composition is basically the same except for the change in the composition ratio associated with not containing the inorganic fine particles (B). In the following description, the photosensitive resin composition constituting the second photosensitive resin layer is simply described as “photosensitive resin composition”.

  Examples of the water-developable resin include (A1) polyamide having a hydrophilic group or partially saponified polyvinyl acetate. Among them, (A1) polyamide having a hydrophilic group, or (A2) crosslinking by a radical reaction. Preferred is a modified partially saponified polyvinyl acetate having a functional group capable of forming in the side chain.

  As the (A1) component (A1), a polyamide having a hydrophilic group, a copolymerized polyamide that can easily introduce a hydrophilic group for imparting water developability is preferably used.

  (A1) The polyamide having a hydrophilic group has a function as a carrier resin for maintaining the form of the photosensitive resin composition in a solid state, and 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 component. Copolyamides containing 6-nylon and hydrophilic components and 6-nylon are chemically modified. Modified polyamides. Moreover, 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 a side chain described in JP-A-48-72250, and a copolymer containing a polyether segment described in JP-A-55-74537. Examples thereof include polyamides and polyamides having basic nitrogen described in JP-A-50-7605.

  Among the polyamides, polyamides containing basic nitrogen and / or polyamides containing polyether segments are preferably used. The polyamide having basic nitrogen is a polymer containing basic nitrogen in a part of the main chain or side chain. Basic nitrogen is a nitrogen atom constituting 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 performing condensation polymerization, polyaddition reaction or the like using a monomer having basic nitrogen alone or using another monomer.

  The basic nitrogen is preferably piperazine or an N, N-dialkylamino group, and more preferably piperazine. Specific examples of the monomer having basic nitrogen for providing the polyamide used in the present invention include N, N′-bis (aminomethyl) -piperazine, 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, '-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-carboxyhexyl) piperazine, N- (ω-carboxyhexyl) piperazine, N- (aminomethyl) -N- (carboxymethyl)- Methylamine, N- (β-aminoethyl) -N- (β-carboxyethyl) -methylamine, N- (aminomethyl) -N- (β-carboxyethyl) -isopropylamine, N, N′-dimethyl- There are ω-amino acids such as N- (aminomethyl) -N ′-(carboxymethyl) -ethylenediamine. In addition to these monomers, those polymerized in combination with diamine, dicarboxylic acid, ω-amino acid, lactam and the like can also be used. These monomer components containing basic nitrogen are all polyamide constituents, that is, 10 to 100 mol% with respect to the sum of aminocarboxylic acid units (including lactam as a raw material), dicarboxylic acid units and diamine units. It is preferable that it is 10 to 80 mol%. It is preferable for the amount to be 10 mol% or more because the water solubility is high and the compatibility with the component (C) is increased.

  Of the polyamides, polyamides containing alicyclic diamine residues and / or alicyclic dicarboxylic acid residues are preferred. By having an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue, the glass transition point of the polyamide is increased, and the wear resistance can be improved. The term “alicyclic group” as used herein refers to a cyclic structure containing carbon or nitrogen.

  Examples of the alicyclic diamine residue include isophorone diamine, 1,4-cyclohexane diamine, 1,3-cyclohexane diamine, 1,3-bis (aminomethyl) cyclohexane, 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) (Cyclohexyl) propane, 1,4-bis (3-aminopropyl) piperazine, N- (2-aminoethyl) piperazine, methylcyclohexanediamine, norbornanediamine, and tricyclodecanediamine.

  Examples of the alicyclic dicarboxylic acid residue include isophorone dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 2,3-norbornane dicarboxylic acid, 1,3-cyclohexane dicarboxylic 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-silane Rhohexanedicarboxylic acid, 2-methyl-3-propyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-butyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-3-propyl-1,4-cyclohexane Dicarboxylic acid, 2-ethyl-3-butyl-1,4-cyclohexanedicarboxylic acid, 2-methyl-3-tert-butyl-1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 2,6-decalin Dicarboxylic acid, 3-methyl-2,6-decalin dicarboxylic acid, 3-ethyl-2,6-decalin dicarboxylic acid, 3-propyl-2,6-decalin dicarboxylic acid, 3-butyl-2,6-decalin dicarboxylic acid 3,4-dimethyl-2,6-decalin dicarboxylic acid, 3,4-diethyl-2,6-decalin dicarboxylic acid, , 4-dipropyl-2,6-decalin dicarboxylic acid, 3,4-dibutyl-2,6-decalin dicarboxylic acid, 3,8-dimethyl-2,6-decalin dicarboxylic acid, 3,8-diethyl-2,6 -Decalin dicarboxylic acid, 3,8-dipropyl-2,6-decalin dicarboxylic acid, 3,8-dibutyl-2,6-decalin dicarboxylic acid, 3-methyl-4-ethyl-2,6-decalin dicarboxylic acid, 3 -Methyl-4-propyl-2,6-decalin dicarboxylic acid, 3-methyl-4-butyl-2,6-decalin dicarboxylic acid, 3-ethyl-4-butyl-2,6-decalin dicarboxylic acid.

  The polyamide used in the present invention is a polyamide containing 30 to 90 mol% of alicyclic diamine residue and / or alicyclic dicarboxylic acid residue and 20 mol% or more of alicyclic dicarboxylic acid residue. It is preferable. By containing the alicyclic diamine residue and / or alicyclic dicarboxylic acid residue in an amount of 30 mol% or more, the glass transition point of the polyamide can be improved and the wear 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 alicyclic dicarboxylic acid residue, the elastic modulus of the polyamide can be controlled and the printing plate precursor can be prevented. Moreover, by containing 20 mol% or more of alicyclic dicarboxylic acid residues, the glass transition point of polyamide can be improved and the wear resistance of the printing plate precursor can be improved.

The mol% of the alicyclic diamine residue and / or alicyclic dicarboxylic acid residue contained in the polyamide is the number of moles of the alicyclic residue relative to the total number of moles obtained from the aminocarboxylic acid, diamine, and dicarboxylic acid. The ratio is shown. 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. Analysis by ¹ H-NMR is a commonly performed analysis method, in which the mol% of each structural unit is calculated from the integral value.

  Moreover, as another aspect which comprises the photosensitive resin composition of this invention, the modified | denatured partially saponified polyvinyl acetate which has a functional group which can be bridge | crosslinked by radical reaction which is (A2) component is contained. Generally, as a functional group that can be crosslinked by such a radical reaction, a non-aromatic unsaturated carbon-carbon bond, especially an ethylenic double bond is often used, and a vinyl group or a (meth) acryloyl group is used. Is mentioned. By using the modified partially saponified polyvinyl acetate having a functional group that can be cross-linked by such a radical reaction in the side chain, the polymer is polymerized with the monomer component, so that the wear resistance is improved.

  As a method for introducing a functional group capable of crosslinking by such a radical reaction into the side chain of partially saponified polyvinyl acetate, for example, the method described in JP-A-3-274558 or JP-A-2007-79494 There is a method.

  In the method described in JP-A-3-274558, a partially saponified polyvinyl acetate is reacted with an acid anhydride to introduce a carboxyl group into a polymer side chain starting from the hydroxyl group of the partially saponified polyvinyl acetate. A functional group that can be crosslinked by a radical reaction by reacting an unsaturated epoxy compound with a carboxyl group is introduced, or a polymer obtained by copolymerizing vinyl acetate and an unsaturated carboxylic acid or salt thereof is partially saponified. In this method, a carboxyl group contained in the obtained anion-modified polyvinyl alcohol having a saponification degree of 60 to 90 mol% is reacted with an unsaturated epoxy compound to introduce a functional group capable of crosslinking by radical reaction. Among these, partially saponified polyvinyl acetate obtained by the former method is preferably used since the effects of the present invention are remarkably exhibited.

  The functional group capable of crosslinking by such a radical reaction is preferably present in the compound (A2) at 0.08 to 0.72 mol / kg, more preferably 0.12 to 0.36 mol / kg. It is. When it is 0.72 mol / kg or less, excellent water developability can be obtained, and when it is 0.08 mol / kg or more, a functional group capable of crosslinking by a radical reaction reacts. This is preferable because an effect such as improvement of relief chipping during development can be obtained. The thus obtained (A2) modified partially saponified polyvinyl acetate having a functional group capable of crosslinking by radical reaction 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 water developability is required for the partially saponified polyvinyl acetate having a functional group capable of being crosslinked by radical reaction, the unit of structure (I) is preferably 60 to 99 mol%, more preferably 70. -95 mol%. When the structural unit (I) is 60 mol% or more, sufficient water developability can be obtained, and when it is 99 mol% or less, 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 of a partially saponified polyvinyl acetate and an acrylic compound having an N-methylol group, and crosslinks to the side chain of the partially saponified polyvinyl acetate by a radical reaction. This is a method of introducing functional groups that can be used. The blending amount of the acrylic compound having an N-methylol group is preferably 2 to 40 parts by weight and more preferably 5 to 30 parts by weight with respect to 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. When the amount is 2 parts by weight or more, an effect such as a lack of relief at the time of development, which is improved by the reaction of a functional group capable of crosslinking by a radical reaction, is exhibited.

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

  The photosensitive resin laminate of the present invention includes both (A1) a polyamide having a hydrophilic group and (A2) a modified partially saponified polyvinyl acetate having a functional group capable of crosslinking by a radical reaction in the side chain. Can also be included.

  The second photosensitive resin layer contains inorganic fine particles (hereinafter referred to as “inorganic fine particles (B)”) having an average particle diameter of 0.5 μm or more and 4 μm or less. The inorganic fine particles (B) preferably have a sphericity of 0.9 or more. By using such inorganic fine particles (B) in the second photosensitive resin layer, it has excellent abrasion resistance and excellent ink scraping property when squeezed with a blade of a pad printing machine. can do.

  The inorganic fine particles (B) have an average particle diameter of 0.5 μm or more, so that wear resistance when bladed by a pad printing machine can be ensured, and by being 4 μm or less, squeezed by the blade of the pad printing machine. The ink on the surface of the plate can be scraped off. The average particle diameter of the inorganic fine particles (B) is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 1.0 μm or more. The average particle size is preferably 4 μm or less, more preferably 4.0 μm or less, further preferably 3 μm or less, and even more preferably 3.0 μm or less. In the present specification, the average particle diameter of the inorganic fine particles (B) is a median diameter measured by a laser diffraction scattering method.

  Furthermore, the surface roughness of the printing plate is small because the sphericity of the inorganic fine particles (B) is preferably 0.9 or more, more preferably 0.90 or more, and further preferably 0.90 to 1.0. Therefore, a better ink scraping property can be achieved. In the present invention, the sphericity is the observation of the shape of 50 inorganic fine particles (B) with a scanning electron microscope, the ratio of the shortest diameter / longest diameter of each inorganic fine particle is determined, and 50 phases are obtained. It is an arithmetic mean value.

  Examples of such inorganic fine particles (B) include simple metal fine particles, inorganic oxide particles, inorganic salt fine particles, fine particles composed of an organic component and an inorganic component. Among these, from the viewpoint of suppressing scattering of ultraviolet light when the photosensitive resin layer is irradiated with light and photocured, (A1) a polyamide having a hydrophilic group, which is an organic component contained in the photosensitive resin layer, ( A2) Comparison of refractive indexes of modified partially saponified polyvinyl acetate having a functional group in the side chain that can be crosslinked by radical reaction, (C) a compound having an ethylenic double bond, and (D) a photopolymerization initiator Nearly suitable silica particles are preferred. Furthermore, amorphous silica is more preferable from the viewpoint of safe handling.

  The method for producing such amorphous silica is not particularly limited. However, as disclosed in JP-A-58-145613, a method of melting silica particles in a flame, JP-A-2006-36915 As disclosed in Japanese Patent Laid-Open Publication No. Hokukai, a method of burning silicon powder by a VMC (Vaporized Metal Combustion) method is known.

The inorganic fine particles (B) preferably have a specific surface area of 10 m ² / g or less. When it is 10 m ² / g or less, the fluidity of a resin solution obtained by dissolving a photosensitive resin composition in a solvent is good, and formation of a smooth film surface is easy. The specific surface area of the inorganic fine particles (B) is more preferably 9 m ² / g or less, and further 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, it is preferable that the maximum particle diameter of the inorganic fine particles (B) is not more than the thickness of the second photosensitive resin layer. By setting the maximum particle size of the inorganic fine particles (B) to be equal to or less than the thickness of the second photosensitive resin layer, the inorganic fine particles (B) are not exposed on the surface of the photosensitive resin laminate, and the blade of the pad printing machine Ink remaining when squeegeeing can be reduced. The maximum particle size was set by passing inorganic fine particles through a sieve having a corresponding size.

  Furthermore, it is preferable that the inorganic fine particles (B) have a pH of the extraction water in the range of 5.5 to 8.5. By being this range, the dispersibility to the other component used for this invention is favorable, and aggregation of an inorganic fine particle is suppressed. The pH of the extracted water is more preferably in the range of 6.0 to 8.0. In this specification, the pH of the extraction water of the inorganic fine particles (B) can be measured with a pH meter after the inorganic fine particle powder is dispersed by 10 mass% in distilled water and stirred for 30 minutes. The pH of the inorganic fine particles can be adjusted by allowing the activity inhibitor to act on the active hydroxyl groups of the inorganic fine particles. Examples of the activity inhibitor may be one or more selected from organic phosphine compounds, sulfide compounds, mercaptan compounds, ketone compounds, and amide compounds, but are not limited thereto. These activity inhibitors can be mixed with the inorganic fine particles (B) and heated at 90 to 180 ° C. for 4 to 24 hours for use.

  When such inorganic fine particles (B) are used, (A1) a polyamide having a hydrophilic group, (A2) a modified partially saponified polyvinyl acetate having a functional group capable of crosslinking by a radical reaction in the side chain, and ( C) In the mixture containing any of the compounds having an ethylenic double bond, aggregation and reaggregation of the inorganic fine particles (B) are suppressed, and the ink on the plate surface can be scraped well with a blade of a 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 constituting the second photosensitive resin layer in order to impart wear resistance. In order to enable the formation, the content is preferably 70% by mass or less. The content of the inorganic fine particles (B) is more preferably 5% by mass or more and 70% by mass or less.

  It is also possible to introduce an ethylenic double bond on the surface of the inorganic fine particles (B) using a surface modifier. Examples of such modifiers include (3-acryloylpropyl) trimethoxysilane, methacryloylpropyltrimethoxysilane, methacryloylpropyltriethoxysilane, methacryloyloxymethyltriethoxysilane, and methacryloyloxymethyltrimethoxysilane. However, this is not a limitation. By modifying the surface of the inorganic fine particles (B), (A1) a polyamide having a hydrophilic group, (A2) a modified partially saponified polyvinyl acetate having a functional group that can be crosslinked by a radical reaction in the side chain, and ( C) The dispersibility of the mixture containing any of the compounds having an ethylenic double bond can be improved, and aggregation / reaggregation can be suppressed.

  In the present invention, the photosensitive resin laminate preferably contains (C) a compound having an ethylenic double bond.

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

  For example, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, phenoxydiethylene glycol (meth) acrylate, 2- (meth) acryloyl Roxyethylphthalic 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 derivatives thereof, N- (meth) acryloxysuccinimide, (meth) acrylic acid-2-naphthyl, N-phenyl (meth) acrylamide, divinylethyleneurea, Vinyl propylene urea, vinyl caprolactam, vinyl carbazole, bicyclopentenyl (meth) acrylate, 1-vinylimidazole, 2-methyl-1-vinylimidazole, (2-methyl-ethyldioxolan-4-yl) methyl acrylate, imide acrylate, (2-oxy-1,3-dioxolan-4-yl) methyl (meth) acrylate, 2- (oxydiimidazolidin-1-yl) ethyl (meth) acrylate, 2,2,6,6-tetramethyl- 4-piperidyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Allyl (meth) acrylate, chloroethyl (meth) acrylate, chloropropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene Glycol (meth) acrylate, methoxydipropylene 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) acrylamid Compounds having only one ethylenic double bond such as 2-hydroxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol diglycidyl ether and compounds with ethylenic double bond and active hydrogen such as unsaturated carboxylic acid and unsaturated alcohol It can be obtained by addition reaction of unsaturated epoxy compounds such as polyvalent (meth) acrylates and glycidyl (meth) acrylates obtained by addition reaction of compounds with active hydrogen compounds such as carboxylic acids and amines. Compounds having two or more ethylenic double bonds, such as polyvalent (meth) acrylates, polyvalent (meth) acrylamides such as methylenebis (meth) acrylamide, polyvalent vinyl compounds such as divinylbenzene, and the like. .

  Of these (C) ethylenic double bond-containing compounds, those having one or more hydroxyl groups in the molecule are crosslinked by (A) polyamides having hydrophilic groups and / or (A2) radical reactions. Good compatibility with modified partially saponified polyvinyl acetate having a functional group capable of forming in the side chain, and good dispersibility of inorganic fine particles (B) having a pH of 5.5 to 8.5 in the extraction water Thus, when blended with the photosensitive resin composition, a uniform composition can be produced. Such (C) ethylenic double bond-containing compounds include 2-hydroxy-3-phenoxypropyl (meth) acrylate, [4- (hydroxymethyl) cyclohexyl] methyl (meth) acrylate, 2-hydroxyethyl (meta) ) 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.

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

  The content of these (C) ethylenic double bond-containing compounds is (A1) a polyamide having a hydrophilic group, and / (A2) a modified partially saponified poly having a functional group in the side chain that can be crosslinked by a radical reaction. It is preferable that it is 5-200 mass parts with respect to 100 mass parts of vinyl acetate. When the amount is 5 parts by mass or more, when printing using ink, the printing plate can be used without swelling, and when it is 200 parts by mass or less, the photosensitive resin composition can be easily molded. . (C) The ethylenic double bond-containing compound is (A1) a polyamide having a hydrophilic group, and (A2) a modified partially saponified polyvinyl acetate having a functional group that can be crosslinked by a radical reaction in the side chain. More preferably, it is 10 parts by mass or more, more preferably 20 parts by mass or more with respect to parts. The content of the (C) ethylenic double bond-containing compound is more preferably 200 parts by mass or less, and still more preferably 100 parts by mass or less.

  (C) The ethylenic double bond-containing compound preferably contains both an acryloyl group and a methacryloyl group, and the number of methacryloyl groups in the (C) ethylenic double bond-containing compound is larger than the number of acryloyl groups. It is preferable. In general, a methacryloyl group has a slower reaction rate than an acryloyl group. Therefore, when ultraviolet rays are irradiated through a positive film, the concave portions of the relief are deepened due to the large number of methacryloyl groups. The depth of the concave portion can be easily adjusted by the screen eyes.

  Moreover, in this invention, the photosensitive resin laminated body contains (D) photoinitiator. (D) Any photopolymerization initiator can be used as long as it can polymerize a polymerizable carbon-carbon unsaturated group by light. Especially, what has the function to produce | generate a radical by self-decomposition or hydrogen abstraction by light absorption is used preferably. (D) Examples of the photopolymerization initiator include benzoin alkyl ethers, benzophenones, anthraquinones, benzyls, acetophenones, and diacetyls.

  (D) As a compounding quantity of a photoinitiator, (A1) the polyamide which has a hydrophilic group, and (A2) modified partially saponified polyvinyl acetate 100 which has a functional group which can be bridge | crosslinked by radical reaction in a side chain. The range of 0.1-20 mass parts is preferable with respect to mass parts. If it is 0.1 parts by mass or more, the relief image formability is improved, and if it is 20 parts by mass or less, precipitation of the photopolymerization initiator can be suppressed. (D) The compounding quantity of a photoinitiator becomes like this. More preferably, it is 0.5 mass part or more, More preferably, it is good in it being 1 mass part or more. The blending amount of (D) the photopolymerization initiator is more preferably 10 parts by mass or less, and further preferably 8 parts by mass or less.

  In the present invention, the photosensitive resin laminate includes ethylene glycol, diethylene glycol, triethylene glycol, glycerin and derivatives thereof, trimethylolpropane and derivatives thereof, trimethylolethane as compatibility aids for enhancing compatibility and flexibility. And polyhydric alcohols such as pentaerythritol and derivatives thereof can be optionally added. It is preferable to add 30% by mass or less of these polyhydric alcohols with respect to the entire photosensitive resin composition. In particular, by improving the compatibility, turbidity of the resin composition and bleeding out of low molecular weight components can be suppressed.

  Further, in the intaglio printing plate formed from the photosensitive resin printing plate precursor in the present invention, an ultraviolet absorber is added for the purpose of suppressing light scattering in the photosensitive resin layer in order to form a concave portion having a good shape. You may mix | blend. Preferred ultraviolet absorbers include benzotriazole-based, triazine-based, and benzophenone-based compounds, and one or more of these can be used. In addition, it is preferable to use the compounding quantity of a ultraviolet absorber in 0.001-5 mass% with respect to all the photosensitive resin compositions.

  Furthermore, in the present invention, conventionally known polymerization inhibitors can be optionally added in order to increase the thermal stability of the photosensitive resin composition. Preferable polymerization inhibitors include phenols, hydroquinones, catechols, N-nitrosamine derivatives and the like. These blending amounts are preferably used in the range of 0.001 to 5 with respect to the total photosensitive resin composition.

  Moreover, in this invention, dye, a pigment, surfactant, an antifoamer, a fragrance | flavor, etc. can be arbitrarily added to the photosensitive resin composition as another component.

  The first photosensitive resin layer is formed of inorganic fine particles (in order to secure adhesion with the second photosensitive resin layer and to prevent migration of low molecular weight compounds between the first and second photosensitive resin layers). It is preferable to contain the same component as the second photosensitive resin component except that it does not contain B). In addition, (A1) a polyamide having a hydrophilic group, and / or (A2) a functional group capable of crosslinking by a radical reaction, contained in a side chain, contained in at least the resin composition constituting the second photosensitive resin layer. By containing the same component as the modified partially saponified polyvinyl acetate in the resin composition constituting the adhesive layer, adhesion between the adhesive layer and the second photosensitive resin layer can be secured.

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

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

Next, the manufacturing method of the photosensitive resin laminated body which consists of a photosensitive resin composition, and the photosensitive resin printing original plate using the same is demonstrated. After (A1) component and / or (A2) component 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, if necessary, Add plasticizer and other additives, stir and mix thoroughly. Next, the inorganic fine particles (B) are added, and mixed and dispersed to obtain a composition solution that becomes the second photosensitive resin layer.
Examples of the method for dispersing the inorganic fine particles include a mechanical stirring method, an ultrasonic dispersion method, a high pressure dispersion method, a media dispersion method, and the like. Among these, a media dispersion method capable of highly dispersing inorganic fine particles is preferable.

  The composition solution to be the first photosensitive resin layer is prepared by dissolving (A1) and / or (A2) in a mixed solvent containing water as a main component, and then (C) having an ethylenic double bond. A compound solution to be a first photosensitive resin layer is obtained by adding a compound having (D) a photopolymerization initiator and, if necessary, a plasticizer and other additives, and mixing sufficiently by stirring. .

  The first photosensitive resin layer can be obtained by casting the composition solution obtained by the above-described method on a support having an adhesive layer and drying it. Then, the 2nd photosensitive resin layer can be obtained by casting the composition solution used as the 2nd photosensitive resin layer on the 1st photosensitive resin layer, and drying. Then, the photosensitive resin laminated body of this invention can be obtained by sticking the cover film which apply | coated the peeling auxiliary layer arbitrarily on the 2nd photosensitive resin layer. Also, the first photosensitive resin sheet and the second photosensitive resin sheet are produced by dry film formation, and the first photosensitive resin sheet and the second photosensitive resin sheet are sandwiched between the cover films on the support. The photosensitive resin printing plate laminate of the present invention can also be obtained by laminating the film.

  When the photosensitive resin printing plate precursor has a peeling auxiliary layer, the method for forming the peeling auxiliary layer is not particularly limited, but for ease of thin film formation, a solution in which the peeling auxiliary layer component is dissolved in a solvent is applied onto the cover film. The method for removing the solvent is particularly preferably carried out. 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 component is not particularly limited, but water, alcohol, or a mixture of water and alcohol is preferably used.

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

  When the photosensitive resin printing plate precursor has a cover film, the second and first photosensitive films are peeled off, and a positive original film is adhered onto the second photosensitive resin layer and irradiated with ultraviolet rays. The resin layer is photocured. Ultraviolet irradiation can be performed using a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, or the like that can usually irradiate a wavelength of 300 to 400 nm.

  Next, the photosensitive printing plate precursor is immersed in a developing solution, and a relief image is formed on the substrate by a brush type developing device that removes uncured portions by rubbing with a brush. In addition to the brush type developing device, it is also possible to use a spray type developing device. As the developer, an aqueous solution or one further containing a surfactant can be used.

  The liquid temperature during development is preferably 15 to 40 ° C. After forming the relief image, it can be dried at 50 to 70 ° C. for about 10 minutes, and further subjected to actinic ray treatment in the air or vacuum as necessary to obtain an intaglio printing plate.

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

  Hereinafter, the present invention will be described in detail with reference to examples.

<Synthesis of (A1) polyamide having hydrophilic group>
Synthesis example 1:
10 parts by weight of ε-caprolactam, 90 parts by weight of N- (2-aminoethyl) piperazine and nylon salt of adipic acid and 100 parts by weight of water were placed in a stainless steel autoclave, and the air inside was replaced with nitrogen gas at 180 ° C. Heating was performed for 1 hour, and then moisture was removed to obtain polyamide 1 having a hydrophilic group as component (A1) and basic nitrogen in the main chain. The content of the alicyclic diamine residue 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 reducing this with hydrogen, and 20 parts by weight of ε-caprolactam And 20 parts by weight of an equimolar salt of hexamethylenediamine and adipic acid were melt-polymerized, and then water was removed to obtain polyamide 2 having a hydrophilic group and a polyether segment in the main chain as component (A1). .

Synthesis Example 3:
ε-Caprolactam 10 parts by weight (30 mol%), N- (2-aminoethyl) piperazine 8 parts by mass (20 mol%), 1,3-bis (aminomethyl) cyclohexane 6 parts by mass (15.4 mol%) , 18 parts by mass (34.6 mol%) of 1,4-cyclohexanedicarboxylic acid was placed in a stainless steel autoclave, the air inside was replaced with nitrogen gas, heated at 180 ° C. for 1 hour, and then water was removed ( 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 residue was 34.6 mol%.

<(A2) Synthesis of Modified Partially Saponified Polyvinyl Acetate Having a Functional Group in the Side Chain that can be Crosslinked by Radical Reaction>
Synthesis Example 4:
Partially saponified polyvinyl acetate “GOHSENOL” (registered trademark) KL-05 (degree of polymerization: about 500, degree of saponification: 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 at 80 ° C. in 200 parts by weight of a mixed solvent of ethanol / water = 30/70 (weight ratio). Here, 6 parts by weight of glycidyl methacrylate was added, and a functional group capable of crosslinking by radical reaction was introduced into partially saponified polyvinyl acetate. Analysis by potentiometric titration confirms that the carboxyl group in the polymer has reacted with the epoxy group of glycidyl methacrylate and the methacryloyl group has been introduced into the polymer side chain. A modified partially saponified polyvinyl acetate 1 having a functional group that can be formed in the side chain was obtained. The resulting modified partially saponified polyvinyl acetate contained 79 mol% of structure (I), 20 mol% of structure (II), and 1 mol% of structure (III).

Synthesis Example 5:
A polymer containing 1 mol% of methacrylic acid as a copolymer 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 at 80 ° C. in 200 parts by weight of a mixed solvent of ethanol / water = 30/70 (weight ratio). Here, 6 parts by weight of glycidyl methacrylate was added, and a functional group capable of crosslinking by radical reaction was introduced into partially saponified polyvinyl acetate. From the analysis result by potentiometric titration method, it is confirmed that the carboxyl group in the polymer has reacted with the epoxy group of glycidyl methacrylate and the methacryloyl group has been introduced into the polymer side chain, and can be crosslinked by the radical reaction as component (A2). A modified partially saponified polyvinyl acetate 2 having a functional group in the side chain was obtained. The resulting modified partially saponified polyvinyl acetate contained 79 mol% of structure (I), 20 mol% of structure (II), and 1 mol% of structure (III).

Synthesis Example 6:
Partially saponified polyvinyl acetate “GOHSENOL” (registered trademark) KL-05 (polymerization degree: about 500, saponification degree: 78-82 mol%) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. in 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 moisture, acrylic system having N-methylol group A modified partially saponified polyvinyl acetate 3 having a functional group capable of crosslinking by a radical reaction as a component (A2) obtained by reaction with a compound in a side chain was obtained. The resulting modified partially saponified polyvinyl acetate contained 79 mol% of structure (I), 20 mol% of structure (II), and 1 mol% of structure (III).

Inorganic fine particles (B):
The inorganic fine particle powder shown in Table 1 was used. Among 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 the dispersion medium set to water and the refractive index set to 1.1. The maximum particle size was set to 20.0 μm by passing through a 20.0 μm mesh screen. The specific surface area was measured by BET method using Tristar 3000 manufactured by Shimadzu Corporation.

  The pH of the water extraction of the inorganic fine particles (B) was measured with D-71LAB manufactured by Horiba, Ltd. after the inorganic fine particle powder was dispersed in 10% by mass in distilled water and stirred for 30 minutes.

(C) Ethylenic double bond-containing compound (in Table 2, described as “component (C)”)
Compound having an ethylenic double bond having one hydroxyl group, glycerol dimethacrylate (Light Ester G101P, manufactured by Kyoeisha Chemical Co., Ltd.)
2-hydroxypropyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester HOP)
Compound with ethylenic double bond having two hydroxyl groups ・ Glycerol monomethacrylate (Blenmer GLM manufactured by NOF Corporation)
Compound having ethylenic double bond having no hydroxyl group, isobutyl methacrylate (Light Ester IB, manufactured by Kyoeisha Chemical Co., Ltd.)
-Triethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd. light ester 3EG).

(D) Photopolymerization initiator (in Table 2, described as “component (D)”)
2,2-dimethoxy-1,1-diphenylethane-1-one (IRGACURE651 manufactured by BASF)
・ Polymerization inhibitor: N- (ammoniumoxy) -N-nitrosophenylamine (Kuperon manufactured by Kanto Chemical Co., Inc.)
UV absorber: 2,4-di-tert-butyl-6- (5-chloro-2H-1,2,3-benzotriazol-2-yl) phenol (TINUVIN 326 manufactured by BASF).

<Preparation of a support having an adhesive layer>
66 parts by weight of “Vinitol” (registered trademark) # 284 (manufactured by Nagoya Oil Chemical Co., Ltd.) and 2 parts by weight of hexamethylenetetramine (manufactured by Kanto Chemical Co., Ltd.) were mixed in a solvent of 16 parts by weight of dimethylformamide and 16 parts by weight of xylene. To the solution, a solution prepared by mixing 90 parts by weight of “jER” (registered trademark) 834 (manufactured by Mitsubishi Chemical Corporation) with a solvent of 30 parts by weight of dimethylformamide and 30 parts by weight of xylene was added. Obtained.

  20 parts by weight of “Amilan” (registered trademark) CM833 (manufactured by Toray Industries, Inc.), 50 parts by weight of ethanol, 10 parts by weight of water, 10 parts by weight of dimethylformamide, and 50 parts of benzyl alcohol by “CJPARL” (manufactured by Automotive & Industrial Systems) The mixture was dissolved in 70 parts by weight in a mixed solvent of parts by weight for 2 hours and dissolved. Thereafter, 5 parts by weight of “jER” (registered trademark) 834 (manufactured by Mitsubishi Chemical Corporation) and 0.3 part by weight of dicyanodiamide (manufactured by Kanto Chemical Co., Ltd.) are added at 25 ° C. Obtained.

  After the adhesive layer coating solution 1 is dried on a 250 μm thick iron plate (manufactured by Nippon Steel & Sumikin Co., Ltd.), it is applied with a bar coater to a film thickness of 10 μm, and heated in an oven at 180 ° C. for 3 minutes. After removing the solvent, the adhesive layer coating liquid 2 is applied thereon with a bar coater so that the dry film thickness is 10 μm, and heated in an oven at 160 ° C. for 3 minutes to form a support having an adhesive layer. Obtained.

  The adhesive layer coating solution 1 is applied to a support having a thickness of 250 μm (manufactured by Nippon Steel & Sumikin Co., Ltd.) with a bar coater so that the film thickness becomes 10 μm after drying. After removing the solvent by heating for 5 minutes, the adhesive layer coating solution 2 is applied thereon with a bar coater so that the dry film thickness is 10 μm, and heated in an oven at 160 ° C. for 3 minutes to form the adhesive layer. A support having was obtained.

<Cover film>
“Lumirror” (registered trademark) S10 (polyester film, manufactured by Toray Industries, Inc.) having a thickness of 100 μm was used as a cover film.

[Evaluation method]
Evaluation in each example and comparative example was performed by the following method.

(1) Abrasion resistance Only the polyester film of the cover film is peeled off from the 7 cm × 14 cm photosensitive printing original (the outermost surface of the photosensitive printing original after peeling is a 1 μm dry auxiliary layer), and the positive film is vacuumed Adhere and expose with chemical lamp FL20SBL-360 20 Watt (manufactured by Mitsubishi Electric Osram Co., Ltd.) under the condition of gray scale sensitivity of 13 ± 1 (main exposure), and light the entire surface of 7cm × 14cm photosensitive resin plate Cured. Then, after developing for 1 minute with an aqueous solution at a liquid temperature of 25 ° C. and drying at 60 ° C. for 10 minutes, the chemical exposure FL20SBL-360 20 Watts (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) is the same as the main exposure. Post-exposure was performed under conditions to obtain a printing plate for wear resistance evaluation.

  The printing plate thus obtained was mounted on a hermetic 6-12 universal (manufactured by TAMPOPRINT), 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 recess for filling the ink becomes shallow during printing, which causes a printing defect. The worn depth is preferably less than 10 μm, more preferably within 8 μm, and even more preferably within 6 μm.

(2) Scraping ability of ink by blade The cover film is peeled off from the photosensitive printing original plate of 7 cm × 14 cm, the positive film is brought into vacuum contact, and the chemical lamp FL20SBL-360 20 Watt (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) is gray. Exposure was performed under the condition of scale sensitivity of 13 ± 1 (main exposure), and the entire surface of the 7 cm × 14 cm photosensitive resin plate was photocured. Then, after developing for 1 minute with an aqueous solution at a liquid temperature of 25 ° C. and drying at 60 ° C. for 10 minutes, the chemical exposure FL20SBL-360 20 Watts (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) is the same as the main exposure. Post-exposure was performed under the conditions to obtain a printing plate for evaluating ink scraping property.

  The printing plate thus obtained is mounted on a hermetic 6-12 universal (manufactured by TAMPOPRINT), squeezed once using PAD-PLV-1 ink white (manufactured by Navitas) as ink, and remains 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 remaining ink is 0.5 μm or more, the ink is transferred to a portion other than the print image portion, and a printing defect occurs.

(3) Evaluation result of printed matter The cover film was peeled off from the photosensitive printing original plate of 7 cm × 14 cm, the positive film was brought into vacuum contact, and the gray scale sensitivity was 13 with a chemical lamp FL20SBL-360 20 watts (Mitsubishi Electric OSRAM Co., Ltd.). Exposure was performed under conditions of ± 1 step (main exposure), and the entire surface of a 7 cm × 14 cm photosensitive resin plate was photocured. Then, after developing for 1 minute with an aqueous solution at a liquid temperature of 25 ° C. and drying at 60 ° C. for 10 minutes, the chemical exposure FL20SBL-360 20 Watts (manufactured by Mitsubishi Electric OSRAM Co., Ltd.) is the same as the main exposure. Post-exposure was performed under conditions to obtain a printing plate for evaluation of printed matter.

  The printing plate thus obtained was mounted on a hermetic 6-12 universal (manufactured by TAMPOPRINT), printed on a 250 μm thick polyester film using PAD-PLV-1 ink white (manufactured by Navitas) as the ink, I examined the images.

(4) Measurement of adhesion between photosensitive resin layer and support The polyester film of the cover film alone was peeled from the 2 cm × 30 cm photosensitive resin laminate. Thereafter, the support having the adhesive layer and the resin layer were peeled from one side having a width of 2 cm, and a Tensilon universal material testing machine UTM-4-100 (manufactured by Toyo Baldwin Co., Ltd.) equipped with a 50N load cell. From the average of the maximum value and the minimum value of the stress when the photosensitive resin layer and the support are respectively set on a chuck with an interval of 36 mm, and pulled at a speed of 100 mm / min, and the adhesion portion between the resin layer and the intermediate layer peels off. The adhesion strength between the resin layer and the intermediate layer was determined and divided by the width of the sample (2 cm) to determine the adhesion strength per 1 cm width. When the adhesion was 1 N / cm or more, it could be used without any problem, so that it was evaluated as ◯. In addition, since it peeled in the process of producing a printing plate when it is smaller than 1 N / cm, it was set as x.
Example 1
<Preparation of composition solution for first photosensitive resin layer>
(A1) component shown in the column of Example 1 in Table 2 was added to a three-necked flask equipped with a stirring spatula and a condenser tube, and “Solmix” (registered trademark) H-11 (alcohol mixture, Japan) was added. A mixed solvent of 50 parts by weight of Alcohol Co., Ltd. and 50 parts by weight of water was mixed and then heated at 90 ° C. for 2 hours with stirring to dissolve the component (A1). After cooling to 70 degreeC, the other component of the column of Example 1 of Table 2 was added, and it stirred for 30 minutes, and obtained the solution of the composition 1-1 for 1st photosensitive resin layers.

  The first photosensitive resin layer was prepared in the same manner as the solution of the composition 1-1 except that the composition solution for the first photosensitive resin layer was changed as shown in the composition 1-2 to the composition 1-10 in Table 2. A solution of the composition for the resin layer was prepared.

<Preparation of composition solution for second photosensitive resin layer>
The component (A1) shown in the column of Example 1 in Table 3 was added to a three-necked flask equipped with a stirring spatula and a condenser tube, and “Solmix” (registered trademark) H-11 (alcohol mixture, Japan) was added. After mixing a mixed solvent of 50 parts by mass of 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 3 were added thereto and stirred for 30 minutes. Furthermore, after cooling to 25 degreeC, it disperse | distributed using the continuous media disperser (NANO GRAIN MILL, Asada Tekko Co., Ltd.), and the solution of the composition 2-1 for 2nd photosensitive resin layers was obtained. .

  The second photosensitive resin layer was treated in the same manner as the solution of the composition 2-1, except that the composition solution for the second photosensitive resin layer was changed as shown in the composition 2-2 to the composition 2-17 in Table 3. A solution of the composition for the resin layer was prepared.

<Manufacture of photosensitive resin printing plate precursor 1>
The composition solution 1-1 was cast on a support having the adhesive layer and dried at 60 ° C. for 1 hour. At this time, the plate thickness of the first photosensitive resin layer after drying was adjusted to 5 μm. The composition solution 2-1 was cast on the first photosensitive resin layer thus obtained and dried at 60 ° C. for 2 hours. At this time, the plate thickness of the second photosensitive resin layer after drying was adjusted to 25 μm. Thereafter, a mixed solvent of water / ethanol = 50/50 (weight ratio) was applied, and a cover film was pressure-bonded to the surface to obtain a photosensitive resin printing plate precursor 1. Table 4 shows the results of evaluating the characteristics of the printing plate by the above method using the resulting photosensitive printing original plate 1.

Examples 2-17
The photosensitive resin sheet and the photosensitive printing original plate were produced like Example 1 except having changed the structure of the photosensitive resin laminated body as Example 2-17 of Table 4. FIG. The evaluation results are shown in Table 4.

Comparative Examples 1-8
A photosensitive resin sheet and a photosensitive printing original plate were produced in the same manner as in Example 1 except that the configuration of the photosensitive resin laminate was changed as shown in Comparative Examples 1 to 9 in Table 4. The evaluation results are shown in Table 4.

Claims (17)

  A photosensitive resin laminate in which a photosensitive resin layer is provided on a support, wherein the photosensitive resin layer is at least above the first photosensitive resin layer on the support side and the first photosensitive resin layer. A multilayer structure including a provided second photosensitive resin layer, wherein the first photosensitive resin layer does not contain inorganic fine particles, and the second photosensitive resin layer has an average particle diameter of 0.5 μm or more and 4 μm or less; Containing the fine particles, the thickness of the second photosensitive resin layer is larger than the thickness of the first photosensitive resin layer, and the thickness of the photosensitive resin layer is 20 μm or more and 50 μm or less, and the photosensitive resin laminate Contains a resin that can be developed with water.   The photosensitive resin laminate according to claim 1, wherein the thickness of the first photosensitive resin layer is 20 µm or less.   The second photosensitive resin layer is (A1) a polyamide having a hydrophilic group, (B) inorganic fine particles having an average particle diameter of 0.5 μm to 4 μm, (C) a compound having an ethylenic double bond, D) A photopolymerization initiator is contained, and the first photosensitive resin layer contains the same components as the second photosensitive resin layer except that the inorganic fine particles of (B) are not contained. The photosensitive resin laminate according to claim 1 or 2.   The photosensitive resin laminate according to claim 3, wherein the polyamide (A1) having a hydrophilic group has basic nitrogen and / or a polyether segment.   The photosensitive resin laminate according to claim 3 or 4, wherein the polyamide (A1) having a hydrophilic group has an alicyclic diamine residue and / or an alicyclic dicarboxylic acid residue.   The photosensitive resin laminate according to any one of claims 3 to 5, wherein the polyamide (A1) having a hydrophilic group has a piperazine ring.   The second photosensitive resin layer is (A2) modified partially saponified polyvinyl acetate having a functional group that can be cross-linked by a radical reaction in the side chain, and (B) an average particle size of 0.5 μm to 4 μm. The inorganic fine particles, (C) a compound having an ethylenic double bond, (D) a photopolymerization initiator, and the first photosensitive resin layer does not contain the inorganic fine particles (B). The photosensitive resin laminate according to claim 1, comprising the same component as the second photosensitive resin layer.   (A2) Modified partially saponified polyvinyl acetate having a functional group that can be cross-linked by radical reaction in its side chain reacts with partially saponified polyvinyl acetate and acid anhydride to introduce a carboxyl group into the polymer side chain The photosensitive resin laminate according to claim 7, wherein the photosensitive resin laminate is a modified partially saponified polyvinyl acetate having a functional group capable of being crosslinked by a radical reaction when an unsaturated epoxy compound reacts with the carboxyl group.   The (A2) modified partially saponified polyvinyl acetate having a functional group capable of crosslinking by radical reaction in the side chain is a copolymer of vinyl acetate and an unsaturated carboxylic acid or a salt thereof, or an unsaturated carboxylic acid ester. The photosensitive resin laminate according to claim 7, which is a modified partially saponified polyvinyl acetate obtained by adding an unsaturated epoxy compound to an anion-modified polyvinyl alcohol having a saponification degree of 60 to 90 mol% obtained by saponifying body. The photosensitive resin laminate according to claim 3, wherein the inorganic fine particles (B) have a specific surface area of 10 m ² / g or less.   The photosensitive resin laminate according to any one of claims 3 to 10, wherein a maximum particle diameter of the inorganic fine particles (B) is equal to or less than a thickness of the second photosensitive resin layer.   The photosensitive resin laminate according to any one of claims 3 to 11, wherein the sphericity of the inorganic fine particles (B) is 0.9 or more.   The photosensitive resin laminate according to any one of claims 3 to 12, wherein the inorganic fine particles (B) are amorphous silica.   The photosensitive resin laminate according to any one of claims 3 to 13, wherein the pH of the extraction water of the inorganic fine particles (B) is 5.5 to 8.5.   The photosensitive resin laminate according to any one of claims 3 to 14, wherein the compound (C) having an ethylenic double bond has one or more hydroxyl groups in the molecule.   The photosensitive resin laminate according to claim 1, wherein the photosensitive resin laminate is an intaglio printing plate material. A photosensitive resin printing plate precursor for use in intaglio printing or pad printing, comprising the photosensitive resin laminate according to any one of claims 1 to 16.