JP5451370B2 - Resin composition for laser engraving, relief printing plate precursor for laser engraving, method for producing relief printing plate precursor for laser engraving, plate making method for relief printing plate, and relief printing plate - Google Patents

Description

  The present invention relates to a resin composition for laser engraving, a relief printing plate precursor for laser engraving, a method for producing a relief printing plate precursor for laser engraving, a method for making a relief printing plate, and a relief printing plate.

Many so-called “direct engraving CTP methods” have been proposed in which a relief forming layer is directly engraved with a laser to make a plate. Unlike the relief formation using the original film, the direct engraving CTP method can freely control the relief shape. For this reason, when an image such as a letter is formed, the area is engraved deeper than other areas, or the fine halftone dot image is engraved with a shoulder in consideration of resistance to printing pressure, etc. Is also possible.
In the case of laser engraving, debris generated during engraving adheres to the plate. Patent Document 1 discloses a method of cleaning using water, soapy water, rinsing water containing a surfactant, and the like, and a method of removing engraving residue by physical removal such as brush rubbing or high-pressure water jetting. Patent Documents 2 and 3 disclose a plate making method including a thermal crosslinking step and a rinsing step as a method for producing a laser-engravable flexographic printing element containing an elastomer binder.

JP 2008-207419 A Special table 2004-506551 gazette JP 2009-227900 A

  If the sculpture residue is thoroughly removed, the uneven shape of the relief plate itself may be damaged. Even if the rinsing process is strengthened chemically and / or mechanically, the relief plate is insoluble in the rinsing liquid in order to achieve good engraving residue removal without impairing the uneven shape of the relief plate itself. It is necessary to simultaneously realize that the engraving residue is easily dispersed with respect to the rinsing liquid and that the mechanical strength of the relief plate is high.

  An object of the present invention is to provide a relief printing plate having excellent tensile strength and debris removal and having no halftone dots, a resin composition for laser engraving, a relief printing plate precursor for laser engraving, and a relief printing plate precursor for laser engraving. A manufacturing method, a plate making method of a relief printing plate, and a relief printing plate are provided.

The above-described problems of the present invention have been solved by means described in the following <1> to <13>.
<1> (Component A) a binder polymer, (Component B) a polymer having at least one of an acidic group and / or an alkali-decomposable group that becomes an acidic group by alkaline hydrolysis in the side chain, and (Component C1) ethylene A resin composition for laser engraving, comprising at least any one of a polymerizable unsaturated compound and (Component C2) a compound having a hydrolyzable silyl group and / or a silanol group,
<2> The resin composition for laser engraving according to <1>, further comprising (Component D) a plasticizer,
<3> The resin composition for laser engraving according to <1> or <2>, wherein the acid dissociation constant (pKa) of the acidic group is in the range of 5.5 to 11.
<4> The resin composition for laser engraving according to any one of <1> to <3>, wherein the acidic group is a phenolic hydroxyl group,
<5> The resin composition for laser engraving according to any one of <1> to <4>, wherein the alkali-decomposable group is represented by formula (B-3).

（式（Ｂ−３）中、Ａ¹は芳香環基又はシクロ環基を表し、ｎは１〜５の整数を表し、Ｘ²は、−ＮＲ¹Ｒ²、−ＳＲ³、−ＯＲ⁴を表し、ここでＲ¹〜Ｒ⁴は、それぞれ独立に、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、及び、ハロゲン原子よりなる群から選択された少なくとも１以上の原子から構成された置換基を表し、Ｙは、単結合、又は、−Ｏ−、−ＮＲ⁵−、アルキレン基、若しくは、これらを組み合わせた二価の連結基を表し、ここでＲ⁵は、水素原子又は炭化水素基を表す。）

(In formula (B-3), A ¹ represents an aromatic ring group or a cyclo ring group, n represents an integer of 1 to 5, and X ² represents —NR ¹ R ² , —SR ³ , —OR ⁴ . Wherein R ^{1 to} R ⁴ are each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. Y represents a single bond, —O—, —NR ⁵ —, an alkylene group, or a divalent linking group obtained by combining these, and R ⁵ represents a hydrogen atom or a hydrocarbon. Represents a group.)

<6> The resin composition for laser engraving according to any one of <1> to <5>, wherein the component A is a non-elastomer.
<7> A relief printing plate precursor for laser engraving, comprising a relief forming layer comprising the resin composition for laser engraving according to any one of <1> to <6> on a support,
<8> A relief printing plate for laser engraving, comprising a crosslinked relief forming layer obtained by thermally crosslinking a relief forming layer comprising the resin composition for laser engraving according to any one of <1> to <6>. Original,
<9> The relief printing plate precursor for laser engraving according to <7> or <8>, which is a flexographic printing plate precursor,
<10> A layer forming step of forming a relief forming layer comprising the resin composition for laser engraving according to any one of <1> to <6>, and a crosslinked relief forming layer obtained by thermally crosslinking the relief forming layer A method for producing a relief printing plate precursor for laser engraving, comprising a crosslinking step of obtaining a relief printing plate precursor having
<11> (1) A step of crosslinking the relief forming layer in the relief printing plate precursor for laser engraving according to <7> with heat and / or light, and (2) laser engraving the crosslinked relief forming layer. Forming a relief layer, and a method for making a relief printing plate,
<12> Furthermore, (3) The plate-making method of the relief printing plate as described in <11> including the process of processing this relief layer with an alkaline liquid of pH 9.5-14,
<13> A relief printing plate made by the plate making method of a relief printing plate according to <11> or <12>.

  According to the present invention, a relief printing plate having excellent tensile strength and debris removal and having no halftone dot is obtained, a resin composition for laser engraving, a relief printing plate precursor for laser engraving, and a method for producing a relief printing plate precursor for laser engraving The method for making a relief printing plate and the relief printing plate could be provided.

(Resin composition for laser engraving)
The resin composition for laser engraving of the present invention (hereinafter also referred to as “resin composition”) comprises (Component C1) an ethylenically unsaturated compound, and (Component C2) a hydrolyzable silyl group and / or silanol group. A polymer having at least one of (component A) a binder polymer, and (component B) an acid group and / or an alkali-decomposable group that becomes an acid group by alkali hydrolysis in the side chain. , Containing. In addition, it is preferable that the resin composition of this invention is a thermosetting resin composition.

Laser engraving-type flexographic printing plate precursor that realizes good engraving residue removal without damaging the uneven shape of the relief plate itself even if the rinsing step is chemically and / or mechanically reinforced by the resin composition of the present invention Can be provided.
The resin composition of the present invention having such characteristics is not particularly limited except for the relief forming layer application of the relief printing plate precursor subjected to laser engraving, and can be widely applied to other applications. The present invention can be applied to the formation of various printing plates and various molded articles that are image-formed by laser engraving, such as other material shapes that form irregularities and openings on the surface, such as intaglio plates, stencil plates, and stamps. Among these, it is a preferable aspect to apply to the formation of a relief forming layer of a flexographic printing plate provided on an appropriate support.

  In this specification, regarding the description of the relief printing plate precursor, the component A is contained, the surface as an image forming layer to be subjected to laser engraving is a flat layer, and an uncrosslinked layer is referred to as a “relief forming layer”. Called. A layer obtained by crosslinking the relief forming layer is referred to as a “crosslinked relief forming layer”. Further, a layer in which irregularities are formed on the surface by laser engraving is referred to as a “relief layer”. Hereinafter, the components of the resin composition for laser engraving will be described. In addition, “A to B” representing the numerical range is synonymous with “A or more and B or less”.

(Component A) Binder Polymer The resin composition of the present invention contains (Component A) a binder polymer. Component A is preferably a non-elastomer. An elastomer is a polymer having a glass transition temperature of room temperature or lower (see Science Dictionary 2nd edition, Editor International Science Promotion Foundation, published by Maruzen Co., Ltd., P154). Therefore, the non-elastomer refers to a polymer having a glass transition temperature exceeding normal temperature (20 ° C.). The glass transition temperature of the non-elastomer is preferably 20 to 200 ° C, more preferably 20 to 170 ° C, and still more preferably 25 to 150 ° C, from the viewpoint of the balance between engraving sensitivity and film property. Component A having a glass transition temperature in the above range improves engraving sensitivity when combined with (Component F) a photothermal conversion agent. Component A in a glass state at room temperature is in a state in which thermal molecular motion is suppressed as compared with a rubber state. In laser engraving, in addition to the heat given by laser irradiation, the heat generated by the function of the photothermal conversion agent used in combination is transferred to the component A present in the surroundings, and the component A is thermally decomposed and dissipated, resulting in To form a recess. If a photothermal conversion agent is present in component A in which thermal molecular motion is suppressed, it is presumed that heat transfer and thermal decomposition to component A occur effectively and engraving sensitivity further increases.

From the viewpoint of achieving both water-based ink suitability and UV ink suitability, and having high engraving sensitivity and good film properties, Component A includes polyvinyl butyral (PVB) and its derivatives, alcohol-soluble polyamides, water-insoluble cellulose derivatives, An acrylic resin having a polar group in the side chain is exemplified. As component A, polyvinyl butyral and its derivatives, alcohol-soluble polyamides, cellulose derivatives, epoxy resins, acrylic resins, polyurethane resins and the like described in paragraphs 0017 to 0139 of JP-A-2009-262526 can be preferably used. Of these, polyvinyl butyral and its derivatives are preferred.
Polyvinyl butyral is represented by the formula (A-1), and the derivative includes a repeating unit represented by the formula (A-1).

式（Ａ−１）中、ｌ、ｍ、ｎは式（Ａ−１）中のそれぞれの繰返し単位のポリビニルブチラール中における含有量（モル％）を表し、ｌ＋ｍ＋ｎ＝１００の関係を満たす。ポリビニルブチラール及びその誘導体中のブチラール含量（式（Ａ−１）中におけるｌの値）は、３０〜９０モル％が好ましく、４０〜８５モル％がより好ましく、４５〜７８モル％が特に好ましい。
彫刻感度と皮膜性とのバランスの観点から、ポリビニルブチラール及びその誘導体の重量平均分子量は、５，０００〜８００，０００が好ましく、８，０００〜５００，０００がより好ましく、彫刻カスのリンス性向上の観点からは、５０，０００〜３００，０００が特に好ましい。

In formula (A-1), l, m, and n represent the content (mol%) of each repeating unit in formula (A-1) in polyvinyl butyral, and satisfy the relationship of l + m + n = 100. The butyral content (value of 1 in formula (A-1)) in polyvinyl butyral and its derivatives is preferably 30 to 90 mol%, more preferably 40 to 85 mol%, and particularly preferably 45 to 78 mol%.
From the viewpoint of balance between engraving sensitivity and film property, the weight average molecular weight of polyvinyl butyral and its derivatives is preferably 5,000 to 800,000, more preferably 8,000 to 500,000, and the rinse property of engraving residue is improved. From this viewpoint, 50,000 to 300,000 are particularly preferable.

  Specific examples of polyvinyl butyral and its derivatives are preferably Sekisui Chemical Co., Ltd. S-LEC B series, S-LEK K (KS) series, Denka Butyral manufactured by Denki Kagaku Kogyo Co., Ltd. As the S-Rec B series, BL-1, BL-1H, BL-2, BL-5, BL-S, BX-L, BM-S, BH-S, and Denkabutyral # 3000-1, # 3000 -2, # 3000-4, # 4000-2, # 6000-C, # 6000-EP, # 6000-CS, # 6000-AS.

  The content of component A in the resin composition of the present invention is preferably from 2 to 95% by mass in the total solid content from the viewpoint of the balance between the shape retention of the relief forming layer, water resistance and engraving sensitivity, 80 mass% is more preferable, and 10-60 mass% is still more preferable.

(Component B) Polymer having at least one of an acidic group and / or an alkali-degradable group that becomes an acidic group by alkaline hydrolysis in the side chain The resin composition of the present invention has an acidic group in (Component B) side chain. And / or a polymer having at least one alkali-decomposable group that becomes an acidic group by alkali hydrolysis. By containing the component B, excellent debris removability is exhibited with respect to an alkaline rinse liquid.

Hereinafter, the acidic group contained in Component B will be described. The acid dissociation constant (pKa) of the acidic group is preferably in the range of 0 to 11, and in order to suppress the dissolution of the relief plate in neutral water, the pKa is more preferably in the range of 5.5 to 11. preferable.
Examples of the acidic group having an acid dissociation constant (pKa) of 0 or more and less than 5.5 include a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group, and a particularly preferable one is a carboxylic acid group.
Examples of the monomer that is a monomer unit containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxylstyrene, and particularly preferred is acrylic acid. Methacrylic acid, p-carboxylstyrene. In the present invention, one or more of these monomers can be used.
Next, an acidic group having an acid dissociation constant (pKa) of 5.5 to 11 will be described. pKa is preferably in the range of 7-11, more preferably in the range of 8-11.
As such an acidic group, a phenol group (pKa = 9.99), a 2-methoxyphenol group (pKa = 9.99), a 2-chlorophenol group (pKa = 8.55), a methyl 2-hydroxybenzoate group (PKa = 9.87), 4-methylphenol group (pKa = 10.28), 1,3-benzenediol group (pKa = 9.20), 1-naphthol group (pKa = 9.30), 1, 2-benzenediol group (pKa = 9.45), benzenesulfonamide group (pKa = 10.00), N-acetylphenylbenzenesulfonamide group (pKa = 6.94), 4-aminobenzenesulfonamide group (pKa = 10.58), N-phenyl-4-aminobenzenesulfonamide group (pKa = 6.30), N- (4-acetylphenyl) -4-aminoben Emissions sulfonamide group (pKa = 7.61), and the like acetyl ethyl acetate group (pKa = 10.68) is. Among these, a phenol group which may have a substituent on the aromatic group is preferable. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom (F, Cl, Br, I), a carboxy group, and an alkoxycarbonyl group having 2 to 5 carbon atoms. Is mentioned.

  An example of the polymer having a phenol group is a phenol resin. Examples of the phenol resin include novolak polymerized under an acid catalyst and resol synthesized under an alkali catalyst, and any of them can be preferably used. Polymers and copolymers having hydroxystyrene as a monomer unit are also preferred. Hydroxystyrene may be unsubstituted or substituted.

  In addition to the phenol resin and the like, as the component B, a polymer containing a monomer unit represented by the formula (B-1) is also preferable.

In formula (B-1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond in which C ^* and Y are directly bonded, and C ^* and ^* are attached. ester bond ^(* -COO-, ^* -COS-) to bind with sites or ^* -CONR ² - (R ² represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms Y represents a single bond directly bonding X and Ar, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, a carbonyl group, an ester bond (—COO—, —OCO). ^{-), - NR 3 -.} (R 3 is representing a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms), ureylene group, and a divalent linking group comprising a combination thereof Ar represents an aryl group having 6 to 20 carbon atoms, and Ac is bonded to Ar to cause acid dissociation. The constant (pKa) represents a group of 5.5 to 11, and n represents an integer of 1 or 2. The monomer unit represented by the formula (B-1) may have a substituent, and examples of the substituent include a hydroxy group, a halogen atom (F, Cl, Br, I), a cyano group, and a nitro group. Is mentioned.

R ¹ is preferably a hydrogen atom or a methyl group. X is preferably a single bond in which C ^* and Y are directly bonded, ^* -COO-, or ^* -CONH-. Y is preferably a single bond directly bonding X and Ar, an alkylene group having 1 to 10 carbon atoms, a ureylene group, or a divalent linking group combining these, and a single bond directly bonding X and Ar. Alternatively, an alkylene group having 1 to 6 carbon atoms is preferable, and a single bond directly bonding X and Ar is more preferable. Ar is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group. Ac preferably represents a group that binds to Ar and has an acid dissociation constant (pKa) of 5.5 to 11. The following are preferable as Ac. In addition, what was illustrated as said acidic group as a combination of Ar and Ac is mentioned.

Specific examples of the monomer unit of the formula (B-1) are shown below. In each specific example, R ¹ represents a hydrogen atom or a methyl group. Monomers serving as monomer units are disclosed in JP-A-7-333839, JP-A-8-339080, JP-B-52-28401, JP-A-4-229661, JP-A-2-866, and JP-A-8-286369. It can be synthesized by the method described in each publication.

  Polymers containing the following monomer units are also preferred as Component B.

  Further, as the component B, a polymer containing an alkali-decomposable group that becomes an acidic group by alkali hydrolysis is also preferable. The alkali-decomposable group means a group that becomes an acidic group by alkaline hydrolysis, and preferably refers to a functional group that becomes an acidic group by being hydrolyzed by an alkaline aqueous solution having a pH of 9.5 to 14. As such a specific functional group, a group represented by the formula (B-2) is preferable.

In formula (B-2), Q represents an (n + 1) -valent linking group that connects the polymer main chain skeleton and n X ^{1 s,} and X ¹ is hydrolyzed by an aqueous alkaline solution having a pH of 9.5 to 14. Represents a protecting group, and n represents an integer of 1 to 5. Here, when the functional group represented by the formula (B-2) becomes -Q (-OH) _n after hydrolysis, -Q (-OH) _n represents an acidic group having a pKa of 11 or less.

Examples of Q include linear, branched, and cyclic alkyl groups, groups containing aromatic ring groups, and the like. Among these, those in which the pKa of the specific functional group after hydrolysis falls within the above range. Selected. Usually, pKa can be made into said range by introduce | transducing an electron-withdrawing substituent into Q. Preferable examples of Q include an aromatic ring group and a group containing a cyclo ring group.
X ¹ is not particularly limited as long as it is a functional group that can function as a protective group until it is hydrolyzed and eliminated by an alkaline aqueous solution at pH 9.5 to 14, for example, a substituted oxy group, a substituted thio group, and a substituted amino group. Group and the like.

  The alkali-decomposable group is more preferably a group represented by the formula (B-3).

（式（Ｂ−３）中、Ａ¹は芳香環基又はシクロ環基を表し、ｎは１〜５の整数を表し、Ｘ²は、−ＮＲ¹Ｒ²、−ＳＲ³、−ＯＲ⁴を表し、ここでＲ¹〜Ｒ⁴は、それぞれ独立に、水素原子、炭素原子、酸素原子、窒素原子、硫黄原子、及び、ハロゲン原子よりなる群から選択された少なくとも１以上の原子から構成された置換基を表し、Ｙは、単結合、又は、−Ｏ−、−ＮＲ⁵−、アルキレン基、若しくは、これらを組み合わせた二価の連結基を表し、ここでＲ⁵は、水素原子又は炭化水素基を表す。）

(In formula (B-3), A ¹ represents an aromatic ring group or a cyclo ring group, n represents an integer of 1 to 5, and X ² represents —NR ¹ R ² , —SR ³ , —OR ⁴ . Wherein R ^{1 to} R ⁴ are each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. Y represents a single bond, —O—, —NR ⁵ —, an alkylene group, or a divalent linking group obtained by combining these, and R ⁵ represents a hydrogen atom or a hydrocarbon. Represents a group.)

In formula (B-3), A ¹ represents an aromatic ring group or a cyclo ring group. Specific examples include an aromatic ring group having 4 to 50 carbon atoms, a heterocyclic group, a condensed polycyclic structure, and an aliphatic cyclic structure. Among them, an aryl group having 6 to 12 carbon atoms, and 3 to 3 carbon atoms. 10 cycloalkyl groups are preferable, and a phenyl group and a cyclohexyl group are more preferable.
n represents an integer selected from 1 to 5, and is preferably 1 to 3 from the viewpoint of the balance between alkali solubility in the unexposed area and alkali developability in the exposed area.
X ² represents —NR ¹ R ² , —SR ³ , or —OR ⁴ . Here, R ^{1 to} R ⁴ each independently represents a substituent composed of one or more atoms selected from the group consisting of carbon atom, hydrogen atom, oxygen atom, nitrogen atom, sulfur atom, and halogen atom. For example, the alkyl group which may have a substituent, the aryl group which may have a substituent, etc. are mentioned.

  Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Among them, a linear chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, and a carbon number of 5 10 to 10 cyclic alkyl groups are more preferable, linear alkyl groups having 1 to 6 carbon atoms and branched alkyl groups having 3 to 6 carbon atoms are more preferable, and methyl groups and ethyl groups are more preferable.

Examples of the substituent that can be introduced into such an alkyl group include a monovalent non-metallic atomic group excluding a hydrogen atom, such as a halogen atom (—F, —Br, —Cl, —I), hydroxy Group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N- Diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyls Hoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N ′ An arylureido group, an N ′, N′-diarylureido group, an N′-alkyl-N′-arylureido group, an N-alkylureido group, an N-arylureido group, an N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxy Carbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group and their conjugates Base group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-ary Rucarbamoyl group, alkyl sulf Inyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group, alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N , N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N-acylsulfamoyl group and conjugation thereof base groups, N- alkylsulfonylsulfamoyl groups (-SO ₂ N SO ₂ (alkyl)) and its conjugated base group, N- aryl sulfonylsulfamoyl group _{(-SO 2 NHSO 2 (aryl)} ) and its conjugated base group, N- alkylsulfonylcarbamoyl group (-CONHSO ₂ (alkyl)) And its conjugate base group, N-arylsulfonylcarbamoyl group (—CONHSO ₂ (aryl)) and its conjugate base group, alkoxysilyl group (—Si (Oalkyl) ₃ ), aryloxysilyl group (—Si (Oaryl) ₃ ) Hydroxysilyl group (—Si (OH) ₃ ) and its conjugated base group, phosphono group (—PO ₃ H ₂ ) and its conjugated base group, dialkylphosphono group (—PO ₃ (alkyl) ₂ ), diarylphosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group (-PO ₃ (alkyl) (a yl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group, monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group, a phosphonooxy group (-OPO ₃ H ₂ ) and its conjugate base group, dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ ( alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group, monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group, cyano Group, nitro group, dialkylboryl group (-B (alkyl) ₂ ), diarylboryl group (-B (aryl) ₂ ), alkylaryl A boryl group (-B (alkyl) (aryl)), a dihydroxyboryl group (-B (OH) ₂ ) and its conjugate base group, an alkylhydroxyboryl group (-B (alkyl) (OH)) and its conjugate base group, An arylhydroxyboryl group (—B (aryl) (OH)) and its conjugate base group, aryl group, alkenyl group, alkynyl group and the like can be mentioned.

  Examples of the aryl group include a benzene ring, a ring in which 2 to 3 benzene rings form a condensed ring, and a ring in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specifically, a phenyl group, A naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group and the like can be mentioned, and among them, a phenyl group and a naphthyl group are preferable. In addition, examples of the substituent that can be introduced into the aryl group include the alkyl group and the substituent that can be introduced into the alkyl group.

Among such X ² , particularly preferred examples of the substituted amino group represented by —NR ¹ R ² include acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N ′ -Alkyl ureido group, N ', N'-dialkyl ureido group, N'-aryl ureido group, N', N'-diaryl ureido group, N'-alkyl-N'-aryl ureido group, N-alkyl ureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl- N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkyl Ureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxy Carbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N- An aryloxycarbonylamino group is mentioned. Examples of the alkyl group and aryl group in these include the aforementioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Further, an acylamino group, N- alkylacylamino group, N- aryl for R ⁸ also acyl group in the acyl amino group (R ⁸ CO-), alkyl group above, a substituted alkyl group, an aryl group, and the substituted aryl group Can be mentioned. Of these, more preferred are N-alkylamino group, N, N-dialkylamino group, N-arylamino group, and acylamino group. Preferred substituted amino groups include methylamino group, ethylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like, and more preferably A dimethylamino group and a diethylamino group;

In Formula (B-3), Y represents a single bond, —O—, —NR ⁵ —, an alkylene group, or a divalent linking group obtained by combining these. Here, R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by R ⁵ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group. Specific examples of the alkyl group include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl. Group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group, etc. Examples thereof include linear, branched or cyclic alkyl groups of 1 to 10. Specific examples of the aryl group include, for example, one hetero atom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. And a heteroaryl group having 1 to 10 carbon atoms, such as a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, and a quinolyl group. Specific examples of the alkenyl group include 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, and the like. Straight-chain, branched, or cyclic alkenyl groups up to and the like. Specific examples of the alkynyl group include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, 1-octynyl group and the like. R ⁵ may have a substituent, and examples of such a substituent are the same as the substituents that can be introduced into the alkyl groups mentioned for R ^{1 to} R ⁴ . However, the carbon number of R ⁵ is 10 or less, including the carbon number of the substituent. Such Y is preferably an oxygen atom or —NH— because synthesis is easy. Among these, R ⁵ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.
The alkylene group for Y is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and still more preferably an ethylene group or a propylene group.

As a method for introducing such a specific functional group into the polymer compound, a monomer having an unsaturated bond copolymerizable with the specific functional group and other copolymerization component in the molecule is used. And a method of copolymerization using these. At this time, if necessary, another monomer having no specific functional group can be copolymerized.
As a monomer unit which has a specific functional group, the monomer unit represented by Formula (B-4) is mentioned.

In formula (B-4), R represents a hydrogen atom or a methyl group, Y ¹ represents —O— or —NR ⁵ —, R ⁵ represents a hydrogen atom or a methyl group, Y ² represents a single bond, C1-C3 alkylene group, phenylene group, ester bond (—COO—, —OCO—), amide bond (—NHCO—, —CONH—), —NH—, ureylene group or a divalent combination thereof Represents a linking group, A represents a cyclohexyl group or a phenyl group, X ² represents —NR ¹ R ² , —SR ³ , —OR ⁴ , and R ^{1 to} R ⁴ each independently represents an alkyl having 1 to 6 carbon atoms. Represents a group, and n represents an integer of 1 or 2. The monomer unit may have a substituent, and examples of the substituent include a hydroxy group and an alkoxy group having 1 to 3 carbon atoms.
Although the preferable specific example of the monomer unit which has a specific functional group is shown below, this invention is not limited to these. R represents a hydrogen atom or a methyl group.

  The monomer unit having an acidic group and / or an alkali hydrolyzable group may be only one type in the polymer of component B, or two or more types. The content of the monomer unit having the above acidic group and / or alkali hydrolyzable group is preferably 20 to 100 mol% with respect to the total molar amount of the polymer component of Component B from the viewpoint of residue removal, and 50 to 50%. 100 mol% is more preferable and 80-100 mol% is still more preferable.

  Furthermore, the polymer of component B may have monomer units composed of other copolymerization components in addition to the monomer units having the exemplified acidic group and / or alkali hydrolyzable group. As an example of the other copolymerization component, a monomer unit represented by the formula (B-4) may be mentioned.

In formula (B-4), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an (n + 1) -valent organic linking group containing an ester group represented by —O (C═O) —. , A represents an oxygen atom or —NR ³ —, wherein R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5. Paragraphs 0025 to 0028 and paragraphs 0095 to 0114 of JP-A-2005-47947 can be referred to for specific examples of monomer units represented by the formula (B-4), synthesis methods, and the like.
In addition, the polymer of component B may have an ethylenically unsaturated group in its side chain. For specific examples of monomers for introducing an ethylenically unsaturated group into the side chain of the component B polymer, specific examples of monomer units, synthesis methods, and the like, paragraphs 0115 to 0123 of JP-A-2005-47947, and Reference may be made to paragraphs 0125-0157.
In addition, a copolymer component described in paragraphs 0158 to 0163 of JP-A-2005-47947 can also be used as a monomer that is a monomer unit of component B.

  The molecular weight of Component B is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and more preferably 10,000 to 200,000 in terms of weight average molecular weight from the viewpoint of image forming properties and printing durability. 000 is more preferable. Usually, when the molecular weight is high, the printing durability is excellent, but the image formability tends to be deteriorated, but if it is within the above range, the balance is good.

  The resin composition for thermosetting laser engraving of the present invention comprises at least one of (Component C1) an ethylenically unsaturated compound and (Component C2) a compound having a hydrolyzable silyl group and / or a silanol group. contains. Hereinafter, the component C1 and the component C2 will be described.

(Component C1) Ethylenically unsaturated compound The resin composition of the present invention preferably contains (Component C1) an ethylenically unsaturated compound. The ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated bond capable of radical polymerization by an initiating radical generated from a polymerization initiator. By containing an ethylenically unsaturated compound, the relief-forming layer can be given characteristics that can be cured by crosslinking.

  The ethylenically unsaturated compound can be arbitrarily selected from compounds having at least 1, preferably 2 or more, more preferably 2 to 6 ethylenically unsaturated bonds. The ethylenically unsaturated compound preferably has a molecular weight (weight average molecular weight) of less than 5,000. Further, the component C1 does not include a compound having an acidic group and / or an alkali-decomposable group that becomes an acidic group by alkaline hydrolysis, and a compound having a hydrolyzable silyl group and / or a silanol group. The ethylenically unsaturated compound is not particularly limited and may be a known compound, and examples thereof include the polymerizable compounds described in paragraphs 0098 to 0124 of JP2009-255510A and JP2009-204962A. it can.

In the relief forming layer in the present invention, it is necessary to form a crosslinked structure, and a polyfunctional monomer is preferably used as the component C1. The molecular weight of these polyfunctional monomers is preferably 120 to 3,000, more preferably 200 to 2,000.
Examples of monofunctional monomers and polyfunctional monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters of polyhydric alcohol compounds, unsaturated carboxylic acids, Examples include amides with polyvalent amine compounds.

Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3 -Butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (( (Meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, tetraethylene Recall di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (Meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate, polyester (meth) acrylate oligomer, bis [p- ( 3- (meth) acryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) pheny ] Di (meth) acrylate of hydrogenated bisphenol A, di (meth) acrylate of hydrogenated bisphenol F, di (meth) acrylate of ethylene oxide adduct of bisphenol A, di (meth) acrylate of propylene oxide adduct of bisphenol A (Meth) acrylate, di (meth) acrylate of bisphenol F ethylene oxide adduct, di (meth) acrylate of bisphenol F propylene oxide adduct, di (meth) acrylate of hydrogenated bisphenol A ethylene oxide adduct, hydrogenated Examples include di (meth) acrylates of propylene oxide adducts of bisphenol A. Among them, 2- (6-) functional (meth) acrylates of pentaerythritol or dipentaerythritol derivatives, and bisphenol type Di (meth) acrylate is preferable, and dipentaerythritol hexa (meth) acrylate or bisphenol A type di (meth) acrylate is more preferable. As the bisphenol A type di (meth) acrylate, those having 1 to 6 ethylene oxide groups added per molecule are more preferable. The ester monomers can also be used as a mixture.
The content of the (component C1) ethylenically unsaturated compound in the resin composition of the present invention is preferably 5 to 60% by mass, 8 to 30% by mass in terms of solid content, from the viewpoint of flexibility and brittleness of the crosslinked film. % Is more preferable.

(Component C2) Compound having a hydrolyzable silyl group and / or silanol group The “hydrolyzable silyl group” in Component C2 is a silyl group having hydrolyzability. Examples of the hydrolyzable group include an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. The silyl group is hydrolyzed to become a silanol group, and the silanol group is dehydrated and condensed to form a siloxane bond. Such a hydrolyzable silyl group or silanol group is preferably represented by the formula (C2-1).

In the formula (C2-1), at least one of R ^{1 to} R ³ is a hydrolysis selected from the group consisting of an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group, an amino group, and an isopropenoxy group. Represents a sex group or a hydroxy group. The remaining R ^{1 to} R ³ are each independently a hydrogen atom, a halogen atom, or a monovalent organic substituent (for example, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group can be exemplified). Represent.
In formula (C2-1), the hydrolyzable group bonded to the silicon atom is particularly preferably an alkoxy group or a halogen atom, and more preferably an alkoxy group. As an alkoxy group, from a viewpoint of rinse property and printing durability, a C1-C30 alkoxy group is preferable, More preferably, it is C1-C15 alkoxy group, More preferably, it is C1-C5, Most preferably An alkoxy group having 1 to 3 carbon atoms, most preferably a methoxy group or an ethoxy group. Examples of the halogen atom include an F atom, a Cl atom, a Br atom, and an I atom. From the viewpoint of ease of synthesis and stability, a Cl atom and a Br atom are preferable, and a Cl atom is more preferable.

Component C2 is preferably a compound having one or more groups represented by formula (C2-1), and more preferably a compound having two or more groups. Particularly preferred are compounds having two or more hydrolyzable silyl groups. That is, a compound having two or more silicon atoms having a hydrolyzable group bonded in the molecule is preferably used. 2-6 are preferable and, as for the number of the silicon atoms which the hydrolyzable group contained in component C2 couple | bonded, 2 or 3 is more preferable.
The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 4, and the total number of hydrolyzable groups in the formula (C2-1) is in the range of 2 or 3. preferable. In particular, it is preferable that three hydrolyzable groups are bonded to a silicon atom. When two or more hydrolyzable groups are bonded to a silicon atom, they may be the same as or different from each other.

Preferred examples of the alkoxy group as the hydrolyzable group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a tert-butoxy group, a phenoxy group, and a benzyloxy group. A plurality of these alkoxy groups may be used in combination, or a plurality of different alkoxy groups may be used in combination.
Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxymonoalkylsilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group.

  Component C2 preferably has at least a sulfur atom, an ester bond, a urethane bond, an ether bond, a urea bond, or an imino group. Among them, the component C2 preferably contains a sulfur atom from the viewpoint of crosslinkability, and from the viewpoint of engraving residue removal (rinsing property), an ester bond, urethane bond, or It preferably contains an ether bond (particularly an ether bond contained in an oxyalkylene group). Component C2 is preferably a compound having no ethylenically unsaturated bond.

Component C2 in the present invention includes a compound in which a plurality of groups represented by the formula (C2-1) are bonded via a divalent linking group, and as such a divalent linking group, From the viewpoint of the effect, a linking group having a sulfide group (—S—), an imino group (—N (R) —), or a urethane bond (—OCON (R) — or —N (R) COO—) is preferable. R represents a hydrogen atom or a substituent. Examples of the substituent in R include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and an aralkyl group.
There is no restriction | limiting in particular as a synthesis method of component C2, It can synthesize | combine by a well-known method. A typical synthesis method of component C2 containing a linking group having the above specific structure is shown below.

<Synthesis Method of Component C2 Having Sulfide Group as Linking Group>
The method for synthesizing component C2 having a sulfide group as a linking group is not particularly limited, but reaction of component C2 having a halogenated hydrocarbon group with an alkali sulfide, reaction of component C2 having a mercapto group with a halogenated hydrocarbon, Reaction of component C2 having a halogenated hydrocarbon group with component C2, reaction of component C2 having a halogenated hydrocarbon group with mercaptans, reaction of component C2 having an ethylenically unsaturated bond with mercaptans, ethylenic unsaturation Reaction of component C2 having a bond and component C2 having a mercapto group, reaction of a compound having an ethylenically unsaturated bond and component C2 having a mercapto group, reaction of ketones and component C2 having a mercapto group, diazonium salt and mercapto group Reaction of component C2 having a component, component C2 having a mercapto group and Examples of reactions, reaction of component C2 having a mercapto group and component C2 having an oxirane group, reaction of a component C2 having mercaptans and an oxirane group, reaction of component C2 having a mercapto group and aziridines, etc. it can.

<Synthesis Method of Component C2 Having Imino Group as Linking Group>
The method for synthesizing component C2 having an imino group as a linking group is not particularly limited, but reaction of component C2 having an amino group with a halogenated hydrocarbon, component C2 having an amino group, and component C2 having a halogenated hydrocarbon group Reaction, reaction between component C2 having halogenated hydrocarbon group and amines, reaction between component C2 having amino group and oxirane, reaction between component C2 having amino group and component C2 having oxirane group, amines and oxirane Reaction of component C2 having a group, reaction of component C2 having an amino group with aziridines, reaction of component C2 having an ethylenically unsaturated bond and amines, component C2 having an ethylenically unsaturated bond and an amino group Reaction of component C2, reaction of compound having ethylenically unsaturated bond and component C2 having amino group, acetylenic unsaturated bond Reaction of component C2 having an amino group with component C2, reaction of component C2 having imine unsaturated bond and organic alkali metal compound, reaction of component C2 having imine unsaturated bond and organic alkaline earth metal compound, and Examples of the synthesis method include a reaction of a carbonyl compound and a component C2 having an amino group.

<Synthesis Method of Component C2 Having Ureylene Group as Linking Group>
The method for synthesizing component C2 having a ureylene group as a linking group is not particularly limited. And the synthesis methods, such as reaction of the component C2 which has amines and isocyanate, can be illustrated.

  Component C2 is preferably a compound represented by the following formula (C2-2) or formula (C2-3).

（式（Ｃ２−２）及び式（Ｃ２−３）中、Ｒ^Bはエステル結合、アミド結合、ウレタン結合、ウレア結合、又は、イミノ基を表し、Ｌ¹はｎ価の連結基を表し、Ｌ²は二価の連結基を表し、Ｌ^s1はｍ価の連結基を表し、Ｌ³は二価の連結基を表し、ｎ及びｍはそれぞれ独立に１以上の整数を表し、Ｒ¹〜Ｒ³はそれぞれ独立に水素原子、ハロゲン原子、又は、一価の有機置換基を表す。ただし、Ｒ¹〜Ｒ³の少なくともいずれか１つは、アルコキシ基、メルカプト基、ハロゲン原子、アミド基、アセトキシ基、アミノ基、及び、イソプロペノキシ基よりなる群から選択される加水分解性基、又は、ヒドロキシ基を表す。）

(In Formula (C2-2) and Formula (C2-3), R ^B represents an ester bond, an amide bond, a urethane bond, a urea bond, or an imino group, L ¹ represents an n-valent linking group, and L ² represents a divalent linking group, L ^s1 represents an m-valent linking group, L ³ represents a divalent linking group, n and m each independently represents an integer of 1 or more, R ^{1 to} R ³ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic substituent, provided that at least one of R ^{1 to} R ³ is an alkoxy group, a mercapto group, a halogen atom, an amide group, an acetoxy group A hydrolyzable group selected from the group consisting of a group, an amino group, and an isopropenoxy group, or a hydroxy group.)

R ¹ to R in the formula (C2-2) and formula (C2-3) ³ has the same meaning as R ¹ to R ³ in Formula (C2-1), and preferred ranges are also the same.
Wherein R ^B is, from the viewpoint of rinsing properties and film strength, it is preferable that an ester bond or a urethane bond, and more preferably an ester bond.
The divalent or n-valent linking group in L ^{1 to} L ³ is a group composed of at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom. It is preferably a group composed of at least one atom selected from the group consisting of carbon atom, hydrogen atom, oxygen atom and sulfur atom. The number of carbon atoms of L ^{1 to} L ³ is preferably 2 to 60, and more preferably 2 to 30.
The m-valent linking group in L ^s1 is a group composed of a sulfur atom and at least one atom selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom and a sulfur atom. Are preferable, and an alkylene group or a group in which two or more alkylene groups, sulfide groups, and imino groups are combined is more preferable. The carbon number of L ^s1 is preferably 2 to 60, and more preferably 6 to 30.
N and m are each independently preferably an integer of 1 to 10, more preferably an integer of 2 to 10, still more preferably an integer of 2 to 6, and particularly preferably 2. preferable.
The n-valent linking group of L ¹ and / or the divalent linking group of L ² or the divalent linking group of L ³ must have an ether bond from the viewpoint of sculpture residue removal (rinse). It is more preferable to have an ether bond contained in the oxyalkylene group.
Among the compounds represented by formula (C2-2) and formula (C2-3), from the viewpoint of crosslinkability and the like, in formula (C2-2), an n-valent linking group of L ¹ and / or L ² The divalent linking group is preferably a group having a sulfur atom.

  Specific examples of component C2 that can be applied to the present invention are shown below. For example, vinyltrichlorosilane, 1,3-bis (trichlorosilane) propane, 1,3-bis (tribromosilane) propane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, p-styryltrimethoxysilane , Γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminop Propylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 2 -(2-aminoethylthioethyl) diethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, 2- (2-aminoethylthioethyl) triethoxysilane, dimethoxymethyl-3- (3- Phenoxypro Luthiopropyl) silane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, 1,4-bis (triethoxysilyl) benzene, bis (triethoxysilyl) ethane, 1,6-bis ( Trimethoxysilyl) hexane, 1,8-bis (triethoxysilyl) octane, 1,2-bis (trimethoxysilyl) decane, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) urea, γ- Examples include chloropropyltrimethoxysilane, γ-triethoxysilylpropyl (meth) acrylate, γ-ureidopropyltriethoxysilane, trimethylsilanol, diphenylsilanediol, and triphenylsilanol. In addition, the compounds shown below are preferred, but the present invention is not limited to these compounds.

In the above formulas, R represents a partial structure selected from the following structures. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

In the above formulas, R represents a partial structure shown below. R ¹ has the same meaning as described above. When a plurality of R and R ¹ are present in the molecule, these may be the same or different from each other, and are preferably the same in terms of synthesis suitability.

  Component C2 can be obtained by appropriately synthesizing, but it is preferable to use a commercially available product from the viewpoint of cost. As component C2, for example, commercially available silane products and silane coupling agents commercially available from Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Co., Ltd., Chisso Co., Ltd., etc. Since the product corresponds to this, these commercially available products may be appropriately selected and used for the resin composition of the present invention according to the purpose.

As component C2 in the present invention, a partial hydrolysis condensate obtained by using one compound having a hydrolyzable silyl group and / or silanol group, or a partial cohydrolysis condensate obtained by using two or more compounds Can be used. Hereinafter, these compounds may be referred to as “partial (co) hydrolysis condensates”.
Among silane compounds as partial (co) hydrolysis condensate precursors, from the viewpoint of versatility, cost, and film compatibility, it has a substituent selected from a methyl group and a phenyl group as a substituent on silicon. It is preferably a silane compound, specifically, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane. Is exemplified as a preferred precursor.
In this case, as a partial (co) hydrolysis condensate, dimers of the silane compound as described above (1 mol of water was allowed to act on 2 mol of the silane compound to remove 2 mol of alcohol to form disiloxane units. To 100-mer, preferably 2 to 50-mer, more preferably 2 to 30-mer, and a partial cohydrolysis condensate using two or more silane compounds as raw materials. It is also possible to use it.

  In addition, as such a partial (co) hydrolysis condensate, you may use what is marketed as a silicone alkoxy oligomer (for example, it is marketed from Shin-Etsu Chemical Co., Ltd.), etc. You may use what was manufactured by removing by-products, such as alcohol and hydrochloric acid, after making the hydrolysis water of less than an equivalent react with a hydrolysable silane compound based on a conventional method. In production, for example, when using alkoxysilanes or acyloxysilanes as described above as the precursor hydrolyzable silane compound, acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, hydroxide Alkaline or alkaline earth metal hydroxides such as potassium, alkaline organic substances such as triethylamine, etc. may be used as a reaction catalyst for partial hydrolysis and condensation. In the case of direct production from chlorosilanes, by-product hydrochloric acid is used as a catalyst. And water and alcohol may be reacted.

  Only 1 type may be used for component C2 in the resin composition of this invention, and 2 or more types may be used together. The content of the component C2 contained in the resin composition of the present invention is preferably in the range of 0.1 to 80% by mass, more preferably in the range of 1 to 40% by mass in terms of solid content. Most preferably, it is the range of 5-30 mass%.

(Component D) Plasticizer The resin composition of the present invention preferably contains (Component D) a plasticizer from the viewpoint of imparting necessary flexibility as a flexographic plate. As the plasticizer, those known as polymer plasticizers can be used, and are not limited. For example, those described in pages 211 to 220 of Polymer Dictionary (First Edition, published by Maruzen Co., Ltd., 1994). Adipic acid derivatives, azelaic acid derivatives, benzoyl acid derivatives, citric acid derivatives, epoxy derivatives, glycol derivatives, hydrocarbons and derivatives, oleic acid derivatives, phosphoric acid derivatives, phthalic acid derivatives, polyesters, ricinoleic acid derivatives, sebacic acid derivatives, Examples include stearic acid derivatives, sulfonic acid derivatives, terpenes and derivatives, and trimellitic acid derivatives. Among these, adipic acid derivatives, citric acid derivatives, and phosphoric acid derivatives are preferable from the viewpoint of the effect of reducing the glass transition temperature.
As the adipic acid derivative, dibutyl adipate and 2-butoxyethyl adipate are preferable, and as the citric acid derivative, tributyl citrate is preferable. Examples of phosphoric acid derivatives include tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, t-butylphenyl phosphate, 2-ethylhexyl phosphate Examples thereof include diphenyl and the like. Among them, triphenyl phosphate, cresyl diphenyl phosphate and tricresyl phosphate are preferable, and cresyl diphenyl phosphate is more preferable.
Component D in the resin composition of the present invention may be used alone or in combination of two or more. The content of the component D contained in the resin composition of the present invention is preferably 1 to 50% by mass and more preferably 10 to 40% by mass in terms of solid content from the viewpoint of lowering the glass transition temperature to room temperature or lower. Preferably, 20 to 30% by mass is more preferable.

(Component E) Polymerization initiator When the resin composition of the present invention is used for producing a relief forming layer, it is preferable to further contain (Component E) a polymerization initiator. As the polymerization initiator, a radical polymerization initiator is preferable, and compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be preferably exemplified.
As radical polymerization initiators, aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens Examples include compounds having a bond, azo compounds, etc. Among them, from the viewpoints of improving engraving sensitivity and the relief edge shape when applied to the relief forming layer of a relief printing plate precursor, organic peroxides or azo compounds Compounds are more preferred, and organic peroxides are particularly preferred. As the organic peroxide, those described in JP-A-2008-63554 and JP-A-2008-233244 are preferable, and among them, t-butylperoxybenzoate is preferable.

Further, as a preferred combination component, it is more preferable to use an organic peroxide and a photothermal conversion agent in combination, since the engraving sensitivity is extremely high, and the organic peroxide and the photothermal conversion agent carbon black are used in combination. The embodiment was most preferred. This is because when an organic peroxide is used to cure the relief forming layer by thermal crosslinking, unreacted organic peroxide that does not participate in radical generation remains, but the remaining organic peroxide is self-reactive. Works as an additive and decomposes exothermically during laser engraving. As a result, the amount of heat generated is added to the irradiated laser energy, so that the engraving sensitivity is estimated to increase.
This effect is remarkable when carbon black is used as the photothermal conversion agent. This is because the heat generated from the carbon black is transferred to the organic peroxide, resulting in heat generation not only from the carbon black but also from the organic peroxide, and generation of thermal energy to be used for decomposition of the component B and the like. This is considered to occur synergistically.
A polymerization initiator may be used individually by 1 type, and can also use 2 or more types together.
The content of the polymerization initiator in the resin composition of the present invention is 0.01 to 10% by mass with respect to the total mass of the solid content of the relief forming layer, from the viewpoint of curing speed and final adjustment of film hardness. Preferably, 0.1-3 mass% is more preferable.

(Component F) Photothermal Conversion Agent The resin composition for laser engraving of the present invention preferably further contains a photothermal conversion agent. It is considered that the photothermal conversion agent promotes thermal decomposition of the cured product during laser engraving by absorbing laser light and generating heat. For this reason, it is preferable to select a photothermal conversion agent that absorbs light having a laser wavelength used for engraving.
The relief printing plate precursor for laser engraving produced using the resin composition for laser engraving of the present invention is irradiated with a laser (YAG laser, semiconductor laser, fiber laser, surface emitting laser, etc.) emitting an infrared ray of 700 to 1,300 nm. As a photothermal conversion agent, it is preferable to use a compound having a maximum absorption wavelength at 700 to 1,300 nm. Various dyes or pigments are used as the photothermal conversion agent.

  Among the photothermal conversion agents, as the dye, commercially available dyes and known ones described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specific examples include those having a maximum absorption wavelength at 700 to 1,300 nm. Azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, diimonium compounds, quinone imine dyes Preferred are dyes such as methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes. Dyes preferably used in the present invention include cyanine dyes such as heptamethine cyanine dyes, oxonol dyes such as pentamethine oxonol dyes, phthalocyanine dyes, and paragraphs 0124 to 0137 of JP-A-2008-63554. Mention may be made of dyes.

Among the photothermal conversion agents used in the present invention, commercially available pigments and color index (CI) manuals, “Latest Pigment Handbook” (edited by the Japan Pigment Technical Association, 1977), “Latest Pigment Application” The pigments described in “Technology” (CMC Publishing, 1986) and “Printing Ink Technology” CMC Publishing, 1984) can be used. Examples of the pigment include pigments described in paragraphs 0122 to 0125 of JP-A-2009-178869.
Of these pigments, carbon black is preferred. As long as the dispersibility in the composition is stable, any carbon black can be used regardless of the application, in addition to the classification based on ASTM. Carbon black includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black and the like. In order to facilitate dispersion, black colorants such as carbon black can be used as color chips or color pastes previously dispersed in nitrocellulose or a binder, if necessary. Such chips and pastes can be easily obtained as commercial products. Examples of carbon black include those described in paragraphs 0130 to 0134 of JP2009-178869A.

  The content of the photothermal conversion agent in the resin composition varies greatly depending on the molecular extinction coefficient inherent to the molecule, but is preferably in the range of 0.01 to 30% by mass of the total solid content of the resin composition, 0.05-20 mass% is more preferable, and 0.1-10 mass% is especially preferable.

(Component G) At least one oxy compound of a metal or metalloid selected from Group 1 to 16 of the periodic table The resin composition of the present invention is preferably selected from Group 1 to 16 of (Component G) the periodic table. Containing at least one oxy compound of a metal or metalloid. The component G is not particularly limited as long as it is selected from the group 1 to 16 of the periodic table, but alkali metals (Li, Na, K, Rb, Cs, Fr), alkaline earth metals (Be, Mg) , Ca, Sr, Ba, Ra), aluminum, silicon, phosphorus, titanium, germanium, arsenic, zirconium, tin, zinc, cadmium, bismuth, indium, scandium or antimony. Preferred in terms of engraving sensitivity are alkaline earth metals, aluminum, silicon, phosphorus, bismuth, titanium, germanium, arsenic, zirconium, tin, zinc, more preferably alkaline earth metals, tin, zinc, bismuth, Zirconium, titanium (preferably valence 4), aluminum, particularly preferably alkaline earth metal, tin, bismuth, zinc, titanium and aluminum.
Examples of the oxy compound (= oxygen-containing compound) include alkoxides, phenoxides, enolates, carbonates, acetates or carboxylates and oxides of the above metals or metalloids.
If desired, the organic portion of the oxy compound can be partially polyvalent, such as those derived from polyhydric alcohols (eg, glycol or glycerol), polyvinyl alcohol, or hydroxycarboxylic acids. Chelate compounds may be used. When carbon atoms are present, typically the number of carbon atoms per metal or metalloid ranges from 4 to 24.
In the present invention, zinc, tin, bismuth, and aluminum carboxylates are preferable, and among them, zinc acetate, zinc 2-ethylhexanoate, tin 2-ethylhexanoate, bismuth tris (2-ethylhexanoate), bis (2 -Ethylhexanoic acid) hydroxyaluminum is particularly preferred.
The content of Component G in the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.5 to 10% by mass, and 1 to 5% by mass from the viewpoint of engraving sensitivity and film property. Further preferred.

<Other ingredients>
In addition to Component A to Component G, the resin composition of the present invention can be used in combination with various compounds depending on the purpose as long as the effects of the present invention are not impaired. In addition to the above components A and B, a known binder polymer can be used in combination with the resin composition for laser engraving of the present invention. For example, from the viewpoint of laser engraving sensitivity, a polymer containing a partial structure that is thermally decomposed by exposure or heating is preferable. In addition, for example, when a soft and flexible film formation is intended, a soft resin is selected. Furthermore, it is preferable to use a hydrophilic or alcoholic polymer from the viewpoint of easy preparation of the composition for a relief forming layer and improvement in resistance to oil-based ink in the obtained relief printing plate. These components are described in JP2008-163081A.

In addition, polyesters composed of hydroxycarboxylic acid units such as polylactic acid can be preferably used. Specific examples of such polyester include polyhydroxyalkanoate (PHA), lactic acid-based polymer, polyglycolic acid (PGA), polycaprolactone (PCL), poly (butylene succinic acid), and derivatives or mixtures thereof. Those selected from the group consisting of
In addition, when used for the purpose of curing by heating or exposure and improving the strength, a polymer having a carbon-carbon unsaturated bond in the molecule is preferably used. Examples of the polymer containing a carbon-carbon unsaturated bond in the main chain include SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene). -Polystyrene) and the like.
The polymer having a carbon-carbon unsaturated bond in the side chain is a carbon-carbon unsaturated group such as an allyl group, an acryloyl group, a methacryloyl group, a styryl group, or a vinyl ether group in the skeleton of the binder polymer applicable in the present invention. It is obtained by introducing a bond into the side chain.
Thus, in consideration of the physical properties according to the application application of the relief printing plate, a binder polymer can be selected according to the purpose, and one or more of the binder polymers can be used in combination.

  In the resin composition for laser engraving of the present invention, various additives usually used in the field of rubber can be appropriately blended within a range that does not impair the effects of the present invention. Examples include vulcanizing agents, fillers, waxes, process oils, organic acids, metal oxides, antiozonants, antiaging agents, thermal polymerization inhibitors, colorants, etc., and these are used alone. Alternatively, two or more kinds may be used in combination.

When process oil is used, for example, aromatic process oil, naphthenic process oil, and paraffinic process oil can be mentioned. The amount added is preferably 1 to 70 parts by mass per 100 parts by mass of component B.
The organic acid can be used as an auxiliary agent for vulcanization acceleration in combination with a conventional vulcanizing agent as a metal salt. Examples of the organic acid include stearic acid, oleic acid, and murastic acid. Examples of the metal source used in combination include metal oxides such as zinc oxide (zinc white) and magnesium oxide. In these vulcanization processes, organic acids and metal oxides form metal salts in the rubber, and the activation of vulcanizing agents such as sulfur is promoted. The amount of the metal oxide added to form such a metal salt in the system is preferably 0.1 to 10 parts by mass and more preferably 2 to 10 parts by mass per 100 parts by mass of the rubber component (component B). 0.1-5 mass parts is preferable per 100 mass parts of rubber components (component B), and, as for the addition amount of an organic acid, 0.1-3 mass parts is more preferable.

  The resin composition of the present invention preferably contains an alcohol exchange reaction catalyst in order to promote the formation of a crosslinked structure of component C2. The alcohol exchange reaction catalyst can be applied without limitation as long as it is a reaction catalyst generally used in a silane coupling reaction. Hereinafter, the acid or basic catalyst which is a typical alcohol exchange reaction catalyst will be sequentially described.

As the catalyst, an acid or a basic compound is used as it is, or a catalyst dissolved in a solvent such as water or an organic solvent (hereinafter also referred to as an acidic catalyst or a basic catalyst, respectively). The concentration at the time of dissolving in the solvent is not particularly limited, and may be appropriately selected according to the characteristics of the acid or basic compound used, the desired content of the catalyst, and the like.
Acidic catalysts include hydrogen halides such as hydrochloric acid, nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, hydrogen peroxide, carbonic acid, carboxylic acids such as formic acid and acetic acid, and R of the structural formula represented by RCOOH. Examples thereof include substituted carboxylic acids substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, phosphoric acid, heteropolyacid, and inorganic solid acids.
Examples of the basic catalyst include ammoniacal bases such as aqueous ammonia, amines, alkali metal hydroxides, alkali metal alkoxides, alkaline earth oxides, quaternary ammonium salt compounds, quaternary phosphonium salt compounds, and the like.

Examples of amines include (a) hydrazine compounds such as hydrazine; (b) aliphatic amines, alicyclic amines or aromatic amines; (c) cyclic amines containing condensed rings; (d) amino acids and amides. Oxygen-containing amines such as alcohol amines, ether amines, imides or lactams; (e) hetero-containing amines having a hetero atom such as S and Se;
As the aliphatic amine (b), an amine compound represented by the formula (D-1) is preferable.
N (R ^d1 ) (R ^d2 ) (R ^d3 ) (D-1)
In formula (D-1), R ^{d1 to} R ^d3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 represents an aryl group, a heterocyclic ring (thiophene) containing a sulfur atom or an oxygen atom having 3 to 10 ring members, and the alkyl group and cycloalkyl group may have at least one unsaturated bond.
The amine compound represented by the formula (D-1) may have a substituent, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group, Examples thereof include (di) alkylamino groups and hydroxy groups having an alkyl group having 1 to 6 carbon atoms.
Two or more groups of R ^{d1 to} R ^d3 may be bonded to form a C═N bond. Examples of the amine compound having a C═N bond include guanidine and 1,1,3,3-tetramethylguanidine.
As the alicyclic amine of (b), an alicyclic compound containing a nitrogen atom in a ring skeleton in which two or more groups out of R ^{d1 to} R ^d3 in the compound represented by the formula (D-1) are bonded. Examples include amines. Examples of the alicyclic amine include pyrrolidine, piperidine, piperazine, and quinuclidine.
Examples of the aromatic amine (b) include imidazole, pyrrole, pyridine, pyridazine, pyrazine, purine, quinoline, and quinazoline. The aromatic amine may have a substituent, and examples of the substituent include the substituent in formula (D-1).
Further, two or more aliphatic amines, alicyclic amines, and aromatic amines that are the same or different may be combined to form a polyamine such as diamine or triamine. The polyamine is preferably a polyamine in which aliphatic amines are bonded to each other, and examples thereof include hexamethylenetetramine and polyethyleneimine (Epomin, manufactured by Nippon Shokubai Co., Ltd.).

The (c) cyclic amine containing a condensed ring is a cyclic amine containing a ring skeleton in which at least one nitrogen atom forms a condensed ring. For example, 1,8-diazabicyclo [5.4.0] undeca- 7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane, among others, 1,8-diazabicyclo [5.4]. 0.0] Undec-7-ene is preferred.
Examples of the oxygen-containing amines such as (d) amino acids, amides, alcohol amines, ether amines, imides or lactams include phthalimide, 2,5-piperazinedione, maleimide, caprolactam, pyrrolidone, morpholine, glycine, Examples include alanine and phenylalanine.
In addition, (c) and (d) may have the said substituent in the compound represented by Formula (D-1), and a C1-C6 alkyl group is especially preferable.
In the present invention, the amine compound is preferably (b) or (c). (B) is preferably an aliphatic amine, more preferably an aliphatic amine polyamine, and still more preferably polyethyleneimine. (C) is preferably 1,8-diazabicyclo [5.4.0] undec-7-ene.

From the viewpoint of film strength after thermal crosslinking, the preferable range of pKaH (acid dissociation constant of conjugate acid) as an amine is preferably 7 or more, more preferably 10 or more.
Among the acid or basic catalysts, methanesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, dodecylbenzenesulfonic acid, phosphoric acid, phosphonic acid are used from the viewpoint of promptly proceeding the alcohol exchange reaction in the membrane. , Acetic acid, polyethyleneimine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,1,3,3- Tetramethylguanidine is preferable, and phosphoric acid, polyethyleneimine, and 1,8-diazabicyclo [5.4.0] undec-7-ene are particularly preferable.

  In the resin composition of the present invention, only one alcohol exchange reaction catalyst may be used, or two or more kinds may be used in combination. The content of the alcohol exchange reaction catalyst in the resin composition is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass in the total solid content of the relief forming layer.

(Relief printing plate precursor for laser engraving)
The first embodiment of the relief printing plate precursor for laser engraving of the present invention has a relief forming layer comprising the resin composition for laser engraving of the present invention. Further, the second embodiment of the relief printing plate precursor for laser engraving of the present invention has a crosslinked relief forming layer obtained by crosslinking the relief forming layer comprising the resin composition for laser engraving of the present invention.
In the present invention, the “relief printing plate precursor for laser engraving” is a state in which a relief forming layer having a crosslinkability made of a resin composition for laser engraving is cured by light and / or heat before being crosslinked. State.
In the present invention, the “relief-forming layer” refers to a layer in a state before being crosslinked, that is, a layer made of the resin composition for laser engraving of the present invention, and may be dried if necessary. Good. In the present invention, the “crosslinked relief forming layer” refers to a layer obtained by crosslinking the relief forming layer. The crosslinking is preferably performed by heat and / or light, and more preferably by heat. Moreover, the said bridge | crosslinking will not be specifically limited if it is reaction by which a resin composition is hardened, It is the concept containing the crosslinked structure by reaction of components C1 and components C2.
A “relief printing plate” is produced by laser engraving a printing plate precursor having a crosslinked relief forming layer. The “relief layer” refers to a layer engraved with a laser in a relief printing plate, that is, the crosslinked relief forming layer after laser engraving.

  The relief printing plate precursor for laser engraving of the present invention has a relief forming layer made of a resin composition for laser engraving containing the above components. The (crosslinked) relief forming layer is preferably provided on the support. The relief printing plate precursor for laser engraving further has an adhesive layer between the support and the (crosslinked) relief forming layer, if necessary, and a slip coat layer and a protective film on the (crosslinked) relief forming layer. May be.

<Relief forming layer>
The relief forming layer is a layer made of the resin composition of the present invention. The relief printing plate precursor for laser engraving of the present invention is a relief forming layer imparted with a crosslinkable function by Component C1 or Component C2.

  As a production mode of a relief printing plate using a relief printing plate precursor for laser engraving, a relief printing plate precursor having a crosslinked relief forming layer is obtained by crosslinking the relief forming layer, and then a crosslinked relief forming layer (hard relief forming layer) is used. An embodiment in which a relief layer is formed by laser engraving to form a relief printing plate is preferred. By crosslinking the relief forming layer, wear of the relief layer during printing can be prevented, and a relief printing plate having a relief layer having a sharp shape after laser engraving can be obtained.

  The relief forming layer is formed by molding the resin composition having the above components for the relief forming layer into a sheet shape or a sleeve shape. The relief forming layer is usually provided on a support which will be described later. However, the relief forming layer can be directly formed on the surface of a member such as a cylinder provided in an apparatus for plate making and printing, or can be arranged and fixed there. It does not necessarily require a support. Hereinafter, the case where the relief forming layer is formed into a sheet shape will be mainly described as an example.

<Support>
The material used for the support of the relief printing plate precursor for laser engraving is not particularly limited, but materials having high dimensional stability are preferably used. For example, metals such as steel, stainless steel and aluminum, polyester (for example, PET (polyethylene terephthalate)) , Plastic resins such as PBT (polybutylene terephthalate), PAN (polyacrylonitrile)) and polyvinyl chloride, synthetic rubbers such as styrene-butadiene rubber, and plastic resins reinforced with glass fibers (such as epoxy resins and phenol resins) It is done. As the support, a PET film or a steel substrate is preferably used. The form of the support is determined depending on whether the relief forming layer is a sheet or a sleeve.

<Adhesive layer>
When the relief forming layer is formed on the support, an adhesive layer may be provided between them for the purpose of enhancing the adhesive strength between the layers. Examples of materials (adhesives) that can be used for the adhesive layer include: Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.

<Protective film, slip coat layer>
For the purpose of preventing scratches or dents on the surface of the relief forming layer or the surface of the crosslinked relief forming layer, a protective film may be provided on the surface of the relief forming layer or the surface of the crosslinked relief forming layer. The thickness of the protective film is preferably 25 to 500 μm, more preferably 50 to 200 μm. As the protective film, for example, a polyester film such as PET, or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used. The surface of the film may be matted. The protective film is preferably peelable.
When the protective film cannot be peeled or when it is difficult to adhere to the relief forming layer, a slip coat layer may be provided between both layers. The material used for the slip coat layer is a resin that can be dissolved or dispersed in water, such as polyvinyl alcohol, polyvinyl acetate, partially saponified polyvinyl alcohol, hydroxyalkyl cellulose, alkyl cellulose, polyamide resin, etc. It is preferable that

(Manufacturing method of relief printing plate precursor for laser engraving)
Formation of the relief forming layer in the relief printing plate precursor for laser engraving is not particularly limited, for example, after preparing a resin composition for laser engraving and removing the solvent from the resin composition for laser engraving, The method of melt-extruding on a support body is mentioned. Alternatively, the resin composition for laser engraving may be cast on a support and dried in an oven to remove the solvent from the resin composition. Among them, the plate making method of the relief printing plate for laser engraving of the present invention comprises a layer forming step for forming a relief forming layer comprising the resin composition for laser engraving of the present invention, and a crosslinked relief formation by thermally crosslinking the relief forming layer. A plate making method including a crosslinking step for obtaining a relief printing plate precursor having a layer is preferable.

  Thereafter, a protective film may be laminated on the relief forming layer as necessary. Lamination can be performed by pressure-bonding the protective film and the relief forming layer with a heated calendar roll or the like, or by bringing the protective film into close contact with the relief forming layer impregnated with a small amount of solvent on the surface. When using a protective film, you may take the method of laminating | stacking a relief forming layer on a protective film first, and laminating a support body then. When providing an adhesive layer, it can respond by using the support body which apply | coated the adhesive layer. When providing a slip coat layer, it can respond by using the protective film which apply | coated the slip coat layer.

<Layer formation process>
The plate making method of the relief printing plate for laser engraving of the present invention preferably includes a layer forming step of forming a relief forming layer comprising the resin composition for laser engraving of the present invention. As a method for forming the relief forming layer, the resin composition for laser engraving of the present invention is prepared. A method of preparing a resin composition for laser engraving, casting the resin composition for laser engraving on a support, drying it in an oven, and removing the solvent is preferable.

  The resin composition for laser engraving can be produced, for example, by dissolving component A, component B, and other optional components in an appropriate solvent, and then dissolving component C1, component C2, and a polymerization initiator. It is preferable to use an amount of solvent such that the viscosity of the resin composition is 10 to 200 poise. For the stirring and mixing, any method suitable for mixing a liquid having the above viscosity range can be used, but mixing with a static mixer or a dynamic mixer is particularly preferable. Most of the solvent component needs to be removed at the stage of producing the relief printing plate precursor. It is preferable to use a solvent that easily volatilizes and suppress the total amount of the solvent as small as possible by adjusting the temperature.

  The thickness of the (crosslinked) relief forming layer in the relief printing plate precursor for laser engraving is preferably 0.05 to 10 mm, more preferably 0.05 to 7 mm, and still more preferably 0.05 to 3 mm before and after crosslinking.

<Crosslinking process>
The plate making method of the relief printing plate for laser engraving of the present invention is preferably a plate making method including a crosslinking step for obtaining a relief printing plate precursor having a crosslinked relief forming layer by thermally crosslinking the relief forming layer. The relief forming layer can be crosslinked by heating the relief printing plate precursor for laser engraving (step of crosslinking by heat). Examples of the heating means for crosslinking by heat include a method of heating the printing plate precursor in a hot air oven or a far infrared oven for a predetermined time, and a method of contacting a heated roll for a predetermined time. By thermally crosslinking the relief forming layer, there is an advantage that, firstly, the relief formed after laser engraving becomes sharp, and secondly, the adhesiveness of engraving residue generated during laser engraving is suppressed.

(Relief printing plate and plate making method)
The plate making method of the relief printing plate of the present invention comprises (1) a step of crosslinking the relief forming layer in the relief printing plate precursor for laser engraving with heat and / or light (crosslinking step), and (2) a crosslinked relief. A step of engraving the formation layer by laser engraving to form a relief layer (engraving step).

  The relief printing plate of the present invention is a relief printing plate having a relief layer obtained by crosslinking and laser engraving a layer made of the resin composition for laser engraving of the present invention. It is preferably a relief printing plate that has been made. The relief printing plate of the present invention can be suitably used during printing with water-based ink. The layer forming step and the cross-linking step in the plate making method of the relief printing plate of the present invention are synonymous with the layer forming step and the cross-linking step in the plate making method of the relief printing plate precursor for laser engraving, and the preferred range is also the same.

<Engraving process>
The plate making method of the relief printing plate of the present invention preferably includes an engraving step of laser engraving the relief printing plate precursor having the crosslinked relief forming layer. The engraving step is a step of forming a relief layer by laser engraving the crosslinked relief forming layer crosslinked in the crosslinking step. Specifically, it is preferable to form a relief layer by engraving a crosslinked crosslinked relief forming layer by irradiating a laser beam corresponding to a desired image. Moreover, the process of controlling a laser head with a computer based on the digital data of a desired image and carrying out scanning irradiation with respect to a bridge | crosslinking relief forming layer is mentioned preferably.
In this engraving process, an infrared laser is preferably used. When irradiated with an infrared laser, the molecules in the crosslinked relief forming layer undergo molecular vibrations and generate heat. When a high-power laser such as a carbon dioxide laser or YAG laser is used as an infrared laser, a large amount of heat is generated in the laser irradiation part, and molecules in the crosslinked relief forming layer are selectively cut by molecular cutting or ionization. That is, engraving is performed. The advantage of laser engraving is that the engraving depth can be set arbitrarily, so that the structure can be controlled three-dimensionally. For example, the portion that prints fine halftone dots can be engraved shallowly or with a shoulder so that the relief does not fall down due to printing pressure, and the portion of the groove that prints fine punched characters is engraved deeply As a result, the ink is less likely to be buried in the groove, and the collapsed characters can be suppressed. In particular, when engraving with an infrared laser corresponding to the absorption wavelength of the photothermal conversion agent, the crosslinked relief forming layer can be selectively removed with higher sensitivity, and a relief layer having a sharp image can be obtained.

As the infrared laser used in the engraving process, a carbon dioxide laser (CO ₂ laser) or a semiconductor laser is preferable from the viewpoints of productivity and cost. In particular, a semiconductor infrared laser with a fiber (FC-LD) is preferably used. In general, a semiconductor laser is more efficient and cheaper than a CO ₂ laser and can be miniaturized, and since it is small, it can be easily arrayed. Furthermore, the beam shape can be controlled by processing the fiber.
The semiconductor laser preferably has a wavelength of 700 to 1,300 nm, more preferably 800 to 1,200 nm, still more preferably 860 to 1,200 nm, and particularly preferably 900 to 1,100 nm.

The semiconductor laser is effective for the engraving process because it can efficiently output laser light by attaching an optical fiber. Furthermore, the beam shape can be controlled by processing the fiber. For example, the beam profile can have a top hat shape, and energy can be stably given to the plate surface. Details of the semiconductor laser are described in “Laser Handbook 2nd Edition” edited by the Laser Society, practical laser technology, and the Institute of Electronics and Communication Engineers of Japan.
Also, a plate making apparatus equipped with a fiber-coupled semiconductor laser that can be suitably used in a plate making method of a relief printing plate using the relief printing plate precursor of the present invention is disclosed in JP 2009-172658 A and JP 2009-214334 A. And can be used for making a relief printing plate according to the present invention.

In the method for making a relief printing plate of the present invention, following the engraving step, the following rinsing step, drying step, and / or post-crosslinking step may be included as necessary.
Rinsing step: a step of rinsing the engraved surface of the relief layer surface after engraving with water or a liquid containing water as a main component.
Drying step: a step of drying the engraved relief layer.
Post-crosslinking step: a step of imparting energy to the relief layer after engraving and further crosslinking the relief layer.
Since the engraving residue adheres to the engraving surface after the above process, a rinsing step of rinsing the engraving residue by rinsing the engraving surface with water or a liquid containing water as a main component may be added. As a means of rinsing, there is a method of washing with tap water, a method of spraying high-pressure water, and a known batch type or conveying type brush type washing machine as a photosensitive resin relief printing machine. For example, when the engraving residue cannot be removed, a rinsing liquid to which soap or a surfactant is added may be used.
When the rinsing process for rinsing the engraving surface is performed, it is preferable to add a drying process for drying the engraved relief forming layer and volatilizing the rinsing liquid.
Furthermore, you may add the post-crosslinking process which further bridge | crosslinks a relief forming layer as needed. By performing the post-crosslinking step, which is an additional cross-linking step, the relief formed by engraving can be further strengthened.

  The rinsing step is preferably a step of treating the relief layer with an alkaline liquid (rinsing liquid) having a pH of 9.5 to 14. The pH of the rinse liquid that can be used in the present invention is preferably 9.5 to 14 and more preferably 11 to 13 from the viewpoint of handleability. What is necessary is just to adjust pH using an acid and / or a base suitably in order to make a rinse liquid into said pH range, and the acid and base to be used are not specifically limited. The rinsing liquid that can be used in the present invention preferably contains water as a main component. Moreover, the rinse liquid may contain water miscible solvents, such as alcohol, acetone, tetrahydrofuran, etc. as solvents other than water.

  It is preferable that the rinse liquid contains a surfactant. As the surfactant that can be used in the present invention, a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or from the viewpoint of reducing engraving residue removal and influence on the relief printing plate, Preferred are betaine compounds (amphoteric surfactants) such as phosphine oxide compounds. The betaine compound is preferably a compound represented by the following formula (1) and / or a compound represented by the following formula (2).

（式（１）中、Ｒ¹〜Ｒ³はそれぞれ独立に、一価の有機基を表し、Ｒ⁴は単結合、又は、二価の連結基を表し、ＡはＰＯ（ＯＲ⁵）Ｏ^-、ＯＰＯ（ＯＲ⁵）Ｏ^-、Ｏ^-、ＣＯＯ^-、又は、ＳＯ₃ ^-を表し、Ｒ⁵は、水素原子、又は、一価の有機基を表し、Ｒ¹〜Ｒ³のうち２つ以上の基が互いに結合し環を形成してもよい。）

(In formula (1), R ^{1 to} R ³ each independently represents a monovalent organic group, R ⁴ represents a single bond or a divalent linking group, and A represents PO (OR ⁵ ) O ^−. , OPO (OR ⁵ ) O ⁻ , O ⁻ , COO ⁻ , or SO ₃ ⁻ , R ⁵ represents a hydrogen atom or a monovalent organic group, and two or more of R ^{1 to} R ³ May be bonded to each other to form a ring.)

（式（２）中、Ｒ⁶〜Ｒ⁸はそれぞれ独立に、一価の有機基を表し、Ｒ⁹は単結合、又は、二価の連結基を表し、ＢはＰＯ（ＯＲ¹⁰）Ｏ^-、ＯＰＯ（ＯＲ¹⁰）Ｏ^-、Ｏ^-、ＣＯＯ^-、又は、ＳＯ₃ ^-を表し、Ｒ¹⁰は、水素原子、又は、一価の有機基を表し、Ｒ⁶〜Ｒ⁸のうち２つ以上の基が互いに結合し環を形成してもよい。）

(In formula (2), R ^{6 to} R ⁸ each independently represents a monovalent organic group, R ⁹ represents a single bond or a divalent linking group, and B represents PO (OR ¹⁰ ) O ^−. , OPO (OR ¹⁰ ) O ⁻ , O ⁻ , COO ⁻ , or SO ₃ ⁻ , R ¹⁰ represents a hydrogen atom or a monovalent organic group, and two or more of R ^{6 to} R ⁸ May be bonded to each other to form a ring.)

The compound represented by the formula (1) or the compound represented by the formula (2) is preferably a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or a phosphine oxide compound. In the present invention, N = O amine oxide compound, and, each structure of the P = O phosphine oxide ^{compounds, N + -O -, P +} -O - shall be regarded as.
R ^{1 to} R ³ in the formula (1) each independently represent a monovalent organic group. Moreover, although two or more groups among R ^{1 to} R ³ may be bonded to each other to form a ring, it is preferable that no ring is formed.
The monovalent organic group in R ^{1 to} R ³ is not particularly limited, but an alkyl group, an alkyl group having a hydroxy group, an alkyl group having an amide bond in the alkyl chain, or an ether bond in the alkyl chain. The alkyl group is preferably an alkyl group, an alkyl group having a hydroxy group, or an alkyl group having an amide bond in the alkyl chain. In addition, the alkyl group in the monovalent organic group may be linear, branched or have a ring structure.
Further, it is particularly preferable that two of R ^{1 to} R ³ are methyl groups, that is, the compound represented by the formula (1) has an N, N-dimethyl structure. With the above structure, particularly good rinsing properties are exhibited.

R ⁴ in the formula (1) represents a single bond or a divalent linking group, and is a single bond when the compound represented by the formula (1) is an amine oxide compound. The divalent linking group in R ⁴ is not particularly limited, but is preferably an alkylene group or an alkylene group having a hydroxy group, and is an alkylene group having 1 to 8 carbon atoms or a carbon having a hydroxy group. It is more preferably an alkylene group having 1 to 8 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms or an alkylene group having 1 to 3 carbon atoms having a hydroxy group.
A in the formula (1) represents PO (OR ⁵ ) O ⁻ , OPO (OR ⁵ ) O ⁻ , O ⁻ , COO ⁻ , or SO ₃ ^−, and represents O ⁻ , COO ⁻ , or SO ₃ ^−. is preferably, COO ^- is more preferable.
When A ⁻ is O ⁻ , R ⁴ is preferably a single bond.
R ⁵ in PO (OR ⁵ ) O ⁻ and OPO (OR ⁵ ) O ⁻ represents a hydrogen atom or a monovalent organic group, and is a hydrogen atom or an alkyl group having one or more unsaturated fatty acid ester structures. It is preferable that
R ⁴ is preferably a group having no PO (OR ⁵ ) O ⁻ , OPO (OR ⁵ ) O ⁻ , O ⁻ , COO ⁻ , and SO ₃ ⁻ .

R ^{6 to} R ⁸ in the formula (2) each independently represent a monovalent organic group. Moreover, although two or more groups among R ^{6 to} R ⁸ may be bonded to each other to form a ring, it is preferable that no ring is formed. The monovalent organic group in R ^{6 to} R ⁸ is not particularly limited, but is preferably an alkyl group, an alkenyl group, an aryl group, or a hydroxy group, and is preferably an alkenyl group, an aryl group, or a hydroxy group. More preferably. In addition, the alkyl group in the monovalent organic group may be linear, branched or have a ring structure. Moreover, it is particularly preferable that two of R ^{6 to} R ⁸ are aryl groups.

R ⁹ in the formula (2) represents a single bond or a divalent linking group, and is a single bond when the compound represented by the formula (2) is a phosphine oxide compound. The divalent linking group for R ⁹ is not particularly limited, but is preferably an alkylene group or an alkylene group having a hydroxy group, and is an alkylene group having 1 to 8 carbon atoms or a carbon having a hydroxy group. It is more preferably an alkylene group having 1 to 8 carbon atoms, and further preferably an alkylene group having 1 to 3 carbon atoms or an alkylene group having 1 to 3 carbon atoms having a hydroxy group.
B in the formula (2) represents PO (OR ¹⁰ ) O ⁻ , OPO (OR ¹⁰ ) O ⁻ , O ⁻ , COO ⁻ , or SO ₃ ^−, and is preferably O ⁻ .
When B ⁻ is O ⁻ , R ⁹ is preferably a single bond.
R ¹⁰ in PO (OR ¹⁰ ) O ⁻ and OPO (OR ¹⁰ ) O ⁻ represents a hydrogen atom or a monovalent organic group, and is a hydrogen atom or an alkyl group having one or more unsaturated fatty acid ester structures. It is preferable that R ⁹ is preferably a group having no PO (OR ¹⁰ ) O ⁻ , OPO (OR ¹⁰ ) O ⁻ , O ⁻ , COO ⁻ , and SO ₃ ⁻ .
The compound represented by the formula (1) is preferably a compound represented by the following formula (3).

（式（３）中、Ｒ¹は一価の有機基を表し、Ｒ⁴は単結合、又は、二価の連結基を表し、ＡはＰＯ（ＯＲ⁵）Ｏ^-、ＯＰＯ（ＯＲ⁵）Ｏ^-、Ｏ^-、ＣＯＯ^-、又は、ＳＯ₃ ^-を表し、Ｒ⁵は、水素原子、又は、一価の有機基を表す。）

(In the formula (3), R ¹ represents a monovalent organic group, R ⁴ represents a single bond or a divalent linking group, and A represents PO (OR ⁵ ) O ⁻ , OPO (OR ⁵ ) O. ^-, O -, COO ^-, or SO ₃ ^- represents, R ⁵ represents a hydrogen atom, or a monovalent organic group).

Equation (3) in R ^1, A and, R ⁵ is, R ^1, A in Formula (1), and has the same meaning as R ^5, a preferred range is also the same.
The compound represented by the formula (2) is preferably a compound represented by the following formula (4).

（式（４）中、Ｒ⁶〜Ｒ⁸はそれぞれ独立に、アルキル基、アルケニル基、アリール基、又は、ヒドロキシ基を表す。ただし、Ｒ⁶〜Ｒ⁸の全てが同じ基となることはない。）

(In formula (4), R ^{6 to} R ⁸ each independently represents an alkyl group, an alkenyl group, an aryl group, or a hydroxy group. However, not all of R ^{6 to} R ⁸ are the same group. .)

R ^{6 to} R ⁸ in the formula (4) each independently represents an alkyl group, an alkenyl group, an aryl group, or a hydroxy group, and preferably an alkenyl group, an aryl group, or a hydroxy group.
Specific examples of the compound represented by the formula (1) or the compound represented by the formula (2) include the following compounds.

Examples of the surfactant include known anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Furthermore, fluorine-based and silicone-based nonionic surfactants can be used in the same manner.
Surfactant may be used individually by 1 type, or may use 2 or more types together. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass and more preferably 0.05 to 10% by mass with respect to the total mass of the rinse liquid. .

  As described above, a relief printing plate having a relief layer on the surface of an arbitrary substrate such as a support can be obtained. The thickness of the relief layer of the relief printing plate is preferably 0.05 to 10 mm, more preferably 0.05 to 7 mm, from the viewpoint of satisfying various printability such as abrasion resistance and ink transferability. Especially preferably, it is 0.05-3 mm.

Moreover, it is preferable that the Shore A hardness of the relief layer which a relief printing plate has is 50-90 degrees. When the Shore A hardness of the relief layer is 50 ° or more, even if the fine halftone dots formed by engraving are subjected to the strong printing pressure of the relief printing press, they do not collapse and can be printed normally. In addition, when the Shore A hardness of the relief layer is 90 ° or less, it is possible to prevent faint printing in a solid portion even in flexographic printing with a kiss touch.
The Shore A hardness in the present specification is a durometer (spring type) in which an indenter (called a push needle or indenter) is pushed and deformed on the surface of the object to be measured, and the amount of deformation (pushing depth) is measured and digitized. It is a value measured by a rubber hardness meter.

  The relief printing plate of the present invention is particularly suitable for printing with water-based ink by a flexographic printing machine, but printing is possible with any of water-based ink, oil-based ink and UV ink by a relief printing press. In addition, printing with UV ink by a flexographic printing machine is also possible. The relief printing plate of the present invention has excellent rinsing properties, no engraving residue remains, and the resulting relief layer is excellent in elasticity, so that it is excellent in water-based ink transfer and printing durability, and has a relief layer over a long period of time. Thus, printing can be carried out without concern for plastic deformation or deterioration of printing durability.

  Hereinafter, the present invention will be described in detail with reference to examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

The structural formulas or compound names of Component A to Component F used in Examples and Comparative Examples are shown below.
<(Component A) Binder polymer>
A-1: Polyvinyl butyral (PVB) (Denka butyral # 3000-2, in the following formula, l: m: n = 56 mol%: 43 mol%: 1 mol%, weight average molecular weight: 90,000, Electrochemical Industry (Made by Co., Ltd.)

<(Component B) Polymer having at least one kind of an alkali-decomposable group which becomes an acid group by alkali hydrolysis in the side chain>
B-1: Sumilite resin M-1 (phenol resin, manufactured by Sumitomo Bakelite Co., Ltd.)
B-2: Sumilite resin PR-53365 (phenol resin, manufactured by Sumitomo Bakelite Co., Ltd.)

(Synthesis of B-3)
(4′-hydroxyphenyl) methacrylate was dissolved in tetrahydrofuran to prepare 100 mL of a solution having a solid content concentration of 20% by mass. To this solution was added 3 mol% of methyl mercaptopropionate and 1 mol% of polymerization initiator V-65 manufactured by Wako Pure Chemical Industries, Ltd., and this was added dropwise to 10 mL of tetrahydrofuran heated to 60 ° C. over 4 hours in a nitrogen atmosphere. did. After completion of the dropwise addition, the reaction solution was heated for 4 hours, 1 mol% of V-65 was added again, and the mixture was stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 3 L of hexane, and the precipitated white powder was collected by filtration. The weight average molecular weight in terms of standard polystyrene was 12,000, and the dispersity (Mw / Mn) was 1.30.

(Synthesis of B-4)
<Synthesis of Raw Material Monomer M-1>
After cooling an acetone solution of methyl 4-aminobenzoate (manufactured by Wako Pure Chemical Industries, Ltd.) (302 g) and sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) (164 g) to 0 ° C., methacrylic acid chloride ( Wako Pure Chemical Industries, Ltd. (220 g) was added dropwise. This solution was filtered, and the obtained filtrate was put into hydrochloric acid water (35 wt% aqueous solution) (8 L), filtered, and the obtained filtrate was vacuum-dried to obtain a white solid raw material monomer M- having the following structure. 1 was obtained. Identification of M-1 was performed by ¹ H-NMR and IR-spectrum.

<Synthesis of B-4>
Light ester HO-MS (manufactured by Kyoeisha Chemical Co., Ltd.) (22 g), raw material monomer M-1 (17 g), raw material monomer M-2 (87 g) and dimethyl-2-2′- obtained as described above. A solution of azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.) (0.7 g) in N, N-dimethylacetamide (156 g) at 80 ° C. in a nitrogen stream at 80 ° C. (156 g) was added dropwise over 2.5 hours. After dropping, the mixture was further stirred at 80 ° C. for 2 hours.

After allowing to cool, N, N-dimethylacetamide (446 g), p-methoxyphenol (manufactured by Wako Pure Chemical Industries, Ltd.) (0.5 g), 1,8-diazabicyclo [5.4.0]- 7-Undecene (manufactured by Wako Pure Chemical Industries, Ltd.) (155 g) was added, and the mixture was stirred at room temperature for 12 hours. Thereafter, methanesulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (98 g) was added dropwise at 0 ° C., and then the solution was poured into vigorously stirred water (8 L) and stirred for 30 minutes. The precipitated white solid was filtered and dried to obtain a specific alkali-soluble polymer B-4.
The specific alkali-soluble polymer B-4 was identified by gel permeation chromatography, acid value titration (0.1 M aqueous sodium hydroxide), NMR, and IR spectrum. The weight average molecular weight in terms of standard polystyrene was 90,000, and Mw / Mn was 1.2.

  B-5 to B-7: Polymer B-5 (weight average molecular weight 50,000, Mw / Mn 1.3), Polymer B-6 (weight average molecular weight 10,000, Mw / Mn 1.3), Polymer B-7 (Weight average molecular weight 80,000, Mw / Mn1.4) is as shown below.

<(Component C1) ethylenically unsaturated compound>

<(Component C2) Compound having hydrolyzable silyl group and / or silanol group>
C2-1: KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<(Component D) Plasticizer>
D-1: Cresyl diphenyl phosphate <(Component E) polymerization initiator>
E-1: Perbutyl Z (t-butyl peroxybenzoate, manufactured by NOF Corporation)
<(Component F) photothermal conversion agent>
F-1: Ketjen Black EC600JD (carbon black, manufactured by Lion Corporation)
<(Component G) at least one oxy compound of metal or metalloid selected from Group 1-16 of the periodic table>
G-1: Zinc 2-ethylhexylate (manufactured by Hope Pharmaceutical Co., Ltd.)
<Other ingredients>
DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene (manufactured by San Apro Co., Ltd.)

Example 1
1. Preparation of resin composition for laser engraving (A-1) 35 parts of polyvinyl butyral (PVB, weight average molecular weight 90,000), (B-1) 5 parts of phenol resin, (D-1) 25 parts of cresyl diphenyl phosphate , (G-1) 2 parts of zinc 2-ethylhexylate and 100 parts of propylglycol monoethyl ether acetate (PGMEA) as a solvent were placed in a three-necked flask equipped with a stirring blade and a condenser and stirred at 70 ° C. For 120 minutes to dissolve. Thereafter, the solution was brought to 40 ° C., 10 parts of (C1-1) ethylenically unsaturated compound and 3 parts of (F-1) ketjen black EC600JD were added and stirred for 30 minutes. Then, 20 parts of (C2-1) KBE-846, 1.6 parts of (E-1) perbutyl Z, and 0.8 part of DBU were added and stirred at 40 ° C. for 10 minutes. By this operation, a fluid resin composition for laser engraving was obtained.
2. Preparation of relief printing plate precursor for laser engraving Place a spacer (frame) of a predetermined thickness on a PET substrate, and gently cast the resin composition for laser engraving so that it does not flow out of the spacer (frame). Then, it was dried for 3 hours to provide a relief forming layer having a thickness of about 1 mm to prepare a relief printing plate precursor for laser engraving.
3. Preparation of relief printing plate The relief forming layer of the obtained original plate was heated at 80 ° C for 3 hours and further at 100 ° C for 3 hours to thermally crosslink the relief forming layer. After peeling off the protective film from the printing plate precursor for laser engraving, a halftone dot pattern (2 × 2 dots, high with the laser engraving machine under the conditions of output: 12 W, head speed: 200 mm / second, pitch setting: 2,400 DPI 300 μm) was engraved. As a laser engraving machine, ADFLEX (commercially available from Comtex) was used.

4). Evaluation of relief printing plate The performance of the relief printing plate was evaluated in the following items, and the results are shown in Table 1.
(Tensile strength)
The tensile strength was measured according to JIS K6251. The results are shown in Table 1.

(Debris removal)
The rinsing liquid is prepared by mixing water and the following betaine compound (1-B), adding a 10% by weight aqueous solution of sodium hydroxide so that the pH becomes the value described in Table 1, and adding the betaine compound (1 The content of -B) was adjusted to 5% by mass of the entire rinse solution. The above rinse solution prepared on each plate engraved by the above method was dropped with a dropper (about 100 ml / m ² ) so that the plate surface was evenly wetted, and allowed to stand for 1 minute. The brush was rubbed 20 times (30 seconds) in parallel with the plate at a load of 200 gf. Thereafter, the plate surface was washed with running water, the water on the plate surface was removed, and air-dried for about 1 hour.

The surface of the rinsed plate was observed with a microscope having a magnification of 100 times (manufactured by Keyence Corporation), and the remaining residue on the plate was evaluated. The criteria are as follows. ◎ and ○ were accepted.
A: No residue remains on the plate.
○: Slight residue remains on the bottom (recess) of the image.
Δ: Waste remains on the plate image convex portion and the image bottom portion (concave portion).
X: Waste is adhered to the entire surface of the plate.

(Halftone dot missing)
The evaluation of halftone dot chipping was performed by observing the plate surface after the evaluation of residue removal with an optical microscope. The evaluation criteria are shown below. ◎, ○, and △ were considered acceptable. Preferred are ◎ and ○.
◎: 1cm square halftone dot area 0
○: 1 to 5 dot missing in 1 cm square area
Δ: In the halftone dot area of 1 cm square, the number of halftone dot missing is 6 to 10.
×: In a 1 cm square halftone dot region, the number of halftone dots missing is 11 or more.

(Examples 2-14, Comparative Examples 1-3)
Except that the components A to C2 were changed as shown in Table 1, relief printing plate precursors / relief printing plates of Examples 2 to 14 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, and relief printing was performed. The plate was evaluated. The contents and evaluation results of the relief printing plate precursor are shown in Table 1.

  It has been found that adding component B significantly improves residue removal without reducing the tensile strength of the film. In particular, when both the component C1 and the component C2 coexist, the effect is great, and it has become possible to realize good debris removability without causing a halftone dot defect, which is a problem.

Claims (12)

(Component C1) at least one of an ethylenically unsaturated compound and (Component C2) a compound having a hydrolyzable silyl group and / or a silanol group,
(Component A) a binder polymer, and
(Component B) a polymer having at least one of an acidic group having an acid dissociation constant (pKa) in the range of 5.5 to 11 and / or an alkali-decomposable group that becomes an acidic group by alkaline hydrolysis in the side chain, A resin composition for laser engraving, comprising:   The resin composition for laser engraving according to claim 1, further comprising (Component D) a plasticizer. The resin composition for laser engraving according to claim 1 or 2 , wherein the acidic group having an acid dissociation constant (pKa) in the range of 5.5 to 11 is a phenolic hydroxyl group. The resin composition for laser engraving according to any one of claims 1 to 3 , wherein the alkali-decomposable group is represented by the formula (B-3).

(In formula (B-3), A ¹ represents an aromatic ring group or a cyclo ring group, n represents an integer of 1 to 5, and X ² represents —NR ¹ R ² , —SR ³ , —OR ⁴ . Wherein R ^{1 to} R ⁴ are each independently composed of at least one atom selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. Represents a substituent, Y represents a single bond, —O—, —NR ⁵ —, an alkylene group, or a divalent linking group obtained by combining these, wherein R ⁵ represents a hydrogen atom or a hydrocarbon. Represents a group.) The resin composition for laser engraving according to any one of claims 1 to 4 , wherein the component A is a non-elastomer. 6. A relief printing plate precursor for laser engraving, comprising a relief forming layer comprising the resin composition for laser engraving according to any one of claims 1 to 5 on a support. A relief printing plate precursor for laser engraving, comprising a crosslinked relief forming layer obtained by thermally crosslinking the relief forming layer comprising the resin composition for laser engraving according to any one of claims 1 to 5 . The relief printing plate precursor for laser engraving according to claim 6 or 7 , which is a flexographic printing plate precursor. A layer forming step of forming a relief forming layer comprising the resin composition for laser engraving according to any one of claims 1 to 5 , and
A method for producing a relief printing plate precursor for laser engraving, comprising a crosslinking step of thermally crosslinking the relief forming layer to obtain a relief printing plate precursor having a crosslinked relief forming layer. (1) The step of crosslinking the relief forming layer in the relief printing plate precursor for laser engraving according to claim 6 with heat and / or light, and
(2) A method for making a relief printing plate, comprising a step of laser engraving a crosslinked relief forming layer to form a relief layer. The method for making a relief printing plate according to claim 10 , further comprising the step of (3) treating the relief layer with an alkaline liquid having a pH of 9.5 to 14. A relief printing plate made by the plate making method of a relief printing plate according to claim 10 or 11 .