JP2011068031A - Resin composition for laser engraving, relief printing plate original plate for laser engraving, manufacturing method of the same, relief printing plate, and plate making method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for laser engraving by which a relief printing plate excellent in a rinsing property of engraving waste generated during laser engraving and excellent in the elasticity and ink transferring property of the formed relief layer can be obtained. <P>SOLUTION: The resin composition for laser engraving includes (a) a compound represented by one of formulae (1) to (4) and (b) a binder polymer. Here, R<SP>1</SP>represents a bonding group, R<SP>2</SP>to R<SP>6</SP>independently represent monovalent organic groups respectively, A represents a (m+n)valent organic bonding group, k represents an integer of 0 to 4, m represents an integer of 1 to 4, n represents an integer of 1 to 4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

As a method for forming a printing plate by forming irregularities on a photosensitive resin layer laminated on a surface area of a support, a relief forming layer formed using a photosensitive composition is exposed to ultraviolet light through an original film. A method of selectively curing an image portion and removing an uncured portion with a developer, so-called “analog plate making” is well known.
The relief printing plate is a relief printing plate having a relief layer having irregularities, and the relief layer having such irregularities includes, for example, an elastomeric polymer such as synthetic rubber, a resin such as a thermoplastic resin, Alternatively, it is obtained by patterning a relief forming layer containing a photosensitive composition containing a mixture of a resin and a plasticizer to form irregularities. Among such relief printing plates, those having a soft relief layer are sometimes referred to as flexographic plates.

When producing a relief printing plate by analog plate making, since an original image film using a silver salt material is generally required, the production time and cost of the original image film are required. Furthermore, since chemical processing is required for development of the original image film and processing of the development waste liquid is also required, a simpler plate preparation method, for example, a method that does not use the original image film, and development processing are required. The method of not doing is examined.
As a plate making method that does not require a development step, a so-called “direct engraving CTP method” is known in which a relief forming layer is directly engraved with a laser to make a plate. The direct engraving CTP method literally engraves with a laser to form reliefs, and has the advantage that the relief shape can be freely controlled, unlike the relief formation using the original film. 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.
The plate material used in the direct engraving CTP method so far uses a hydrophobic elastomer (rubber) as a binder for determining the properties of the plate material (see, for example, Patent Document 1) or hydrophilic polyvinyl. Many things using an alcohol derivative (for example, refer to patent documents 2) etc. are proposed.

Patent Documents 3 to 5 are known as methods for easily removing engraving debris generated by laser engraving in a relief printing plate using the direct engraving CTP method.
In Patent Document 3, in a printing original plate capable of laser engraving made of a photocured product of a photosensitive resin composition containing inorganic porous fine particles, the printing original plate is subjected to a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The laser engraving printing original plate is characterized in that when the temperature is increased from room temperature and thermogravimetric analysis (TGA) is performed, the temperature at which the weight reduction rate is 50% is 150 ° C. or more and 400 ° C. or less.
Patent Document 4 includes (A) a polymer compound having at least one of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2) in the main chain, and (B) a binder polymer. A laser-decomposable resin composition is described, which contains

On the other hand, Patent Document 5 is known as a lithographic printing plate precursor.
In Patent Document 5, on a support having a hydrophilic surface, (a) a functional group that changes from hydrophobic to hydrophilic on the side chain by heat and a hydrophobic polymer compound having a hydrophilic functional group (b) ) A lithographic printing plate precursor having a layer containing a light absorber capable of absorbing laser light and converting it into heat is described.

US Pat. No. 5,798,202 JP 2006-2061 A JP 2004-174758 A JP 2008-45102 A JP 2000-39708 A

  An object of the present invention is to provide a resin composition for laser engraving, which is excellent in rinsing property of engraving residue generated during laser engraving, and can provide a relief printing plate excellent in elasticity and ink transferability of a formed relief layer, It is to provide a relief printing plate precursor for laser engraving using a resin composition for engraving and a production method thereof, and a relief printing plate and a plate making method thereof.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <9>, <10>, <12>, <14> or <16>. It is described below together with <2> to <8>, <11>, <13> and <15> which are preferred embodiments.
<1> (a) a resin composition for laser engraving, comprising a compound represented by any one of the following formulas (1) to (4), and (b) a binder polymer;

（式（１）〜（４）中、Ｒ¹は結合性基を表し、Ｒ²〜Ｒ⁶はそれぞれ独立に、一価の有機基を表し、Ａは（ｍ＋ｎ）価の有機連結基を表し、ｋは０〜４の整数を表し、ｍは１〜４の整数を表し、ｎは１〜４の整数を表す。）

(In formulas (1) to (4), R ¹ represents a binding group, R ^{2 to} R ⁶ each independently represents a monovalent organic group, and A represents an (m + n) -valent organic linking group. , K represents an integer of 0 to 4, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)

<2> The binding group is —SiR ⁷ R ⁸ R ⁹ , acid anhydride residue, methacryloyl group, acryloyl group, styryl group, vinyloxy group, isocyanate group, blocked isocyanate group, amino group, hydroxy group, —C (= O) -R ¹⁰ , the resin composition for laser engraving according to <1>, which is at least one group selected from the group consisting of an epoxy group and a mercapto group,
(In each of R ⁷ to R ⁹ independently of the -SiR ⁷ R ⁸ R ^9, a hydrogen atom, a halogen atom, or represents a monovalent organic group, at least one of R ⁷ to R ⁹ is an alkyl group , an alkoxy group, or a halogen atom, R ¹⁰ in the -C (= O) -R ¹⁰ represents a hydrogen atom, or an alkyl group.)
<3> The resin composition for laser engraving according to <1> or <2>, wherein m is 1.
<4> (c) The resin composition for laser engraving according to any one of the above <1> to <3>, further containing a crosslinking agent,
<5> (d) The resin composition for laser engraving according to any one of the above <1> to <4>, further containing a crosslinking accelerator,
<6> (e) The resin composition for laser engraving according to any one of the above <1> to <5>, further containing a photothermal conversion agent,
<7> The resin composition for laser engraving according to any one of the above <1> to <6>, further comprising (f) a polymerization initiator and (g) a polymerizable compound,
<8> A relief printing plate precursor for laser engraving having a relief forming layer comprising the resin composition for laser engraving according to any one of <1> to <7> above,
<9> A relief printing plate precursor for laser engraving having a crosslinked relief forming layer obtained by crosslinking the relief forming layer comprising the resin composition for laser engraving according to any one of <1> to <7> above,
<10> The relief printing plate precursor for laser engraving according to <9>, wherein the Shore A hardness of the crosslinked relief forming layer is 50 ° or more and 90 ° or less,
<11> A layer forming step of forming a relief forming layer comprising the resin composition for laser engraving according to any one of the above <1> to <7>, and the relief forming layer with heat and / or light A method for producing a relief printing plate precursor for laser engraving, comprising a crosslinking step of obtaining a relief printing plate precursor that is crosslinked and has a crosslinked relief-forming layer,
<12> The method for producing a relief printing plate precursor for laser engraving according to <11>, wherein the crosslinking step is a step of crosslinking the relief forming layer with heat,
<13> A layer forming step of forming a relief forming layer comprising the resin composition for laser engraving according to any one of the above <1> to <7>, and crosslinking the relief forming layer with heat and / or light. A method for making a relief printing plate comprising a crosslinking step for obtaining a relief printing plate precursor having a crosslinked relief forming layer, and a engraving step for laser engraving the relief printing plate precursor having the crosslinked relief forming layer to form a relief layer,
<14> The plate-making method of the relief printing plate according to <13>, wherein the relief layer has a thickness of 0.05 mm or more and 10 mm or less,
<15> A relief printing plate made by the plate making method of a relief printing plate according to <13> or <14> above.

  According to the present invention, the resin composition for laser engraving capable of obtaining a relief printing plate excellent in rinsing property of engraving residue generated during laser engraving and excellent in elasticity and ink transferability of the formed relief layer, the laser It was possible to provide a relief printing plate precursor for laser engraving using a resin composition for engraving and a production method thereof, and a relief printing plate and a plate making method thereof.

It is a schematic block diagram (perspective view) which shows a plate making apparatus provided with the semiconductor laser recording apparatus with a fiber which can be used for this invention.

  Hereinafter, the present invention will be described in detail.

(Resin composition for laser engraving)
The resin composition for laser engraving of the present invention (hereinafter also simply referred to as “resin composition of the present invention”) is a compound represented by (a) any of the following formulas (1) to (4) (hereinafter, It is also called “specific compound”) and (b) a binder polymer.

（式（１）〜（４）中、Ｒ¹は結合性基を表し、Ｒ²〜Ｒ⁶はそれぞれ独立に、一価の有機基を表し、Ａは（ｍ＋ｎ）価の有機連結基を表し、ｋは０〜４の整数を表し、ｍは１〜４の整数を表し、ｎは１〜４の整数を表す。）

(In formulas (1) to (4), R ¹ represents a binding group, R ^{2 to} R ⁶ each independently represents a monovalent organic group, and A represents an (m + n) -valent organic linking group. , K represents an integer of 0 to 4, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.)

The resin composition for laser engraving of the present invention contains a compound represented by any one of the above formulas (1) to (4), whereby the ester moiety is thermally decomposed by heat in laser exposure, and sulfone It is presumed that acidic functional groups such as acid groups, phosphonic acid groups, carboxylic acid groups, and phenolic hydroxyl groups are generated, and the hydrophilicity of the engraving residue is improved.
Furthermore, the compounds represented by the formulas (1) to (4) have a binding group, so that during mixing, heating and / or laser engraving, (b) binder polymer and (c) crosslinking It is presumed that a part derived from a specific compound in a state where an acidic functional group is generated in the engraving residue after laser engraving is likely to remain in the engraving residue after laser engraving, and that the engraving residue itself is promoted to be hydrophilic. .
As a result of these, it is presumed that the water solubility and water dispersibility of the engraving residue are improved, and the rinse property of the engraving residue is excellent.
Moreover, although the polymer described in Patent Document 4 has an effect of improving rinsing properties, it has a rigid chemical structure because it has a sulfonic acid ester group in the main chain, and the flexibility of the film is insufficient when used as a flexographic printing plate. It becomes a trend. As a result, the flexographic printing plate may have insufficient ink transfer properties (transfer of ink from the plate material to the printing material). In the resin composition of the present invention, by using the compound represented by any one of the following formulas (1) to (4), not only rinse properties but also ink transfer properties are improved.

The resin composition of the present invention can be applied to a wide range of applications for forming a resin shaped article subjected to laser engraving without any particular limitation. For example, as an application mode of the resin composition of the present invention, specifically, an image forming layer of an image forming material that forms an image by laser engraving, a relief forming layer of a printing plate precursor that forms a convex relief by laser engraving , Intaglio, stencil, stamp and the like, but are not limited thereto. The resin composition of the present invention can be particularly suitably used for an image forming layer of an image forming material for forming an image by laser engraving and a relief forming layer in a relief printing plate precursor for laser engraving.
Hereinafter, the components of the resin composition for laser engraving will be described.

(A) Compounds represented by formulas (1) to (4) (specific compounds)
The resin composition for laser engraving of the present invention contains (a) a compound represented by any one of formulas (1) to (4).
R ¹ in the compounds represented by the formulas (1) to (4) represents a binding group, —SiR ⁷ R ⁸ R ⁹ , an acid anhydride residue, a methacryloyl group, an acryloyl group, a styryl group, a vinyloxy group. , An isocyanate group, a blocked isocyanate group, an amino group, a hydroxy group, —C (═O) —R ¹⁰ , an epoxy group, and a mercapto group, and preferably at least one group selected from the group consisting of — It is more preferably at least one group selected from the group consisting of SiR ⁷ R ⁸ R ⁹ , methacryloyl group, and acryloyl group, and more preferably —SiR ⁷ R ⁸ R ⁹ .
Wherein the -SiR ⁷ R ^{7 ~R 9} in R ⁸ R ⁹ are each independently a hydrogen atom, a halogen atom, or represents a monovalent organic group, at least one of R ⁷ to R ⁹ is an alkyl group, An alkoxy group or a halogen atom.
In the —SiR ⁷ R ⁸ R ^9, at least one of R ^{7 to} R ⁹ is preferably an alkoxy group or a halogen atom, and at least two of R ^{7 to} R ⁹ are an alkoxy group or halogen. It is more preferably an atom, all of R ^{7 to} R ⁹ are more preferably an alkoxy group or a halogen atom, and most preferably all of R ^{7 to} R ⁹ are an alkoxy group.
R ¹⁰ in the -C (= O) -R ¹⁰ represents a hydrogen atom or an alkyl group.
The number m of the binding groups in the compounds represented by the formulas (1) to (4) is an integer of 1 to 4, preferably an integer of 1 to 3, and preferably 1 or 2. More preferably, 1 is even more preferable.

R ^{2 to} R ⁶ in the compounds represented by the formulas (1) to (4) each independently represent a monovalent organic group.
The monovalent organic group in R ^{2 to} R ⁵ is not particularly limited, but is preferably an alkyl group, and is a secondary alkyl group, a tertiary alkyl group, or a 1-alkoxy substituted primary group. It is more preferably an alkyl group, and further preferably a secondary alkyl group or a tertiary alkyl group.
The alkyl group in the monovalent organic group may be linear, branched or cyclic, and even if it has a substituent, some of the carbon atoms of the alkyl group are ether-bonded oxygen atoms. May be substituted.
Preferred examples of the alkyl group in the monovalent organic group include an alkyl group having 1 to 20 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.
The substituent that the alkyl group may have is not particularly limited, but is preferably an alkoxy group.
As the alkoxy group, those having 1 to 10 carbon atoms are preferable, those having 1 to 8 carbon atoms are more preferable, and those having 1 to 5 carbon atoms are particularly preferable from the viewpoints of thermal decomposability and film property.
In the monovalent organic group, an alkoxy group and an alkyl group may be bonded to form a ring structure.

R ² and R ³ in the formula (1) are preferably a secondary alkyl group or a 1-alkoxy substituted primary alkyl group, and a 1-methoxy-2-propyl group or a cyclohexyl group. It is more preferable that it is 1-methoxy-2-propyl group.
In addition, R ⁴ in the formula (3) is preferably a tertiary alkyl group and more preferably a t-butyl group from the viewpoint of rinsing properties.
R ⁵ in the formula (4) is preferably a tertiary alkyl group or a 1-alkoxy substituted primary alkyl group, more preferably a 1-alkoxy substituted primary alkyl group. preferably, 1-methoxy-2-propyl group, or, more preferably a 2-tetrahydropyranyl group.
The number n of groups that form an acidic functional group in the compounds represented by the formulas (1) to (4) represents an integer of 1 to 4, and is preferably an integer of 1 to 2. More preferably, it is more preferably 1.
R ⁶ in the compound represented by the formula (4) independently represents a monovalent organic group, preferably an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. .

A in the compounds represented by the formulas (1) to (4) represents an (m + n) -valent organic linking group, and includes an ester bond, a thioester bond, an amide bond, an ether bond, a thioether bond, a urethane bond, and a thiourethane bond. , A urea bond, a thiourea bond, and an amino bond (—N (H) —, —N (R ¹¹ ) —; R ¹¹ represents a monovalent organic group), at least one bond selected from the group consisting of In terms of engraving sensitivity, at least one selected from the group consisting of an ester bond, an ether bond, a thioether bond, a urethane bond, a urea bond, and an amino bond is preferable. More preferably, it is an (m + n) -valent organic linking group containing one bond, and is selected from the group consisting of an ester bond, an ether bond, a thioether bond, and an amino bond. More preferably, it is an (m + n) -valent organic linking group containing at least one selected bond. In addition, the (m + n) -valent organic linking group may be linear, branched, or have a ring structure, and may have a substituent. . Further, the (m + n) -valent organic linking group may be a group including a polymer structure.
The molecular weight (or weight average molecular weight (Mw)) of A is preferably 14 or more and 100,000 or less, more preferably 14 or more and 20,000 or less, and more preferably 14 or more and 800 or less. More preferably, it is 24 or more and 500 or less.
The number of carbon atoms contained in A is preferably 1 to 8,000, more preferably 1 to 1,000, still more preferably 1 to 50, and 2 to 30. It is particularly preferred.

The resin composition for laser engraving of the present invention contains compounds represented by formulas (1) to (3) from the viewpoint of rinsing properties among the compounds represented by formulas (1) to (4). It is preferable to contain the compound represented by the formula (1) and / or the compound represented by the formula (3), and it is particularly preferable to contain the compound represented by the formula (1). .
Specific examples of the compounds represented by the formulas (1) to (4) include the following A-1 to A-11, (1) -1 to (1) -56, and (2) -1 to (2). ) -29, (3) -1 to (3) -37, and (4) -1 to (4) -26 are preferred, but the formulas (1) to (4) that can be used in the present invention. It goes without saying that the compound represented by is not limited thereto. In the present invention, in the chemical formula, the hydrocarbon chain may be described by a simplified structural formula in which symbols of carbon (C) and hydrogen (H) are omitted. In the following chemical formula, Me represents a methyl group, Et represents an ethyl group, and the content ratio of each monomer unit in the following specific examples may be any ratio as long as the formulas (1) to (4) are satisfied. That's fine.

  The total addition amount of the compounds represented by the formulas (1) to (4) to the resin composition for laser engraving of the present invention is the total solid excluding the solvent in terms of the balance between film strength and film flexibility. When the amount is 100% by weight, it is preferably 0.1 to 70% by weight, more preferably 1 to 40% by weight, and still more preferably 5 to 20% by weight.

(B) Binder polymer The resin composition for laser engraving of the present invention contains (b) a binder polymer.
(B) The binder polymer is a polymer component (binder resin) contained in the resin composition for laser engraving, and a general polymer compound is appropriately selected and used alone or in combination of two or more. be able to. In particular, when the resin composition for laser engraving is used for a printing plate precursor, it can be selected in consideration of various performances such as laser engraving property, ink acceptability, and engraving residue dispersibility.
The weight average molecular weight of the (b) binder polymer that can be used in the present invention is preferably 1,000 or more, more preferably 1,500 or more, and particularly preferably 3,000 or more. preferable.

The binder polymer that can be used in the present invention preferably has a reactive group capable of reacting with the binding group of the compounds represented by the formulas (1) to (4).
The reactive groups in the binder polymer, -SiR ⁷ R ⁸ R ^9, acid anhydride residue, a methacryloyl group, an acryloyl group, a styryl group, a vinyloxy group, an isocyanate group, blocked isocyanate group, an amino group, hydroxy group, -C Preferred examples include at least one group selected from the group consisting of (═O) —R ¹⁰ , an epoxy group, and a mercapto group. Preferred examples include hydroxy groups.
A -SiR ⁷ R ^{7 ~R 9} in R ⁸ R ⁹ are each independently a hydrogen atom, a halogen atom, or represents a monovalent organic group, at least one of R ⁷ to R ⁹ is an alkyl group, an alkoxy A group or a halogen atom. Further, R ¹⁰ in the -C (= O) -R ¹⁰ represents a hydrogen atom or an alkyl group.
The blocked isocyanate group is a group obtained by reacting an isocyanate group with a blocking agent, and is a group that can be decomposed by heat to regenerate the isocyanate group.
Examples of the blocking agent include alcohol compounds, cyclic amide compounds, ketoxime compounds, phenol compounds, and secondary amine compounds. Japanese Patent No. 3095227 can also be referred to as the blocked isocyanate group.
The temperature at which the isocyanate group is regenerated from the blocked isocyanate group is not particularly limited, and may be selected depending on the structure of the blocked isocyanate group.
When the binder polymer has a blocked isocyanate group, it is preferable that the relief forming layer formed from the resin composition of the present invention is crosslinked by heat.

  As the binder polymer, polystyrene resin, polyester resin, polyamide resin, polyurea resin, polyamideimide resin, polyurethane resin, polysulfone resin, polyethersulfone resin, polyimide resin, polycarbonate resin, hydrophilic polymer containing hydroxyethylene units, acrylic resin, Acetal resin, epoxy resin, polycarbonate resin, rubber, thermoplastic elastomer, cellulose and the like can be selected and used.

The binder polymer preferably has a glass transition temperature (Tg) of 20 ° C. or higher in order to improve engraving sensitivity. When combined with a photothermal conversion agent described later, the glass transition temperature (Tg) is 20 ° C. or higher. It is particularly preferable that Hereinafter, a polymer having a glass transition temperature of 20 ° C. or higher is also referred to as a non-elastomer. In other words, an elastomer is generally defined academically as a polymer having a glass transition temperature of room temperature or lower (see Science Univ. 2nd edition, edited by International Science Promotion Foundation, published by Maruzen Co., Ltd., page 154). ). Therefore, the non-elastomer refers to a polymer having a glass transition temperature exceeding normal temperature. Although there is no restriction | limiting in the upper limit of the glass transition temperature of the said polymer, it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.
When a polymer having a glass transition temperature of room temperature (20 ° C) or higher is used, the binder polymer takes a glass state at room temperature, and therefore, thermal molecular motion is considerably suppressed as compared with a rubber state. It is in. In laser engraving, in addition to the heat imparted by the laser during laser irradiation, the heat generated by the function of the photothermal conversion agent used in combination is transmitted to the binder polymer and its cross-linked body present in the surroundings, which is thermally decomposed, Dissipates and results in engraving to form a recess. When the photothermal conversion agent is present in a state where thermal molecular motion of the binder polymer or its crosslinked product is suppressed, it is considered that heat transfer and thermal decomposition to the binder polymer or its crosslinked product occur effectively, It is presumed that the engraving sensitivity is further increased by such an effect.

When the binder polymer has the reactive group, the content of the reactive group contained in the binder polymer is preferably 0.1 to 15 mmol / g, and more preferably 0.5 to 7 mmol / g. .
The weight average molecular weight (polystyrene conversion by GPC measurement) of the binder polymer is preferably from 50,000 to 500,000, more preferably from 10,000 to 400,000, and further preferably from 15,000 to 300,000. . When the weight average molecular weight is 50,000 or more, the form retainability as a single resin is excellent, and when it is 500,000 or less, it is easy to dissolve in a solvent such as water, which is convenient for preparing a resin composition for laser engraving. is there.

  The total content of the binder polymer in the resin composition for laser engraving of the present invention is preferably from 5 to 80% by weight, more preferably from 15 to 75% by weight, based on the total solid content of the resin composition for laser engraving. More preferred is ˜65% by weight. By making the content of the binder polymer 5% by weight or more, printing durability sufficient to use the obtained relief printing plate as a printing plate can be obtained, and by making the content 80% by weight or less, other components can be contained. There is no shortage, and even when the relief printing plate is a flexographic printing plate, flexibility sufficient for use as a printing plate can be obtained.

<Polymer having hydroxy group>
The resin composition for laser engraving of the present invention preferably contains a polymer having a hydroxy group as a binder polymer.
The skeleton of the polymer having a hydroxy group is not particularly limited, but an acrylic resin, an epoxy resin, a hydrophilic polymer containing a hydroxyethylene unit, a polyvinyl acetal, a polyester resin, a polyurethane resin, and cellulose are preferable.
Examples of acrylic monomers used for the synthesis of acrylic resins having a hydroxy group include (meth) acrylic acid esters, crotonic acid esters, and (meth) acrylamides that have a hydroxyl group in the molecule. Is preferred. Specific examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. A copolymer obtained by polymerizing these and a known (meth) acrylic monomer or vinyl monomer can be preferably used.
It is also possible to use an epoxy resin having a hydroxy group in the side chain as the polymer having a hydroxy group. As a preferred specific example, an epoxy resin obtained by polymerizing an adduct of bisphenol A and epichlorohydrin as a raw material monomer is preferable.
As the polyester resin having a hydroxy group, a polyester resin containing a hydroxylcarboxylic acid unit such as polylactic acid can be preferably used. Specific examples of the polyester resin include polyhydroxyalkanoate (PHA), lactic acid-based polymer, polyglycolic acid (PGA), polycaprolactone (PCL), poly (butylene succinic acid), derivatives thereof, and Preferred are those selected from the group consisting of these mixtures.

Furthermore, as the polymer having a hydroxy group, a hydrophilic polymer containing a hydroxyethylene unit can be preferably used. As the hydrophilic polymer containing a hydroxyethylene unit, polyvinyl alcohol (PVA) and its derivatives are preferably used.
Examples of PVA derivatives include acid-modified PVA obtained by modifying at least a part of the hydroxy group of a hydroxyethylene unit to an acid group such as a carboxyl group (also referred to as “carboxylic acid group”), and a part of the hydroxy group (meta ) Modified PVA modified to acryloyl group, modified PVA modified with at least part of said hydroxy group to amino group, modified PVA introduced with ethylene glycol, propylene glycol and multimers thereof into at least part of said hydroxy group, polyvinyl Examples thereof include polyvinyl acetal obtained by treating alcohol with aldehydes. Among these, polyvinyl acetal is particularly preferably used. As aldehydes used for the acetal treatment, acetaldehyde and butyraldehyde are preferably used because they are easy to handle. In particular, polyvinyl butyral (PVB) is a PVA derivative that is preferably used.

Moreover, as a polymer which has a hydroxyl group, a cellulose and a cellulose derivative can be used preferably, and a cellulose derivative can be used more preferably.
Ordinary cellulose is very difficult to dissolve in water or alcohol, but the solubility of water or solvent can be controlled by modifying the residual OH of the glucopyranose unit with a specific functional group. Cellulose derivatives that are insoluble but soluble in alcohols having 1 to 4 carbon atoms are also suitable as binder polymers that can be used in the present invention.
Examples of the cellulose derivative include alkyl celluloses such as ethyl cellulose and methyl cellulose, hydroxyethylene cellulose, hydroxypropylene cellulose, cellulose acetate butyrate, and the like. Furthermore, as a specific example, Shin-Etsu Chemical Co., Ltd. Metro's series is mentioned. The content of this series is that part of the hydrogen atom of the hydroxy group of cellulose is substituted with a methyl group (—CH ₃ ), a hydroxypropyl group (—CH ₂ CHOHCH ₃ ) or a hydroxyethyl group (—CH ₂ CH ₂ OH). Is.
Among these, alkyl cellulose is preferable, and ethyl cellulose and / or methyl cellulose are more preferable.

<Polymer having ethylenically unsaturated group>
The resin composition for laser engraving of the present invention preferably contains a polymer having an ethylenically unsaturated group as a binder polymer.
As the polymer having an ethylenically unsaturated group, the polymer having an ethylenically unsaturated bond in the main chain includes, for example, SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene). ), SEBS (polystyrene-polyethylene / polybutylene-polystyrene) and the like.
As a polymer having an ethylenically unsaturated group in the side chain, an ethylenically unsaturated group such as an allyl group, an acryloyl group, a methacryloyl group, a styryl group or a vinyl ether group is introduced into the side chain of the binder polymer. can get.
The skeleton of the polymer having an ethylenically unsaturated group is not particularly limited, but polystyrene resin, polyester resin, polyamide resin, polyurea resin, polyamideimide resin, polyurethane resin, polysulfone resin, polyethersulfone resin, polyimide resin, polycarbonate resin Hydrophilic polymers containing hydroxyethylene units, acrylic resins, acetal resins, epoxy resins, polycarbonate resins, rubbers, thermoplastic elastomers and the like are preferable.
The method for introducing an ethylenically unsaturated group into the side chain of the binder polymer is as follows: (1) a structural unit having a precursor structure of an ethylenically unsaturated group is copolymerized with the polymer, and then the precursor structure of the ethylenically unsaturated group is converted. Method of converting to ethylenically unsaturated group, (2) Preparation of polymer compound having plural groups such as hydroxy group, amino group, epoxy group, carboxyl group, group reacting with these groups and ethylenically unsaturated group A known method such as a method of introducing a compound having a polymer by a polymer reaction can be employed. According to these methods, the amount of ethylenically unsaturated groups introduced into the polymer compound can be controlled.
Among these, the polymer having an ethylenically unsaturated group is preferably a polymer having an acryloyl group, a methacryloyl group, a styryl group, and / or a vinyl ether group.

<Polymer having carboxyl group>
The resin composition for laser engraving of the present invention may contain a polymer having a carboxyl group as a binder polymer.
Although there is no restriction | limiting in particular as a polymer which has a carboxyl group, The acrylic resin which has a carboxyl group, the polyurethane resin which has a carboxyl group, the polyester resin which has a carboxyl group, etc. can illustrate preferably.
Examples of the acrylic resin having a carboxyl group include an acrylic resin obtained by copolymerizing acrylic acid and methacrylic acid, and an ester compound derived from a (meth) acrylate of the acrylic resin that has been converted to a carboxyl group.
Examples of the polyurethane resin having a carboxyl group include a polyurethane resin obtained by polymerizing a polyhydric alcohol having one or more carboxyl groups and a polyvalent isocyanate.
As the polyester resin having a carboxyl group, a polyester resin obtained by polycondensation of a trivalent or higher polyvalent carboxylic acid and a diol, or the amount of the carboxyl group of the polyvalent carboxylic acid was used more than the amount of the hydroxy group of the polyvalent alcohol. A polyester resin etc. are mentioned.

<Polymer having isocyanate group>
The resin composition for laser engraving of the present invention may contain a polymer having an isocyanate group as a binder polymer.
Although there is no restriction | limiting in particular as a polymer which has an isocyanate group, The polyurethane resin which has an isocyanate group, the polyester resin which has an isocyanate group, etc. can illustrate preferably.
Examples of the polyurethane resin having an isocyanate group include a polyurethane resin in which the amount of isocyanate group of the polyvalent isocyanate compound is larger than the amount of hydroxy group of the polyhydric alcohol.
Examples of the polyester resin having an isocyanate group include a polyester resin obtained by reacting a polyester resin having two or more hydroxy groups such as polyester diol and a polyvalent isocyanate compound. As the polyester resin having two or more hydroxy groups, those described in the polymer having a hydroxy group can be suitably used.
Specific examples of the polymer having an isocyanate group include Coronate L, Coronate HL, Coronate 2030, Aquanate 100, Aquanate 105, and Aquanate 120 manufactured by Nippon Polyurethane Industry Co., Ltd.

<Polymer having epoxy group>
The resin composition for laser engraving of the present invention may contain a polymer having an epoxy group as a binder polymer.
Although there is no restriction | limiting in particular as a polymer which has an epoxy group, A novolak-type epoxy resin, a bisphenol-type epoxy resin, a cycloaliphatic epoxy resin, a hydantoin type epoxy resin, a polyurethane resin which has an epoxy group, a polyester resin which has an epoxy group Etc. can be preferably exemplified, bisphenol-based epoxy resins can be illustrated more preferably, and bisphenol A-based epoxy resins can be illustrated more preferably.

<Polymer having acid anhydride residue>
The resin composition for laser engraving of the present invention may contain a polymer having an acid anhydride residue as a binder polymer.
The polymer having an acid anhydride residue is not particularly limited, but a polymer having a carboxylic acid anhydride residue is preferable, and a polymer having a carboxylic acid anhydride residue having a 5- or 6-membered ring structure is preferable. It is more preferable.
Examples of the polymer having an acid anhydride residue include a polymer having an acid anhydride residue obtained by reacting the above polymer having an isocyanate group with a compound having a hydroxy group and an acid anhydride residue, acrylic acid and methacrylic acid. Examples thereof include a polymer having an acid anhydride residue obtained by dehydrating a part of carboxyl groups of an acrylic resin copolymerized with an acid.

<Polymer having amino group>
The resin composition for laser engraving of the present invention may contain a polymer having an amino group as a binder polymer.
Although there is no restriction | limiting in particular as a polymer which has an amino group, The acrylic resin which has a polyalkyleneimine, a polyallylamine, and an aminoalkyl group in a side chain can illustrate preferably.
As monomers used for the synthesis of an acrylic resin having an aminoalkyl group in the side chain, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N- Preferred is dimethylaminopropyl (meth) acrylate.

<Polymer having —SiR ⁷ R ⁸ R ⁹ >
The resin composition for laser engraving of the present invention may contain a polymer having —SiR ⁷ R ⁸ R ⁹ as a binder polymer.
R ^{7 to} R ⁹ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. However, at least one of R ^{7 to} R ⁹ is an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.
The polymer having a -SiR ⁷ R ⁸ R ^9, is not particularly limited, and a polymer having a silanol group, polymers having a trialkoxysilyl group can be preferably exemplified.
The alkoxy group in R ^{7 to} R ⁹ is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, from the viewpoint of rinsing properties and printing durability. And more preferably an alkoxy group having 1 to 5 carbon atoms.
Examples of the halogen atom in R ^{7 to} R ⁹ include an F atom, a Cl atom, a Br atom, and an I atom, and a Cl atom and a Br atom are preferable from the viewpoint of ease of synthesis and stability. And Cl atoms are more preferable.
As the -SiR ⁷ R ⁸ R ^9, at least one hydroxy group of R ⁷ to R ^9, is preferably a methoxy group or an ethoxy group.

<Combination of the binding group and the reactive group>
In the resin composition for laser engraving of the present invention, when the binder polymer has a reactive group, the combination of the reactive group in the binder polymer and the binding group in the compounds represented by formulas (1) to (4) Is not particularly limited as long as it is a combination of a reactive group and a binding group capable of reacting with the reactive group, but is selected from the group consisting of the following (ab-1) to (ab-21) It is preferably a combination, more preferably a combination selected from the group consisting of the following (ab-1) to (ab-13), and from a group consisting of the following (ab-1) to (ab-4) The selected combination is more preferable, and the following combination (ab-1) is particularly preferable.

(C) Crosslinking agent The resin composition of the present invention preferably contains a crosslinking agent in order to form a crosslinked structure in the relief forming layer to form a crosslinked relief forming layer. However, the crosslinking agent in the present invention does not include a compound corresponding to the compound represented by any one of the formulas (1) to (4).
The crosslinking agent that can be used in the present invention is a compound having two or more crosslinking groups capable of reacting with the binder polymer. A crosslinkable group possessed by the crosslinking agent and a group capable of reacting with the crosslinkable group possessed by the binder polymer react to form a crosslinked structure.
As such a compound, —SiR ⁷ R ⁸ R ⁹ (R ^{7 to} R ⁹ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. However, among R ^{7 to} R ⁹ , At least one is an alkyl group, an alkoxy group, or a halogen atom.), An isocyanate group, a block isocyanate group, an amino group, a hydroxy group, a carboxyl group, an epoxy group, and a mercapto group. A compound having two or more crosslinkable groups is preferred.
In addition, the compound which has 2 or more of ethylenically unsaturated groups, such as a methacryloyl group, an acryloyl group, a styryl group, a vinyl ether group, shall correspond to the polymeric compound mentioned later in this invention.

The crosslinkable group is —SiR ⁷ R ⁸ R ⁹ (R ^{7 to} R ⁹ each independently represents a hydrogen atom, a halogen atom, or a monovalent organic group in terms of the strength of the crosslinked film. , R ^{7 to} R ⁹ are preferably an alkyl group, an alkoxy group, or a halogen atom.), An isocyanate group, a carboxyl group, an epoxy group, or an amino group, and —SiR ⁷ R ⁸ R ⁹ , a carboxyl group, an epoxy group, or an amino group is more preferable, and —SiR ⁷ R ⁸ R ⁹ is particularly preferable.
In the -SiR ⁷ R ⁸ R ^9, at least one of R ^{7 to} R ⁹ is preferably an alkoxy group or a halogen atom, and at least two of R ^{7 to} R ⁹ are an alkoxy group or a halogen. It is more preferably an atom, all of R ^{7 to} R ⁹ are more preferably an alkoxy group or a halogen atom, and most preferably all of R ^{7 to} R ⁹ are an alkoxy group.
The number of crosslinkable groups in the crosslinking agent that can be used in the present invention is 2 or more, preferably 2 to 10, more preferably 2 to 6, and further preferably 2 or 3. preferable.

Although it does not specifically limit as a crosslinking agent which can be used for this invention, A so-called silane coupling agent is used preferably.
In the silane coupling agent, it is essential that the functional group directly bonded to the Si atom has at least one functional group of an alkoxy group or a halogen atom (such a silyl group is hereinafter referred to as “silane”). From the viewpoint of easy handling of the compound, those having an alkoxy group are preferred.
As an alkoxy group in a silane coupling group, a C1-C30 alkoxy group is preferable from a viewpoint of rinse property and printing durability, A C1-C15 alkoxy group is more preferable, A C1-C5 alkoxy group Is particularly preferred.
Examples of the halogen atom in the silane coupling group include F atom, Cl atom, Br atom, and I atom. From the viewpoint of ease of synthesis and stability, Cl atom and Br atom are preferably exemplified. More preferred are atoms.

The silane coupling agent that can be used in the present invention preferably contains 1 to 10 silane coupling groups in the molecule from the viewpoint of maintaining a good balance between the degree of crosslinking and flexibility of the film. More preferably, it is more preferably 5 or more and more preferably 2 or more and 4 or less.
The two or more silane coupling groups in the silane coupling agent are preferably linked by a linking group. Examples of the linking group include a divalent or higher-valent organic group that may have a substituent such as a heteroatom or a hydrocarbon. In terms of high engraving sensitivity, a divalent or higher-valent containing a heteroatom (N, S, O) is used. The organic group is preferably a divalent or higher-valent organic group containing an S atom.
From such a viewpoint, as the silane coupling agent in the present invention, an alkoxy group is preferably a methoxy group or an ethoxy group. Among them, the methoxy group has two silane coupling groups bonded to the Si atom in the molecule, and these silane coupling groups are bonded via an alkylene group containing a hetero atom, particularly preferably an S atom. More preferably, the compound is

  Specific examples of the silane coupling agent that can be used in the present invention include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, and γ-glycol. Sidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Propylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltri Examples include methoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane.

As the crosslinking agent that can be used in the present invention, the -SiR ⁷ R ⁸ R ⁹ 2 or more having crosslinking agent can be preferably exemplified.
The group linking two or more -SiR ⁷ R ⁸ R ⁹ in the cross-linking agent having a -SiR ⁷ R ⁸ R ⁹ 2 or more, include divalent or higher organic group, from the high engraving sensitivity standpoint, A divalent or higher organic group containing a hetero atom (N, S, O) is preferred, and a divalent or higher organic group containing an S atom is more preferred.
The crosslinking agent having at least -SiR ⁷ R ⁸ R ⁹ has two groups in which a methoxy group or an ethoxy group is bonded to an Si atom in the molecule, and these groups are preferably heteroatoms, particularly preferably A compound containing an S atom and bonded via an alkylene group is preferred.

Specific examples of the crosslinking agent having two or more —SiR ⁷ R ⁸ R ⁹ that can be used in the present invention include compounds represented by the following formulas, but the present invention is limited to these compounds. is not. In the following formulae, Et represents an ethyl group, and Me represents a methyl group.

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.

In the present invention, from the viewpoint of forming a crosslinked structure in the relief forming layer, the relief forming layer coating liquid preferably contains a polymerizable compound in order to form the crosslinked structure.
The polymerizable compound that can be used in the present invention can be arbitrarily selected from compounds having at least one ethylenically unsaturated group, preferably two or more, and more preferably 2 to 6.
Further, in the present invention, a compound having only one ethylenically unsaturated group (monofunctional polymerizable compound, monofunctional monomer) from the viewpoint of film physical properties such as flexibility and brittleness in addition to the purpose of forming a crosslinked structure. ) May be used.

Hereinafter, a compound (monofunctional monomer) having one ethylenically unsaturated group in the molecule and a compound (polyfunctional monomer) having two or more ethylenically unsaturated groups in the molecule used as a polymerizable compound explain.
Since the relief forming layer is required to have a crosslinked structure in the film, a polyfunctional monomer is preferably used. The molecular weight of these polyfunctional monomers is 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.

In the present invention, from the viewpoint of improving engraving sensitivity, a compound having a sulfur atom in the molecule is preferably used as the polymerizable compound.
Thus, as a polymeric compound which has a sulfur atom in a molecule | numerator, from a viewpoint of engraving sensitivity improvement, it has two or more ethylenically unsaturated groups especially, and connects between two ethylenically unsaturated groups among them. It is preferable to use a polymerizable compound having a sulfur atom at the site (hereinafter also referred to as “sulfur-containing polyfunctional monomer” as appropriate).

The functional group having a sulfur atom in the sulfur-containing polyfunctional monomer in the present invention includes sulfide, disulfide, sulfoxide, sulfonyl, sulfonamide, thiocarbonyl, thiocarboxylic acid, dithiocarboxylic acid, sulfamic acid, thioamide, thiocarbamate, dithiocarbamate. Or a functional group containing a structure such as thiourea.
Moreover, as a structure containing the sulfur atom in the coupling group which has a sulfur atom in a sulfur-containing polyfunctional monomer, -S-, -SS-, -NH (C = S) O-, -NH (C = O) S- , —NH (C═S) S—, and —SO ₂ — are preferably at least one structure selected from the group consisting of —SO ₂ —.

In addition, the number of sulfur atoms contained in the molecule of the sulfur-containing polyfunctional monomer is not particularly limited as long as it is 1 or more, and can be appropriately selected according to the purpose. From the viewpoint of balance, 1 to 10 is preferable, 1 to 5 is more preferable, and 1 or 2 is more preferable.
On the other hand, the number of ethylenically unsaturated groups contained in the molecule is not particularly limited as long as it is 2 or more, and can be appropriately selected according to the purpose. 10 is preferable, 2-6 is more preferable, and 2-4 is still more preferable.

The molecular weight of the sulfur-containing polyfunctional monomer in the present invention is preferably 120 to 3,000, more preferably 120 to 1,500, from the viewpoint of the flexibility of the formed film.
Moreover, although the sulfur-containing polyfunctional monomer in this invention may be used independently, you may use it as a mixture with the polyfunctional polymerizable compound and monofunctional polymerizable compound which do not have a sulfur atom in a molecule | numerator.
From the viewpoint of engraving sensitivity, an embodiment using a sulfur-containing polyfunctional monomer alone or an embodiment using a mixture of a sulfur-containing polyfunctional monomer and a monofunctional ethylenic monomer is preferable. A sulfur-containing polyfunctional monomer and a monofunctional ethylenic monomer are preferred. The embodiment used as a mixture with is more preferable.

In the relief forming layer, film properties such as brittleness and flexibility can be adjusted by using a polymerizable compound such as a sulfur-containing polyfunctional monomer.
Moreover, the total content of the polymerizable compound including the sulfur-containing polyfunctional monomer in the resin composition of the present invention is 10 to 60 based on the total weight of the solid content from the viewpoint of flexibility and brittleness of the crosslinked film. % By weight is preferred, and a range of 15 to 45% by weight is more preferred.
In addition, when using together a sulfur-containing polyfunctional monomer and another polymeric compound, 5 weight% or more is preferable and, as for the quantity of the sulfur-containing polyfunctional monomer in all the polymeric compounds, 10 weight% or more is more preferable.

Only 1 type may be used for the crosslinking agent which can be used for the resin composition of this invention, and 2 or more types may be used together.
The content of the crosslinking agent contained in the resin composition of the present invention is preferably in the range of 0.1 to 80% by weight, more preferably in the range of 1 to 40% by weight in terms of solid content. The range of 5 to 30% by weight is particularly preferable.

(D) Crosslinking accelerator The resin composition of the present invention preferably contains (d) a crosslinking accelerator (hereinafter also referred to as “catalyst”).
The crosslinking accelerator that can be used in the present invention is not particularly limited as long as it is a compound capable of promoting the reaction between the crosslinking agent and the binder polymer and / or the reaction between the specific compound and the binder polymer. (1) An acidic catalyst or a basic catalyst, and (2) a metal complex catalyst are used.
As the crosslinking accelerator, (1) an acidic catalyst or a basic catalyst is preferable. When a hydroxy group is involved in the reaction, a basic catalyst is particularly preferable from the viewpoint of the crosslinking rate of the hydroxy group.

(1) Acidic catalyst or basic catalyst As the catalyst, an acidic compound or basic compound is used as it is or dissolved in a solvent such as water or an organic solvent (hereinafter referred to as acidic catalyst or basic catalyst, respectively). Also called). 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 acidic compound or basic compound used, the desired content of the catalyst, and the like.
The type of acidic catalyst or basic catalyst is not particularly limited. Specifically, examples of the acidic catalyst 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, substituted carboxylic acids in which R in the structural formula represented by RCOOH is substituted with other elements or substituents, sulfonic acids such as benzenesulfonic acid, phosphoric acid, heteropolyacids, inorganic solid acids, etc. Examples of basic catalysts include ammoniacal bases such as aqueous ammonia, amines such as ethylamine and aniline, alkali metal hydroxides, alkali metal alkoxides, alkaline earth oxides, quaternary ammonium salt compounds, fourth compounds. Grade phosphonium salt compounds.

Examples of amines are shown below. What are amines?
(Aa) Nitrogen hydride compounds such as hydrazine;
(Ab) aliphatic, aromatic or alicyclic primary, secondary or tertiary monoamines, diamines or polyamines such as triamines;
(Ac) a monoamine or polyamine which is a cyclic amine containing a condensed ring and in which at least one nitrogen atom is contained in the ring skeleton;
(Ad) oxygen-containing amines such as amino acids, amides, alcohol amines, ether amines, imides or lactams;
(Ae) a hetero-containing amine having a hetero atom such as O, S, Se;
In the case of a secondary or tertiary amine, each substituent for N may be the same or different, or may have one or more different substituents. .
Specific examples include hydrazine and primary amines; monomethylamine, monoethylamine, monopropylamines, monobutylamines, monopentylamines, monohexylamines, monoheptylamines, vinylamine, allylamine, butenylamines , Pentenylamines, hexenylamines, pentadienylamines, hexadienylamines, cyclopentylamine, cyclohexylamine, cyclooctylamine, p-menthylamine, cyclopentenylamines, cyclohexenylamines, cyclohexadienylamine Aniline, benzylamine, naphthylamine, naphthylmethylamine, toluidine, tolylenediamine, ethylenediamine, ethylenetriamine, monoethanolamine, aminothiophene, Lysine, alanine, phenylalanine, and an amino acetone.

  Secondary amines include: dimethylamine, diethylamine, dipropylamines, dibutylamines, dipentylamines, dihexylamines, methylethylamine, methylpropylamines, methylbutylamines, methylpentylamines, methylhexyl Amines, ethylpropylamines, ethylbutylamines, ethylpentylamines, propylbutylamines, propylpentylamines, propylhexylamines, butylpentylamines, pentylhexylamines, divinylamine, diallylamine, dibutenylamines, dibutylamine Pentenylamines, dihexenylamines, methylvinylamine, methylallylamine, methylbutenylamines, methylpentenylamines, methylhexenylamines, ethyl Nilamine, ethylallylamine, ethylbutenylamine, ethylpentenylamines, ethylhexenylamines, propylvinylamines, propylallylamines, propylbutenylamines, propylpentenylamines, propylhexenylamines, butylvinylamines, Butylallylamines, butylbutenylamines, butylpentenylamines, butylhexenylamines, vinylallylamine, vinylbutenylamines, vinylpentenylamines, vinylhexenylamines, allylbutenylamines, allylpentenylamines, Allylhexenylamines, butenylpentenylamines, butenylhexenylamines, dicyclopentylamine, dicyclohexyl, methylcyclopentylamine, methyl Hexylamine, methylcyclooctylamine, ethylcyclopentylamine, ethylcyclohexylamine, ethylcyclooctylamine, propylcyclopentylamines, propylcyclohexylamines, butylcyclopentylamines, butylcyclohexylamines, hexylcyclopentylamines, hexylcyclohexylamines , Hexylcyclooctylamines, vinylcyclopentylamine, vinylcyclohexylamine, vinylcyclooctylamine, allylcyclopentylamine, allylcyclohexylamine, allylcyclooctylamine, butenylcyclopentylamines, butenylcyclohexylamines, butenylcyclooctylamine , Dicyclopentenylamines, dicyclohexenylamines , Dicyclooctenylamines, methylcyclopentenylamines, methylcyclohexenylamines, methylcyclooctenylamines, ethylcyclopentenylamines, ethylcyclohexenylamines, ethylcyclooctenylamines, propylcyclopentenylamine Propylcyclohexenylamines, butylcyclopentenylamines, butylcyclohexenylamines, vinylcyclopentenylamines, vinylcyclohexenylamines, vinylcyclooctenylamines, allylcyclopentenylamines, allylcyclohexenylamines , Butenylcyclopentenylamines, butenylcyclohexenylamines,

  Dicyclopentadienylamine, dicyclohexadienylamines, dicyclooctadienylamines, methylcyclopentadienylamine, methylcyclohexadienylamines, ethylcyclopentadienylamine, ethylcyclohexadienylamines, Propylcyclopentadienylamines, propylcyclohexadienylamines, dicyclooctatrienylamines, methylcyclooctatrienylamines, ethylcyclooctatrienylamines, vinylcyclopentadienylamine, vinylcyclohexadienyl Amines, allylcyclopentadienylamine, allylcyclohexadienylamines, diphenylamine, ditolylamines, dibenzylamine, dinaphthylamines, N-methylaniline, N-ethylamine Phosphorus, N-propylanilines, N-butylanilines, N-methyltoluidine, N-ethyltoluidine, N-propyltoluidines, N-butyltoluidines, N-methylbenzylamine, N-ethylbenzylamines, N -Propylbenzylamines, N-butylbenzylamines, N-methylnaphthylamines, N-ethylnaphthylamines, N-propylnaphthylamines, N-vinylaniline, N-allylaniline, N-vinylbenzylamine, N-allyl Benzylamine, N-vinyltoluidine, N-allyltoluidine, phenylcyclopentylamine, phenylcyclohexylamine, phenylcyclooctylamine, phenylcyclopentenylamine, phenylcyclohexenylamine, phenylcyclopentadienyl amine N-methylanisole, N-ethylanisole, N-vinylanisole, N-allylanisole, N-methylethylenediamine, N, N′dimethylethylenediamine, N-ethylethylenediamine, N, N′-diethylethylenediamine, N, N'-dimethyltolylenediamine, N, N'-diethyltolylenediamine, N-methylethylenetriamine, N, N'-dimethylethylenetriamine, pyrrole, pyrrolidine, imidazole, piperidine, piperazine, methylpyrroles, methyl Pyrrolidines, methylimidazoles, methylpiperidines, methylpiperazines, ethylpyrroles, ethylpyrrolidines, ethylimidazoles, ethylpiperidines, ethylpiperazines, phthalimide, maleimide, caprolacta , Pyrrolidone, morpholine, N-methylglycine, N-ethylglycine, N-methylalanine, N-ethylalanine, N-methyl-aminothiophene, N-ethylaminothiophene, 2,5-piperazinedione, N-methylethanol Examples include amines, N-ethylethanolamine, and purines.

  Tertiary amines include: trimethylamine, triethylamine, tripropylamines, tributylamines, tripentylamines, trihexylamines, dimethylethylamine, dimethylpropylamines, dimethylbutylamines, dimethylpentylamines, dimethyl Hexylamines, diethylpropylamines, diethylbutylamines, diethylpentylamines, diethylhexylamines, dipropylbutylamines, dipropylpentylamines, dipropylhexylamines, dibutylpentylamines, dibutylhexylamines, Dipentylhexylamines, methyldiethylamine, methyldipropylamines, methyldibutylamines, methyldipentylamines, methyldihexylamines, ethyl Dipropylamines, ethyldibutylamines, ethyldipentylamines, ethyldihexylamines, propyldibutylamines, propyldipentylamines, propyldihexylamines, butyldipentylamines, butyldihexylamines, pentyldihexylamines, Methylethylpropylamines, methylethylbutylamines, methylethylhexylamines, methylpropylbutylamines, methylpropylhexylamines, ethylpropylbutylamine, ethylbutylpentylamines, ethylbutylhexylamines, propylbutylpentylamines, propyl Butylhexylamines, butylpentylhexylamines, trivinylamine, triallylamine, tributenylamines, tripentenyl Min acids, tri-hexenyl amine,

  Dimethylvinylamine, dimethylallylamine, dimethylbutenylamines, dimethylpentenylamines, diethylvinylamine, diethylallylamine, diethylbutenylamines, diethylpentenylamines, diethylhexenylamines, dipropylvinylamines, dipropylallylamine , Dipropylbutenylamines, methyldivinylamine, methyldiallylamine, methyldibutenylamines, ethyldivinylamine, ethyldiallylamine, tricyclopentylamine, tricyclohexylamine, tricyclooctylamine, tricyclopentenylamine, tricyclohexenyl Amine, tricyclopentadienylamine, tricyclohexadienylamines, dimethylcyclopentylamine, diethylcyclopent Ruamine, dipropylcyclopentylamine, dibutylcyclopentylamine, dimethylcyclohexylamine, diethylcyclohexylamine, dipropylcyclohexylamine, dimethylcyclopentenylamine, diethylcyclopentenylamine, dipropylcyclopentenylamine, dimethylcyclohexenylamine , Diethylcyclohexenylamines, dipropylcyclohexenylamines, methyldicyclopentylamine, ethyldicyclopentylamine, propylcyclopentylamines, methyldicyclohexylamine, ethyldicyclohexylamine, propylcyclohexylamines, methyldicyclopentenylamines, Ethyl dicyclopentenyl amines, propyl dicyclopentenyl amines N, N-dimethylaniline, N, N-dimethylbenzylamine, N, N-dimethyltoluidines, N, N-dimethylnaphthylamines, N, N-diethylaniline, N, N-diethylbenzylamine, N, N- Diethyltoluidines, N, N-diethylnaphthylamines, N, N-dipropylanilines, N, N-dipropylbenzylamines, N, N-dipropyltoluidines, N, N-dipropylnaphthylamines,

  N, N-divinylaniline, N, N-diallylaniline, N, N-divinyltoluidines, N, N-diallylaniline, diphenylmethylamine, diphenylethylamine, diphenylpropylamines, dibenzylmethylamine, dibenzylethylamine, Dibenzylcyclohexylamine, dibenzylvinylamine, dibenzylallylamine, ditolylmethylamines, ditolylethylamines, ditolylcyclohexylamines, ditolylvinylamines, triphenylamine, tribenzylamine, tri (tolyl) amine , Trinaphthylamines, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetraethylethylenediamine, N, N, N ′, N′-tetramethyltolylenediamines, N, N, N ' N′-tetraethyltolylenediamine, N-methylpyrrole, N-methylpyrrolidine, N-methylimidazole, N, N′-dimethylpiperazine, N-methylpiperidine, N-ethylpyrrole, N-methylpyrrolidine, N-ethyl Imidazole, N, N′-diethylpiperazine, N-ethylpiperidine, pyridine, pyridazine, pyrazine, quinoline, quinazoline, quinuclidine, N-methylpyrrolidone, N-methylmorpholine, N-ethylpyrrolidone, N-ethylmorpholine, N, N -Dimethylanisole, N, N-diethylanisole, N, N-dimethylglycine, N, N-diethylglycine, N, N-dimethylalanine, N, N-diethylalanine, N, N-dimethylethanolamine, N, N -Dimethylaminothiophene, 1,1 3,3-tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [ 2.2.2] octane, hexamethylenetetramine and the like.

  Therefore, the above amines are aliphatic or alicyclic, saturated or unsaturated hydrocarbon groups; aromatic hydrocarbon groups; oxygen-containing, sulfur-containing and / or selenium-containing hydrocarbon groups having one or more nitrogen atoms. Is a compound bound to. From the viewpoint of film strength after thermal crosslinking, the range of amine pKa (acid dissociation constant of conjugate acid) is preferably 7 or more, and more preferably 10 or more.

  From the viewpoint of rapidly proceeding the alcohol exchange reaction in the membrane, methanesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, dodecylbenzenesulfonic acid, phosphoric acid, phosphonic acid, acetic acid, 1,8-diazabicyclo [ 5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,1,3,3-tetramethylguanidine are preferred, methanesulfonic acid, p- Toluenesulfonic acid, phosphoric acid, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferred.

(2) Metal Complex Catalyst The metal complex catalyst that can be used in the present invention is a metal element selected from the group consisting of groups 2, 4, 5, and 13 of the periodic table, and β-diketone, ketoester, hydroxycarboxylic acid. And an ester thereof, an amino alcohol, and an oxo or hydroxy oxygen compound selected from the group consisting of enolic active hydrogen compounds.
Furthermore, among the constituent metal elements, group 2 elements such as Mg, Ca, St, and Ba, group 4 elements such as Ti and Zr, group 5 elements such as V, Nb, and Ta, and 13 such as Al and Ga. Group elements are preferred and each form a complex with an excellent catalytic effect. Among them, complexes obtained from Zr, Al, and Ti are excellent and preferable (such as ethyl orthotitanate).

  Examples of the oxo or hydroxy oxygen-containing compound constituting the ligand of the metal complex include acetylacetone, acetylacetone (2,4-pentanedione), β-diketones such as 2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, Ketoesters such as butyl acetoacetate, hydroxycarboxylic acids and esters such as lactic acid, methyl lactate, salicylic acid, ethyl salicylate, phenyl salicylate, malic acid, tartaric acid, methyl tartrate, 4-hydroxy-4-methyl-2-pentanone, 4- Ketoalcohols such as hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, 4-hydroxy-2-heptanone, monoethanolamine, N, N-dimethylethanolamine, N-methyl-monoethanolamine , Gietano Amino alcohols such as ruamine, triethanolamine, enol active compounds such as methylol melamine, methylol urea, methylol acrylamide, diethyl malonate, methyl group, methylene group or carbonyl carbon of acetylacetone (2,4-pentanedione) The compound which has a substituent is mentioned.

A preferred ligand is acetylacetone or an acetylacetone derivative.
In the present invention, an acetylacetone derivative refers to a compound having a substituent on the methyl group, methylene group or carbonyl carbon of acetylacetone. As a substituent which substitutes for the methyl group of acetylacetone, all are a C1-C3 linear or branched alkyl group, an acyl group, a hydroxyalkyl group, a carboxyalkyl group, an alkoxy group, and an alkoxyalkyl group.
Substituents for substitution on the methylene group of acetylacetone are carboxyl groups, both linear or branched carboxyalkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms, and substituents for substitution on the carbonyl carbon of acetylacetone. An alkyl group having 1 to 3 carbon atoms. In this case, a hydrogen atom is added to carbonyl oxygen to form a hydroxyl group.
Specific examples of preferred acetylacetone derivatives include ethylcarbonylacetone, n-propylcarbonylacetone, i-propylcarbonylacetone, diacetylacetone, 1-acetyl-1-propionylacetylacetone, hydroxyethylcarbonylacetone, hydroxypropylcarbonylacetone, acetoacetic acid, Examples include acetopropionic acid, diacetacetic acid, 3,3-diacetpropionic acid, 4,4-diacetbutyric acid, carboxyethylcarbonylacetone, carboxypropylcarbonylacetone, and diacetone alcohol.
Among these, acetylacetone and diacetylacetone are particularly preferable as the ligand.
The complex of the above acetylacetone or acetylacetone derivative and the above metal element is preferably a mononuclear complex in which 1 to 4 molecules of acetylacetone or an acetylacetone derivative are coordinated per metal element, and the metal element can be coordinated. When the number of bonds capable of coordination of acetylacetone or acetylacetone derivatives is larger than the total number of bonds that can be coordinated, ligands commonly used for ordinary complexes such as water molecules, halogen ions, nitro groups, and ammonio groups may coordinate. .

  Examples of preferred metal complexes include tris (acetylacetonato) aluminum complex, di (acetylacetonato) aluminum / aqua complex, mono (acetylacetonato) aluminum / chloro complex, di (diacetylacetonato) aluminum complex, ethylacetate Acetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), cyclic aluminum oxide isopropylate, tris (acetylacetonato) barium complex, di (acetylacetonato) titanium complex, tris (acetylacetonato) titanium complex, di-i -Propoxy bis (acetylacetonato) titanium complex salt, zirconium tris (ethyl acetoacetate), zirconium tris (benzoic acid) complex salt, etc. are mentioned. These are excellent in stability in water-based coating solutions and in gelation promotion effect in sol-gel reaction during heat drying, but in particular, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), diester (Acetyl acetonato) titanium complex salt and zirconium tris (ethyl acetoacetate) are preferable.

(E) Photothermal Conversion Agent The resin composition for laser engraving of the present invention preferably contains (e) a photothermal conversion agent.
The photothermal conversion agent is considered to promote thermal decomposition of the cured product of the resin composition for laser engraving of the present invention by absorbing laser light and generating heat. Therefore, it is preferable to select a photothermal conversion agent that absorbs light having a laser wavelength used for engraving.

When a laser (YAG laser, semiconductor laser, fiber laser, surface emitting laser, etc.) emitting an infrared ray having a wavelength of 700 nm to 1,300 nm is used as a light source for laser engraving, the relief forming layer in the present invention has a thickness of 700 nm to 1,300 nm. It is preferable to contain the photothermal conversion agent which can absorb the light of this wavelength.
Various dyes or pigments are used as the photothermal conversion agent in the present invention.

  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 nm to 1,300 nm. Azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, diimmonium compounds, quinone imine dyes , Methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, and metal thiolate complexes. In particular, cyanine dyes such as heptamethine cyanine dye, oxonol dyes such as pentamethine oxonol dye, and phthalocyanine dyes are preferably used. Examples thereof include the dyes described in paragraphs 0124 to 0137 of JP-A-2008-63554.

  Among the photothermal conversion agents used in the present invention, commercially available pigments and color index (CI) manuals, “latest pigment manuals” (edited by the Japan Pigment Technical Association, published in 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 black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is preferable.

  As long as the dispersibility in the composition is stable, carbon black can be used regardless of the classification according to ASTM and the use (for example, for color, for rubber, for dry battery, etc.). 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.

  In the present invention, it is also possible to use carbon black having a relatively low specific surface area and relatively low DBP absorption and even finer carbon black having a large specific surface area. Examples of suitable carbon blacks include Printex® U, Printex® A, or Specialschwarz® 4 (from Degussa).

The carbon black that can be used in the present invention has a specific surface area of 150 m ² / g or more and DBP from the viewpoint of improving engraving sensitivity by efficiently transferring heat generated by photothermal conversion to surrounding polymers. Conductive carbon black having a number of 150 ml / 100 g or more is preferred.

The specific surface area is preferably 250 m ² / g or more, and more preferably 500 m ² / g or more. The number of DBPs is preferably 200 m ² / g or more, and more preferably 250 ml / 100 g or more. The carbon black described above may be acidic or basic carbon black. The carbon black is preferably basic carbon black. Of course, mixtures of different binders can also be used.

Conductive carbon black having a specific surface area of 150 to about 1,500 m ² / g and a DBP number of 150 to about 550 ml / 100 g are, for example, Ketjenblack (registered trademark) EC300J, Ketjenblack (registered trademark) EC600J ( (From Akzo), Princex (registered trademark) XE (from Degussa) or Black Pearls (registered trademark) 2000 (from Cabot), Ketjen Black (manufactured by Lion Corporation), and commercially available is there.

  The content of the photothermal conversion agent in the resin composition for laser engraving of the present invention varies greatly depending on the size of the molecular extinction coefficient inherent to the molecule, but is 0.01 to the total solid weight of the resin composition. It is preferably 20% by weight, more preferably 0.05 to 10% by weight, and still more preferably 0.1 to 5% by weight.

(F) Polymerization initiator When the resin composition for laser engraving of the present invention is used for producing a relief forming layer, it preferably further contains (f) a polymerization initiator, and is polymerized with a compound having an ethylenically unsaturated group. More preferably, an initiator is used in combination.
A well-known thing can be used for a polymerization initiator without a restriction | limiting. Hereinafter, although the radical polymerization initiator which is a preferable polymerization initiator is explained in full detail, this invention is not restrict | limited by these description.

  In the present invention, preferred radical polymerization initiators include (Ia) aromatic ketones, (Ib) onium salt compounds, (Ic) organic peroxides, (Id) thio compounds, ( I-e) hexaarylbiimidazole compound, (If) ketoxime ester compound, (Ig) borate compound, (Ih) azinium compound, (Ii) metallocene compound, (I-j) ) Active ester compounds, (Ik) compounds having a carbon halogen bond, (I-1) azo compounds, and the like. Specific examples of the above (Ia) to (I-1) are shown below, but the present invention is not limited thereto.

  In the present invention, (Ic) organic peroxide and (Il) azo are used from the viewpoint of engraving sensitivity and a good relief edge shape when applied to the relief forming layer of the relief printing plate precursor. Type compounds are more preferred, and (Ic) organic peroxides are particularly preferred.

(Ia) aromatic ketones, (Ib) onium salt compounds, (Id) thio compounds, (Ie) hexaarylbiimidazole compounds, (If) ketoxime ester compounds, Ig) borate compounds, (Ih) azinium compounds, (Ii) metallocene compounds, (j) active ester compounds, and (Ik) compounds having a carbon halogen bond are disclosed in JP-A-2008-63554. The compounds listed in paragraphs 0074 to 0118 of the publication can be preferably used.
In addition, as the (Ic) organic peroxide and the (I-1) azo compound, the following compounds are preferable.

(Ic) Organic peroxide The (Ic) organic peroxide that can be used in the present invention includes 3,3′4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3, 3'4,4'-tetra (t-amylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra (t -Octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t -Peroxide esters such as butyl diperoxyisophthalate are preferred.

(I-l) Azo-Based Compound Examples of (I-l) azo-based compounds that can be used in the present invention include 2,2'-azobisisobutyronitrile, 2,2'-azobispropionitrile, , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′- Azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (2-methylpropionamide) Oxime), 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydroxyethyl] Pro Onamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (2,4,4-trimethylpentane) Etc.

  In the present invention, the (Ic) organic peroxide is preferably used as a polymerization initiator in the present invention from the viewpoint of the crosslinkability of the film (relief-forming layer), and as an unexpected effect, engraving sensitivity. It was found that it is particularly preferable from the viewpoint of improvement.

From the viewpoint of engraving sensitivity, an embodiment in which the (Ic) organic peroxide and a polymer having a glass transition temperature of room temperature or higher as a binder polymer is particularly preferable.
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, it is presumed that the engraving sensitivity is increased because the heat generated is added to the irradiated laser energy.
In particular, when the glass transition temperature of the binder polymer is above room temperature, the heat generated from the decomposition of the organic peroxide is efficiently transferred to the binder polymer and is effectively used for the thermal decomposition of the binder polymer itself. Therefore, it is estimated that the sensitivity will be higher.
In addition, although explained in full detail in description of a photothermal conversion agent, this effect is remarkable when using carbon black as a photothermal conversion agent. This is because heat generated from carbon black is transferred to (Ic) organic peroxide, and heat is generated not only from carbon black but also from organic peroxide. This is thought to be due to the synergistic generation of heat energy.

The (f) polymerization initiator in the present invention may be used alone or in combination of two or more.
The content of the polymerization initiator (f) in the relief forming layer is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 10% by weight, based on the total solid content of the relief forming layer. By making the content of the polymerization initiator 0.01% by weight or more, the effect of adding this is obtained, and the crosslinkable relief forming layer is rapidly crosslinked. Further, when the content is 10% by weight or less, other components are not deficient, and printing durability sufficient for use as a relief printing plate can be obtained.

(G) Solvent The resin composition of the present invention is a relief-forming layer that promotes the reaction between the binder polymer and the specific compound, the reaction between the binder polymer and the crosslinking agent, the adjustment of the viscosity of the resin composition, coating and casting, etc. In order to facilitate the formation of, a solvent may be contained. The solid content of the resin composition is an amount excluding volatile components such as a solvent.
As the solvent, aprotic organic solvent / protic organic solvent = 100/0 to 50/50 (weight) from the viewpoint of promptly proceeding the reaction between the binder polymer and the specific compound and the reaction between the binder polymer and the crosslinking agent. Ratio), preferably 100/0 to 70/30, more preferably 100/0 to 90/10.
Preferred specific examples of the aprotic organic solvent include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide, Examples thereof include N-methylpyrrolidone and dimethyl sulfoxide.
Preferable specific examples of the protic organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol and 1,3-propanediol.

(H) Other additives The resin composition for laser engraving of the present invention preferably contains a plasticizer.
The plasticizer has a function of softening a film formed of the resin composition for laser engraving, and needs to be compatible with the binder polymer.
As the plasticizer, for example, dioctyl phthalate, didodecyl phthalate or the like, polyethylene glycols, polypropylene glycol (monool type or diol type), polypropylene glycol (monool type or diol type) are preferably used.

In the resin composition for laser engraving of the present invention, it is more preferable to add nitrocellulose or a highly thermally conductive substance as an additive for improving engraving sensitivity. Since nitrocellulose is a self-reactive compound, it generates heat during laser engraving and assists in thermal decomposition of a binder polymer such as a hydrophilic polymer. As a result, it is estimated that the engraving sensitivity is improved. The high thermal conductive material is added for the purpose of assisting heat transfer, and examples of the thermal conductive material include inorganic compounds such as metal particles and organic compounds such as conductive polymers. As the metal particles, the conductive polymer is preferably a gold fine particle, a silver fine particle, or a copper fine particle having a particle size of micrometer order to several nanometer order. Particularly, a conjugated polymer is preferable, and specifically, polyaniline and polythiophene are mentioned. It is done.
Colorants such as dyes or pigments may be added for the purpose of coloring the resin composition for laser engraving. Thereby, properties such as the visibility of the image portion and the suitability of the image density measuring device can be improved.
Furthermore, in order to improve the physical properties of the cured film of the resin composition for laser engraving, a known additive such as a filler may be added.

[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.
In addition, 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” means a state in which a relief-forming layer having a crosslinkability made of a resin composition for laser engraving is in a state before being crosslinked and cured by light or heat. Both or either one.
In the present invention, the “relief-forming layer” refers to a layer in a state before being crosslinked, that is, a layer composed of the resin composition for laser engraving of the present invention, and if necessary, may be dried. 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. Needless to say, the crosslinking is a crosslinked structure formed by the reaction of the crosslinking agent in the resin composition and the polymer.
A “relief printing plate” is produced by laser engraving a printing plate precursor having a crosslinked relief forming layer.
In the present invention, 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 forming layer is preferably provided on a support.
If necessary, the relief printing plate precursor for laser engraving may further have an adhesive layer between the support and the relief forming layer, and a slip coat layer and a protective film on the relief forming layer.

<Relief forming layer>
The relief forming layer is a layer made of the resin composition for laser engraving of the present invention, and is preferably a layer that is cured by at least one of light and heat, that is, a layer having crosslinkability.
The method for producing a relief printing plate using the relief printing plate precursor of the present invention is preferably a production method for producing a relief printing plate by forming a relief layer by crosslinking a relief forming layer and then laser engraving. . 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.
In addition, a relief forming layer can be formed by using the coating liquid composition for relief forming layers, and shape | molding this to a sheet form or a sleeve form.

<Support>
The support that can be used for the relief printing plate precursor for laser engraving will be described.
The material used for the support for 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, aluminum, polyester (for example, polyethylene terephthalate (PET) ), Polybutylene terephthalate (PBT), polyacrylonitrile (PAN)), plastic resins such as polyvinyl chloride, synthetic rubbers such as styrene-butadiene rubber, and plastic resins reinforced with glass fibers (such as epoxy resins and phenol resins) Can be mentioned. 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.
Moreover, it was prepared by applying a crosslinkable resin composition for laser engraving and curing from the back surface (opposite surface to which laser engraving is performed, including a cylindrical one) with heat and / or light. In the relief printing plate precursor for laser engraving, since the back side of the cured resin composition for laser engraving functions as a support, the support is not necessarily essential.

<Adhesive layer>
An adhesive layer may be provided between the relief forming layer and the support for the purpose of enhancing the adhesive force between the two layers. Examples of the material (adhesive) that can be used for the adhesive layer include: Those described in Skeist ed., “Handbook of Adhesives”, 2nd edition (1977) can be used.

<Protective film, slip coat layer>
A protective film may be provided on the surface of the relief forming layer or the surface of the crosslinked relief forming 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. 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)
Next, a method for producing a relief printing plate precursor for laser engraving will be described.
Formation of the relief forming layer in the relief printing plate precursor for laser engraving is not particularly limited. For example, a relief forming layer coating liquid composition (containing a resin composition for laser engraving) is prepared, and this relief is formed. The method of melt-extruding on a support body after removing a solvent from the coating liquid composition for forming layers is mentioned. Or the method of casting the coating liquid composition for relief forming layers on a support body, drying this in oven, and removing a solvent from a coating liquid composition may be sufficient.
Among these, the method for producing a 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 the relief forming layer by heat and / or light. It is preferable that the production method includes a crosslinking step of obtaining a relief printing plate precursor that is crosslinked and has a crosslinked relief forming layer.

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 method for producing a 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 a relief forming layer, the resin composition for laser engraving of the present invention is prepared. A method of preparing the resin composition for laser engraving of the present invention, casting the resin composition for laser engraving of the present invention on a support and drying it in an oven to remove the solvent is preferably exemplified.
For example, the coating composition for the relief forming layer is prepared by dissolving the cross-linking agent, the polymer, and, as an optional component, a photothermal conversion agent and a plasticizer in an appropriate solvent, and then dissolving the polymerizable compound and the polymerization initiator. Can be manufactured. Since most of the solvent components need to be removed at the stage of producing the relief printing plate precursor, the solvent may be a low-molecular alcohol that easily volatilizes (for example, methanol, ethanol, n-propanol, isopropanol, propylene glycol monomethyl). It is preferable to keep the total amount of solvent added as small as possible by adjusting the temperature.

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

<Crosslinking process>
The method for producing a relief printing plate for laser engraving of the present invention is preferably a production method including a crosslinking step of obtaining a relief printing plate precursor having a crosslinked relief forming layer by crosslinking the relief forming layer with heat and / or light. .
The term “crosslinking” as used herein is not particularly limited as long as the relief forming layer is cured. Curing by the reaction between compounds represented by formulas (1) to (4), formulas (1) to (4) It represents curing by reaction of the compound represented by the above and a binder polymer, and further curing by adding a crosslinking agent to form a crosslinked structure.

The light irradiation is preferably performed on the entire surface of the relief forming layer.
Examples of light include visible light, ultraviolet light, and electron beam, but ultraviolet light is most preferable. If the support side of the relief forming layer is the back side, the surface may only be irradiated with light, but if the support is a transparent film that transmits light, it is preferable that the back side is further irradiated with light. When the protective film exists, the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. If there is a possibility that the crosslinking reaction may be inhibited in the presence of oxygen, the relief forming layer may be covered with a vinyl chloride sheet and evacuated and then irradiated with light.
When the relief-forming layer contains a thermal polymerization initiator (the above-mentioned photopolymerization initiator can also be a thermal polymerization initiator), the relief-forming layer is heated by heating the relief printing plate precursor for laser engraving. It can be crosslinked (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.

As a crosslinking method of the relief forming layer in the crosslinking step, crosslinking by heat is preferable from the viewpoint that the relief forming layer can be uniformly cured (crosslinked) from the surface to the inside.
By crosslinking the relief forming layer, there is an advantage that the relief formed first after laser engraving becomes sharp, and secondly, the adhesiveness of engraving residue generated during laser engraving is suppressed.

(Relief printing plate and manufacturing method thereof)
The method for producing a relief printing plate of the present invention comprises a layer forming step of forming a relief forming layer comprising the resin composition for laser engraving of the present invention, and the crosslinked relief forming layer is formed by crosslinking the relief forming layer with heat and / or light. A crosslinking step for obtaining the relief printing plate precursor having the above-mentioned structure, and a engraving step for laser engraving the relief printing plate precursor having the crosslinked relief-forming layer.
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 comprising the resin composition for laser engraving of the present invention. It is preferably a relief printing plate that has been made.
The layer forming step and the crosslinking step in the method for producing a relief printing plate of the present invention are synonymous with the layer forming step and the crosslinking step in the method for producing a relief printing plate precursor for laser engraving, and the preferred range is also the same.

<Engraving process>
The method for producing a 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. Preferably, a step of controlling the laser head with a computer based on the digital data of a desired image and irradiating the crosslinked relief forming layer with scanning is exemplified.
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, a 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 a portion of a groove that prints fine punched characters is engraved deeply As a result, the ink is less likely to be buried in the groove, and it is possible to suppress the crushing of the extracted characters.
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.

The infrared laser used in the engraving process is preferably a carbon dioxide laser or a semiconductor laser from the viewpoint of productivity, cost, and the like. In particular, a semiconductor infrared laser with a fiber is preferably used. In general, a semiconductor laser can be downsized with high efficiency and low cost in laser oscillation as compared with a CO ₂ laser. Moreover, since it is small, it is easy to form an array. Furthermore, the beam shape can be controlled by processing the fiber.
The semiconductor laser can be used if it has a wavelength of 700 to 1,300 nm, preferably 800 to 1,200 nm, more preferably 860 to 1,200 nm, and 900 to 1,100 nm. Some are particularly preferred.

In the method for producing a relief printing plate of the present invention, after 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 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.

When the engraving residue is attached to the engraving surface, 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, a method of washing with tap water, a method of spraying high-pressure water, a known batch type or conveying type brush type washing machine as a developing device for photosensitive resin relief printing, the surface of engraving is mainly present For example, when the engraving residue cannot be removed, a rinsing solution to which 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 a post-crosslinking step, which is an additional cross-linking step, the relief formed by engraving can be further strengthened.

The rinsing liquid that can be used in the present invention is preferably water or a liquid containing water as a main component.
The pH of the rinsing liquid is preferably 9 or more, more preferably 10 or more, and still more preferably 11 or more. Moreover, it is preferable that the pH of a rinse liquid is 14 or less, It is more preferable that it is 13 or less, It is still more preferable that it is 12.5 or less. Within the above range, sufficient rinsing properties (cleaning properties) can be obtained, and handling is easy.
What is necessary is just to adjust pH using an acid and 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. As the base for adjusting pH, an inorganic base is preferable, and examples thereof include KOH and NaOH. Further, when an acid is used for adjusting the pH, inorganic acids are preferred, for example, HCl, H ₂ SO _3, phosphoric acid, HNO ₃ is illustrated.

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.
The pH of the rinse liquid is preferably 9 or more, more preferably 9 to 14, and still more preferably 9 to 12.5.
The rinsing liquid for relief printing plate making of the present invention preferably contains a basic compound, and more preferably contains a water-soluble basic compound.
There is no restriction | limiting in particular as a basic compound, Although a well-known basic compound can be used, It is preferable that it is an inorganic basic compound, and it is an alkali metal salt compound and an alkaline-earth metal salt compound Is more preferable, and an alkali metal hydroxide is more preferable.
Examples of basic compounds include sodium hydroxide, ammonium, potassium, lithium, sodium silicate, potassium, tribasic sodium phosphate, potassium, ammonium, dibasic sodium phosphate, potassium, Examples include inorganic alkali salts such as ammonium, sodium carbonate, potassium, ammonium, sodium hydrogen carbonate, potassium, ammonium, sodium borate, potassium, and ammonium.
Moreover, when using an acid for adjustment of pH, an inorganic acid is preferable, for example, hydrochloric acid, a sulfuric acid, phosphoric acid, and nitric acid are illustrated.

The rinsing liquid preferably contains a surfactant.
There is no restriction | limiting in particular as surfactant, A well-known surfactant can be used, Anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant etc. can be illustrated.
Anionic surfactants include fatty acid salts, abietic acid salts, hydroxyalkane sulfonates, alkane sulfonates, α-olefin sulfonates, dialkyl sulfosuccinates, alkyl diphenyl ether disulfonates, linear alkyl benzene sulfonates, Branched alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamides Sodium salts, petroleum sulfonates, sulfated castor oil, sulfated beef tallow oil, fatty acid alkyl ester sulfate esters, alkyl sulfate esters, polio Siethylene alkyl ether sulfates, fatty acid monoglyceride sulfates, polyoxyethylene alkylphenyl ether sulfates, polyoxyethylene styrylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxy Examples thereof include ethylene alkylphenyl ether phosphate esters, partially saponified products of styrene-maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, naphthalene sulfonate formalin condensates, and the like.

Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
Examples of amphoteric surfactants include alkyl carboxybetaines, alkyl imidazolines, and alkylaminocarboxylic acids.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, glycerin fatty acid partial esters, sorbitan fatty acid partial esters , Pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid partial esters , Fatty acid diethanolamides, N, N-bis-2-hydroxyalkylamines, polyoxyethylene alkyl Min, triethanolamine fatty acid esters, trialkylamine oxides, molecular weight of polypropylene glycol 200 to 5,000, trimethylolpropane, adduct of glycerin or sorbitol polyoxyethylene or polyoxypropylene, acetylene glycol, and the like.

  The surfactant that can be used in the present invention is preferably a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or a phosphine oxide compound.

  The rinsing liquid that can be used in the present invention is, in particular, an amphoteric surfactant represented by the following formula (1) (compound represented by formula (1)) and / or an amphoteric interface represented by formula (2). It is preferable that an activator (compound represented by Formula (2)) is included. Among these, it is more preferable to contain at least an amphoteric surfactant represented by the formula (1) (a compound represented by the formula (1)).

（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 rinsing liquid that can be used in the present invention is a compound represented by the formula (1) and / or a compound represented by the formula (2), which may be used alone or in combination of two or more. However, it is preferable to contain at least the compound represented by the formula (1).
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 phosphine oxide compound P = O ^{is, 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 2 ^— and OPO (OR ¹⁰ ) O 2 ^— represents a hydrogen atom or a monovalent organic group, and represents 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 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 the formula (4), R ^{6 to} R ⁸ each independently represents an alkyl group, an alkenyl group, an aryl group, or a hydroxy group. However, all of R ^{6 to} R ⁸ do not become the same group. .)

R ^{6 to} R ⁸ in the formula (4) each independently represent 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.

  When the compound represented by the formula (1) and / or the compound represented by the formula (2) is used in the rinse liquid, the compound represented by the formula (1) and / or the formula (2) in the rinse liquid is used. The total content of the compound to be formed is preferably 0.1 to 20% by weight, more preferably 0.3 to 10% by weight, and further preferably 0.5 to 7% by weight.

Moreover, you may use surfactant other than the compound represented by the compound represented by Formula (1), and Formula (2) for a rinse liquid.
In the rinsing solution, when a surfactant other than the compound represented by the formula (1) and the compound represented by the formula (2) is used, the addition amount thereof is the compound represented by the formula (1) and the formula ( 2) Total weight of compound represented by: Total weight of surfactant other than compound represented by formula (1) and compound represented by formula (2) = 1: 1.2 to 1: 0.1 Is preferable, and 1: 1 to 1: 0.1 is more preferable.

Fluorine-based and silicone-based nonionic surfactants can also 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 weight, more preferably 0.05 to 10% by weight, based on the total weight of the rinse liquid. .

The rinse liquid preferably contains an antifoaming agent.
As the antifoaming agent, a general silicone-based self-emulsifying type, emulsifying type, surfactant nonionic HLB (Hydrophile-Lipophile Balance) value of 5 or less can be used. Silicone defoamers are preferred. Among them, an emulsified dispersion type and a solubilized type can be used.
Specific examples of the antifoaming agent include TSA 731 and TSA 739 (manufactured by Toray Dow Corning Co., Ltd.).
The content of the antifoaming agent is preferably 0.001 to 1.0% by weight in the rinsing liquid for relief printing plate making.

Hereinafter, with reference to FIG. 1, the configuration of a plate making apparatus 11 including a fiber-coupled semiconductor laser recording apparatus 10 that can be used for producing a relief printing plate using the relief printing plate precursor of the present invention will be described. To do.
A plate making apparatus 11 including a fiber-coupled semiconductor laser recording apparatus 10 that can be used in the present invention rotates a drum 50 having a relief printing plate precursor F (recording medium) of the present invention mounted on its outer peripheral surface in the main scanning direction. At the same time, a plurality of laser beams corresponding to the image data of the image to be engraved (recorded) are simultaneously emitted onto the relief printing plate precursor F, and the exposure head 30 is scanned in the sub-scanning direction orthogonal to the main scanning direction at a predetermined pitch. Thus, the two-dimensional image is engraved (recorded) on the relief printing plate precursor F at high speed. Further, when engraving a narrow area (precision engraving such as fine lines or halftone dots), the relief printing plate precursor F is shallowly engraved, and when engraving a wide area, the relief printing plate precursor F is deeply engraved.

  As shown in FIG. 1, the plate making apparatus 11 has a relief printing plate precursor F on which an image is recorded by engraving with a laser beam, and the relief printing plate precursor F moves in the main scanning direction in the direction of arrow R in FIG. A drum 50 that is rotationally driven and a laser recording device 10 are included. The laser recording apparatus 10 includes a light source unit 20 that generates a plurality of laser beams, an exposure head 30 that exposes the plurality of laser beams generated by the light source unit 20 onto a relief printing plate precursor F, and the exposure head 30 in a sub-scanning direction. And an exposure head moving unit 40 that is moved along the direction.

  The light source unit 20 includes semiconductor lasers 21A and 21B each composed of a broad area semiconductor laser in which one ends of the optical fibers 22A and 22B are individually coupled, and a light source substrate 24A on which the semiconductor lasers 21A and 21B are arranged. , 24B, adapter boards 23A, 23B that are vertically attached to one end of the light source boards 24A, 24B and that are provided with a plurality of adapters of the SC type optical connectors 25A, 25B (the same number as the semiconductor lasers 21A, 21B), and light source boards LD driver circuits (not shown) for driving the semiconductor lasers 21A and 21B according to the image data of the image engraved (recorded) on the relief printing plate precursor F are provided at the other ends of the 24A and 24B horizontally. LD driver boards 27A and 27B are provided. .

  The exposure head 30 includes a fiber array unit 300 that collects and emits laser beams emitted from the plurality of semiconductor lasers 21A and 21B. In this fiber array section 300, laser beams emitted from the respective semiconductor lasers 21A and 21B are received by a plurality of optical fibers 70A and 70B connected to SC type optical connectors 25A and 25B connected to adapter boards 23A and 23B, respectively. Is transmitted.

  As shown in FIG. 1, in the exposure head 30, a collimator lens 32, an aperture member 33, and an imaging lens 34 are arranged in order from the fiber array unit 300 side. The opening member 33 is arranged so that the opening is positioned at the far field as viewed from the fiber array unit 300 side. As a result, the same light quantity limiting effect can be given to all laser beams emitted from the optical fiber end portions (not shown) of the plurality of optical fibers 70A and 70B in the fiber array section 300.

The laser beam is imaged in the vicinity of the exposure surface (front surface) FA of the relief printing plate precursor F by the imaging means composed of the collimator lens 32 and the imaging lens 34.
In the present invention, since the beam shape can be changed in the semiconductor laser with a fiber, in the present invention, the imaging position is set within the range from the exposure surface FA to the inner side (laser beam traveling direction side). It is preferable to control the beam diameter of the surface (relief-forming layer surface) FA in the range of 10 μm to 80 μm from the viewpoints of performing efficient engraving and improving fine line reproducibility.

  The exposure head moving unit 40 includes a ball screw 41 and two rails 42 arranged so that the longitudinal direction thereof is along the sub-scanning direction, and operates a sub-scanning motor (not shown) that rotationally drives the ball screw 41. By doing so, the pedestal portion 310 provided with the exposure head 30 can be moved in the sub-scanning direction while being guided by the rail 42. Further, the drum 50 can be rotated in the direction of arrow R in FIG. 1 by operating a main scanning motor (not shown), thereby performing main scanning.

In the control of the shape to be engraved, it is also possible to change the shape of the engraving region by changing the amount of energy supplied to the laser without changing the beam shape of the semiconductor laser with fiber.
Specifically, there are a method of controlling by changing the output of the semiconductor laser, and a method of controlling by changing the laser irradiation time.

In the method for producing a relief printing plate of the present invention, after 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 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.

When the engraving residue is attached to the engraving surface, 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, a method of washing with tap water, a method of spraying high-pressure water, a known batch type or conveying type brush type washing machine as a developing device for photosensitive resin relief printing, the surface of engraving is mainly present For example, when the engraving residue cannot be removed, a rinsing solution to which 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 a post-crosslinking step, which is an additional cross-linking step, the relief formed by engraving can be further strengthened.

As described above, the relief printing plate of the present invention having a relief layer can be produced.
The thickness of the relief layer of the relief printing plate is preferably 0.05 mm or more and 10 mm or less, and preferably 0.05 mm or more and 7 mm or less from the viewpoint of satisfying various flexographic printing aptitudes such as abrasion resistance and ink transferability. More preferably, it is 0.05 mm or more and 0.3 mm or less.

The Shore A hardness of the relief layer of the relief printing plate is preferably 50 ° or more and 90 ° or less. 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 printing pressure of kiss touch.
The Shore A hardness in this specification is measured by measuring the amount of deformation (indentation depth) by indenting and deforming an indenter (called a push needle or indenter) on the surface of the object to be measured under the condition of 25 ° C. and 50% RH. And a value measured by a durometer (spring type rubber hardness meter) to be digitized.

  The relief printing plate produced by the method for producing a relief printing plate of the present invention can be printed with oil-based ink or UV ink by a relief printing press, and can also be printed with UV ink by a flexographic printing press. is there.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example.
In addition, the weight average molecular weight (Mw) of the polymer in an Example is displaying the value measured by the gel permeation chromatography (GPC) method unless there is particular notice.
A-1 to A-11 used in Examples are the same as A-1 to A-11 described as specific examples of the compounds represented by the formulas (1) to (4).

<Synthesis Example 1: Synthesis of A-1>
1-Methoxy-2-propanol: 121.2 parts by weight and pyridine: 141.6 parts by weight were placed in a three-necked flask and stirred for 30 minutes under ice cooling. To this solution, 181.7 parts by weight of 3-methacryloyloxypropyl chloride was added dropwise under ice-cooling, and the mixture was stirred for 6 hours after the completion of the addition. The reaction mixture was poured into 500 parts by weight of ice water, extracted with ethyl acetate, and washed with saturated brine. The organic layer was dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain an oily substance. This oily substance was purified by column chromatography using silica gel to obtain Compound A as a colorless oily substance.
To a three-necked flask equipped with a stirrer and a condenser, 26.4 parts by weight of Compound A, KBM-803 (18.7 parts by weight, 3-mercaptopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), V-65 (0 .2 parts by weight, 2,2′-azobis (2,4-dimethylvaleronitrile), manufactured by Wako Pure Chemical Industries, Ltd.), 2-butanone (105 parts by weight, manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was stirred at 75 ° C. for 7 hours under a nitrogen stream. Thereafter, the mixture was allowed to cool to room temperature to obtain a light yellow oily liquid compound A-1.

<Synthesis Examples 2 to 11: Synthesis of A-2 to A-11>
A-2 to A-11 were synthesized by the same method as the synthesis of A-1, except that the raw materials were changed.

(Examples 1 to 26 and Comparative Examples 1 to 5)
Resins for laser engraving of Examples 1 to 26 and Comparative Examples 1 to 5 by using the (A) specific compound, (B) binder, and (C) cross-linking agent described in Table 2 by the method shown below. A composition, a relief printing plate precursor for laser engraving, and a relief printing plate were prepared. Each relief printing plate obtained had a relief layer thickness of about 1 mm.

<Preparation of resin composition 1 for laser engraving>
In a three-necked flask equipped with a stirring blade and a condenser tube, (B) 50 parts by weight of a binder and 47 parts by weight of propylene glycol monomethyl ether acetate as a solvent were added and heated at 70 ° C. for 120 minutes with stirring (B) The binder was dissolved. Thereafter, the solution is brought to 40 ° C., 20 parts by weight of tributyl citrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a plasticizer, and (G) ketjen black EC600JD (carbon black, manufactured by Lion Corporation) as a photothermal conversion agent. 1 part by weight was added and stirred for 30 minutes. Thereafter, (A) 10 parts by weight of the specific compound, (C) 15 parts by weight of the crosslinking agent (but not used in Example 1) and (D) 1,8-diazabicyclo [5.4.0] 0.4 parts by weight of undec-7-ene (DBU, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 40 ° C. for 10 minutes. By this operation, a fluid relief-forming layer coating solution 1 (laser engraving resin composition) was obtained.
In addition, the thing of Table 2 was used for (A) specific compound, (B) binder, and (C) crosslinking agent.

<Preparation of relief printing plate precursor for laser engraving>
A spacer (frame) having a predetermined thickness is placed on the PET substrate, and the coating solution 1 for the crosslinkable relief forming layer obtained above is gently cast to such an extent that it does not flow out of the spacer (frame). Then, a relief forming layer having a thickness of about 1 mm was provided to prepare a relief printing plate precursor for laser engraving.

<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.
The relief forming layer after crosslinking was engraved with a carbon dioxide laser (CO ₂ laser) or a semiconductor laser with a fiber as shown in Table 2 to obtain a relief printing plate.
<Carbon dioxide laser engraving>
-As a carbon dioxide laser engraving machine, engraving by laser irradiation was performed using a high-quality CO ₂ laser marker ML-9100 series (manufactured by Keyence Corporation). After peeling off the protective film from the printing plate precursor 1 for laser engraving, a carbon dioxide laser engraving machine is used to raster engrave a 1 cm square solid part under the conditions of output: 12 W, head speed: 200 mm / sec, pitch setting: 2,400 DPI did.
<Semiconductor laser engraving>
As the semiconductor laser engraving machine, the laser recording apparatus shown in FIG. 1 equipped with a fiber-coupled semiconductor laser (FC-LD) SDL-6390 (JDSU, wavelength 915 nm) with a maximum output of 8.0 W was used. A 1 cm square solid part was raster engraved with a semiconductor laser engraving machine under conditions of laser output: 7.5 W, head speed: 409 mm / second, pitch setting: 2,400 DPI.

  The following evaluation was performed using the relief printing plate precursors and relief printing plates obtained in Examples 1 to 26 and Comparative Examples 1 to 5. The evaluation results are collectively shown in Table 2.

<Evaluation method for rinse performance of engraving residue>
The relief printing plate engraved with laser was immersed in water or alkaline water listed in Table 2, and the engraved part was rubbed 10 times with a toothbrush (Lion Corporation, Clinica Habrush Flat). The alkaline water was prepared by mixing distilled water and sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and adjusting the pH with a pH meter so that the pH was 12.5.
Thereafter, the presence or absence of residue was confirmed with an optical microscope. The case where there was no residue was marked with ◎, the case where there was almost no residue, ○, the residue with a little residue left, and the case where the residue was not removed was marked with ×.

<Membrane elasticity>
Indentation in the non-engraving part of the relief printing plate obtained with a microhardness meter (Shimazu Seisakusho Co., Ltd. DUH series) was pushed at an indentation load of 300 mN and relaxed after 10 seconds. The plastic deformation rate (%) shown below before and after was measured.
Plastic deformation rate (%) = (deformation amount that does not completely return to plastic deformation when the load is removed x 100) ÷ indentation depth when a load is applied (maximum value)

<Ink transfer properties>
The obtained relief printing plate is set in a printing machine (ITM-4 type, manufactured by Iyo Machinery Co., Ltd.), and water-based ink Aqua SPZ16 Beni (manufactured by Toyo Ink Manufacturing Co., Ltd.) is used as the ink without dilution. Then, printing was continued using full-color foam M70 (manufactured by Nippon Paper Industries Co., Ltd., thickness: 100 μm) as printing paper. The degree of ink adhesion in the solid part on the printed matter at 500 m from the start of printing was compared visually. The case where there was no density unevenness was indicated as ◯, the case where there was density unevenness as x, and the intermediate degree between ○ and x as Δ.

The details of the abbreviations in Table 2 are as follows.
B-1: Polyvinyl butyral (Denka butyral # 3000-2, manufactured by Denki Kagaku Kogyo Co., Ltd.)
B-2: Acrylic resin (Acrylic resin having a weight average molecular weight of 50,000, which is a copolymer of cyclohexyl methacrylate / 2-hydroxyethyl methacrylate = 70/30 (mol%))
B-3: Bisphenol A type epoxy resin (EPCLON 2050, manufactured by DIC Corporation)
B-4: Styrene-butadiene rubber (SBR, TR2000, manufactured by JSR Corporation)
B-5: Viro Ecole BE-450 (manufactured by Toyobo Co., Ltd.)
B-6: Polyurethane resin (tolylene diisocyanate / polypropylene glycol (average molecular weight 2,000) = 50/50 (mol%) polycondensate polycondensate with isocyanate group at the main chain end sealed with 2-hydroxyethyl acrylate Stopped polyurethane resin (weight average molecular weight: 90,000))
C-1: Z-6940 ( (H 5 C 2 O) 3 Si-C 3 H 6 -S 4 -C 3 H 6 -Si (OC 2 H 5) 3, manufactured by Dow Corning Toray Co.)
C-2: X-12-965 (Tris- (3-trimethoxysilylpropyl) isocyanurate, manufactured by Shin-Etsu Chemical Co., Ltd.)
P-1: Resin shown below

10: Laser recording device (exposure device)
11: Plate making apparatus 20: Light source unit 21A, 21B: Semiconductor laser 22A, 22B: Optical fiber 23A, 23B: Adapter substrate 24A, 24B: Light source substrate 25A, 25B: SC type optical connector 27A, 27B: LD driver substrate 30: Exposure head 32: Collimator lens (imaging means)
33: Aperture member 34: Imaging lens (imaging means)
40: exposure head moving part 41: ball screw 42: rail 50: drum 70A, 70B: optical fiber 300: fiber array part 310: pedestal part F: relief printing plate precursor FA: exposure surface (surface of relief printing plate precursor)
R: Direction of rotation

Claims (15)

(A) a compound represented by any one of the following formulas (1) to (4), and
(B) A resin composition for laser engraving, comprising a binder polymer.

(In formulas (1) to (4), R ¹ represents a binding group, R ^{2 to} R ⁶ each independently represents a monovalent organic group, and A represents an (m + n) -valent organic linking group. , K represents an integer of 0 to 4, m represents an integer of 1 to 4, and n represents an integer of 1 to 4.) The bonding group is —SiR ⁷ R ⁸ R ⁹ , acid anhydride residue, methacryloyl group, acryloyl group, styryl group, vinyloxy group, isocyanate group, blocked isocyanate group, amino group, hydroxy group, —C (═O The resin composition for laser engraving according to claim 1, which is at least one group selected from the group consisting of —R ¹⁰ , an epoxy group, and a mercapto group.
(In each of R ⁷ to R ⁹ independently of the -SiR ⁷ R ⁸ R ^9, a hydrogen atom, a halogen atom, or represents a monovalent organic group, at least one of R ⁷ to R ⁹ is an alkyl group , an alkoxy group, or a halogen atom, R ¹⁰ in the -C (= O) -R ¹⁰ represents a hydrogen atom, or an alkyl group.)   The resin composition for laser engraving according to claim 1 or 2, wherein m is 1.   (C) The resin composition for laser engraving according to any one of claims 1 to 3, further comprising a crosslinking agent.   (D) The resin composition for laser engraving according to any one of claims 1 to 4, further comprising a crosslinking accelerator.   (E) The resin composition for laser engraving according to any one of claims 1 to 5, further comprising a photothermal conversion agent.   (F) The resin composition for laser engraving according to any one of claims 1 to 6, further comprising a polymerization initiator.   A relief printing plate precursor for laser engraving having a relief forming layer comprising the resin composition for laser engraving according to any one of claims 1 to 7.   A relief printing plate precursor for laser engraving, comprising a crosslinked relief forming layer obtained by crosslinking the relief forming layer comprising the resin composition for laser engraving according to any one of claims 1 to 7.   The relief printing plate precursor for laser engraving according to claim 9, wherein the Shore A hardness of the crosslinked relief forming layer is from 50 ° to 90 °. 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 7, and
A method for producing a relief printing plate precursor for laser engraving, comprising a crosslinking step of crosslinking the relief forming layer with heat and / or light to obtain a relief printing plate precursor having a crosslinked relief forming layer.   The method for producing a relief printing plate precursor for laser engraving according to claim 11, wherein the crosslinking step is a step of crosslinking the relief forming layer with heat. 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 7,
A crosslinking step of crosslinking the relief forming layer with heat and / or light to obtain a relief printing plate precursor having a crosslinked relief forming layer; and
A method for making a relief printing plate, comprising: engraving a relief printing plate precursor having the crosslinked relief forming layer by laser engraving to form a relief layer.   The plate making method of the relief printing plate of Claim 13 whose thickness of the said relief layer is 0.05 mm or more and 10 mm or less.   A relief printing plate made by the plate making method of a relief printing plate according to claim 13 or 14.

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