JP2009262370A - Original printing plate for laser engraving and resin composition used for manufacturing this original printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an original printing plate for laser engraving which is appropriate to near infrared laser engraving and is of high definition type and almost surface stickiness-free, as well as a resin composition which is suitable for the manufacture of the original printing plate. <P>SOLUTION: This original printing plate for laser engraving can be obtained by thermally curing a resin layer made up of a resin composition. This resin composition contains 0.1 to 150 pts.mass of a polyfunctional thiol compound (b) which has two or more polymerizable functional groups, in one molecule, at least, one of which is a thiol group, to 100 pts.mass of a resin (a) with a number-average molecular weight of 300 to 300,000, 1 to 100 pts.mass of a laser absorbent (c) and 0.1 to 10 pts.mass of a heat polymerization initiator (d). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a printing plate and printing plate for laser engraving with high definition and little surface stickiness, and a resin composition suitable for their production.

In recent years, flexographic printing and gravure printing have been widely used as methods for printing on soft packaging such as films. The intaglio used for gravure printing is generally a metal intaglio. A chrome plating layer is usually provided on the surface of the intaglio. Although this metal intaglio is resistant to wear and has high durability, the plate making process is very complicated, and a large amount of wastewater treatment is required in the plating process and the like. Therefore, Patent Document 1 proposes a method in which an intaglio is directly formed by a laser on a resin layer based on a thermoplastic resin, and gravure printing is performed using the intaglio.
Patent Document 2 discloses an example in which conductive carbon black is used as a laser absorbent as a high-resolution printing plate for laser engraving in the flexographic printing field.
Japanese Patent Laid-Open No. 7-276837 International Publication No. 2004/091927 Pamphlet

However, Patent Document 1 discloses a composition comprising a thermoplastic resin, nitrocellulose, and carbon black. However, when a plate is formed, a large amount of solvent is used, and since a solvent is used, a thick film is used. There is a problem that it is very difficult to produce a printing plate. In the technique disclosed in Patent Document 2, there is a description relating to conductive carbon black as a binder. However, the primary aggregate of carbon black is large, and the primary aggregate lacks when engraving with high definition. There is a problem that a print pattern cannot be obtained. Further, when the composition is thermally cured in the atmosphere, the stickiness of the surface becomes a problem.
When the surface is sticky, there are problems such as difficulty in polishing the printing original plate and an increase in the amount of resin required for polishing. When an electron beam is used as a crosslinking method, not only a crosslinking reaction but also a decomposition reaction occurs, resulting in problems such as a decrease in hardness and bubbles. Therefore, it has been difficult to produce a high-resolution printing master for laser engraving.

From the above, the surface stickiness after curing is reduced, and in consideration of environmental friendliness, a resin-made printing original plate that can be engraved with a laser that does not require a solvent in the plate-making process, and also a high-resolution engraving with a near-infrared laser There is a need for the development of possible resin printing masters.
That is, the present invention provides a high-resolution printing original plate for laser engraving and a printing plate that have less surface stickiness and can form uneven portions by near infrared laser engraving in consideration of environmental compatibility. Furthermore, the present invention also provides a resin composition suitable for producing the printing original plate.

  As a result of intensive studies on the resin composition in order to solve the above problems, the present inventors have found that a resin having a number average molecular weight of 300 to 300,000 (a) and having two or more thiol groups in one molecule. The above problems can be solved by using a laser engraving printing original plate obtained by thermosetting a resin layer comprising a resin composition containing a functional thiol compound (b), a laser absorber (c), and a thermal polymerization initiator (d). As a result, the present invention was completed.

That is, the present invention is as follows.
[1]
Polyfunctional thiol having two or more polymerizable functional groups in one molecule and at least one of the functional groups being a thiol group with respect to 100 parts by mass of the resin (a) having a number average molecular weight of 300 to 300,000 A resin layer comprising a resin composition containing 0.1 to 150 parts by mass of the compound (b), 1 to 100 parts by mass of the laser absorber (c), and 0.1 to 10 parts by mass of the thermal polymerization initiator (d). Printing master plate for laser engraving obtained by heat curing.
[2]
2. The printing original plate for laser engraving according to item 1, wherein the polyfunctional thiol compound (b) is a thioglycolic acid derivative and / or a mercaptopropionic acid derivative.
[3]
3. The printing original plate for laser engraving according to item 1 or 2, wherein the resin composition further comprises 1 to 300 parts by mass of a monomer (e) having a polymerizable unsaturated group and a number average molecular weight of 10,000 or less.
[4]
The printing original plate for laser engraving according to any one of the preceding items 1 to 3, wherein the resin composition further comprises 0.01 to 10 parts by mass of a stabilizer.
[5]
(A) The printing original plate for laser engraving as described in any one of 1 to 4 above, wherein the component has a urethane bond and / or an ester bond.
[6]
(D) The printing original plate for laser engraving as described in any one of 1 to 5 above, wherein the component is an organic peroxide.
[7]
8. The printing original plate for laser engraving as described in any one of 1 to 7 above, wherein the center line average roughness Ra of the surface of the printing original plate is from 0.01 μm to 0.4 μm.
[8]
A printing plate obtained by engraving the laser engraving printing original plate according to any one of the preceding items 1 to 7 with a laser having a wavelength of 2 μm or less.
[9]
Polyfunctional having two or more polymerizable functional groups in one molecule and at least one of the functional groups is a thiol group with respect to 100 parts by mass of the resin (a) having a number average molecular weight of 300 to 300,000 Resin composition for printing original plate containing 0.1 to 150 parts by mass of thiol compound (b), 1 to 100 parts by mass of laser absorber (c), and 0.1 to 10 parts by mass of thermal polymerization initiator (d). .
[10]
10. The resin composition for printing original plate as described in 9 above, wherein the resin composition further contains 1 to 300 parts by mass of a monomer (e) having a polymerizable unsaturated group and a number average molecular weight of 10,000 or less.
[11]
11. The resin composition for a printing original plate as described in 9 or 10 above, wherein the resin composition further comprises 0.01 to 10 parts by mass of a stabilizer.
[12]
(A) The resin composition for printing original plates as described in any one of 9 to 11 above, wherein the component has a urethane bond and / or an ester bond.
[13]
13. The resin composition for a printing original plate as described in any one of 9 to 12 above, wherein the component (d) is an organic peroxide.
[14]
Forming a resin layer by applying the resin composition according to any one of the preceding items 9 to 13 to a thickness of 50 μm or more and less than 7 mm on a cylindrical support, and molding into the cylindrical shape And a step of heating and curing the formed resin layer.
[15]
15. The method for producing a printing plate precursor for laser engraving according to 14 above, further comprising a step of adjusting the surface roughness after the step of heating and curing.
[16]
16. The method for producing a printing plate precursor for laser engraving according to item 15 above, wherein the step of adjusting the surface roughness includes at least one step selected from the group consisting of cutting, grinding, and polishing.
[17]
A method for producing a printing plate comprising a step of engraving the printing plate precursor for laser engraving according to any one of items 1 to 7 with a laser having an oscillation wavelength of 2 μm or less.

  According to the present invention, it is possible to provide a printing original plate and a printing plate that have less surface stickiness and can form an uneven portion by near infrared laser engraving, and a resin composition suitable for their production.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
[Resin composition]
In the resin composition of the present embodiment, the resin (a) having a number average molecular weight of 300 to 300,000 has two or more polymerizable functional groups in one molecule, and at least one of the functional groups is a thiol group. At least one of each component of the polyfunctional thiol compound (b), the laser absorber (c), and the thermal polymerization initiator (d).

[Resin (a)]
The resin (a) of the present embodiment is a resin having a number average molecular weight of 300 to 300,000, preferably 500 to 200,000, more preferably 1000 to 100,000. The number average molecular weight is 300 or more because the strength of the printing original plate and the printing plate is improved and it tends to withstand repeated use. On the other hand, the viscosity at the time of molding of the resin composition does not increase excessively, and is 300,000 or less because it tends to easily produce a printed body in a cylindrical shape at a temperature at which thermal polymerization initiation reaction does not occur. . The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

  In addition, when the resin (a) is cured by heat, it may not be necessary to have a polymerizable unsaturated group in the molecule, but it is preferable to have a polymerizable unsaturated group in the molecule. It is preferable to have 0.3 or more polymerizable unsaturated groups on an average per molecule. When it has an average of 0.3 or more polymerizable unsaturated groups per molecule, it is preferable because the mechanical strength of the printing original plate and the printing plate is improved and the durability tends to be good. In consideration of the mechanical strength of the printing original plate and the printing plate, the number of polymerizable unsaturated groups in the resin (a) is more preferably 0.5 or more, more preferably 0.7 or more per molecule. The number of polymerizable unsaturated groups in the resin (a) is 2 or less per molecule from the viewpoint of improving the mechanical properties of the cured resin and simplifying the process of adding polymerizable unsaturated groups. preferable. Here, the “polymerizable unsaturated group” means a polymerizable functional group involved in radical polymerization reaction or addition polymerization reaction. The position of the polymerizable unsaturated group is preferably directly bonded to the polymer main chain, the end of the polymer side chain, or the polymer main chain or side chain. The average number of polymerizable unsaturated groups contained in one molecule of the resin (a) can be determined by a molecular structure analysis method using a nuclear magnetic resonance spectrum method (NMR method).

  Specific examples of the resin (a) include polyolefins such as polyethylene and polypropylene, polydienes such as polybutadiene and polyisoprene, polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride, polystyrene, polyacrylonitrile, and polyvinyl alcohol. In addition to C-C chain polymers such as polyvinyl acetate, polyvinyl acetal, polyacrylic acid, poly (meth) acrylic esters, poly (meth) acrylamide, and polyvinyl ether, polyethers such as polyphenylene ether, polyethylene terephthalate , Polymers having a hetero atom in the main chain, such as polycarbonate, polyacetal, polyurethane, polyamide, polyurea and polyimide. As the resin (a), one type or two or more types of polymers can be used. As a form in the case of using a plurality of polymers, either a copolymer or a blend may be used.

Furthermore, the resin (a) preferably has at least one bond selected from the group consisting of a carbonate bond, a urethane bond, and an ester bond in the molecule. It is preferable that the resin (a) has the above bond because the printing plate has a tendency to improve resistance to aromatic hydrogen and ester solvents used in printing.
The method for producing the resin (a) is not particularly limited. For example, the resin (a) has a carbonate bond and an ester bond, and has a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid anhydride group, a ketone group, and a hydrazine residue. A compound having a molecular weight of about several thousand having a plurality of reactive groups such as a group, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, and an alkoxycarbonyl group, and a compound having a plurality of functional groups capable of binding to the reactive group (for example, A polyisocyanate having a hydroxyl group or an amino group, etc.), adjusting the molecular weight, converting the molecular end to a binding group at the molecular end, and the like, and then reacting with the functional group capable of reacting with this terminal binding group and polymerizable unsaturated For example, a method of introducing a polymerizable unsaturated group at the terminal by reacting with an organic compound having a group can be used.

  Examples of the compound having a carbonate bond used in the production of the resin (a) include aliphatic polycarbonates such as 4,6-polyalkylene carbonate diol, 8,9-polyalkylene carbonate diol, and 5,6-polyalkylene carbonate diol. A diol etc. can be mentioned. Moreover, you may use the aliphatic polycarbonate diol which has an aromatic type molecular structure in a molecule | numerator. The terminal hydroxyl groups of these compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, trimethylhexamethylene diisocyanate, p-phenylene diisocyanate, cyclohexylene. Diisocyanate compounds such as diisocyanate, lysine diisocyanate, triphenylmethane diisocyanate, triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-2,4 , 4'-Triisocyanate, etc. By condensation reaction of the cyanate compound, together with introducing a urethane bond may be high molecular weight. Furthermore, a terminal hydroxyl group or isocyanate group can also be used for introducing a polymerizable unsaturated group.

Examples of the compound having an ester bond used in the production of the resin (a) include adipic acid, phthalic acid, malonic acid, succinic acid, itaconic acid, oxalic acid, glutaric acid, pimelic acid, speric acid, azelanic acid, and sebacin. Dicarboxylic acid compounds such as acid, fumaric acid, isophthalic acid, terephthalic acid and the like, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, piconal, cyclopentanediol, cyclohexanediol, etc. Has a hydroxyl group Polyesters obtained a compound with condensation reaction, polyesters such as polycaprolactone and the like. By subjecting a diisocyanate compound to a condensation reaction with the terminal hydroxyl group or carboxyl group of these compounds, a urethane bond can be introduced and the molecular weight can be increased. Furthermore, a terminal hydroxyl group, carboxyl group or isocyanate group can also be used for introducing a polymerizable unsaturated group.
In addition, the resin (a) of the present embodiment is manufactured from a polycarbonate diol composed of a repeating unit represented by the following formula (1) in order to develop excellent solvent resistance with respect to various solvents of the printing original plate. Can do.

(In the formula, R1 represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms, and n represents an integer of 2 to 50.)
In the formula (1), R ₁ represents a linear or branched hydrocarbon group having 2 to 50 carbon atoms. R ₁ may contain an unsaturated bond. R1 preferably has 2 or more carbon atoms from the viewpoints of stability and solvent resistance. When the carbon number of R ₁ is 50 or less, the industrial production of polycarbonate diol can be performed satisfactorily.
In the formula (1), R ₁ may be a single component or a plurality of components. The R _1, the following formula (2)
(CH ₂ ) _x (2)
(In the formula, x represents an integer of 2 to 50.)
The polymethylene group represented by these is preferable, More preferably, x is a polymethylene group of 2-30.

In said Formula (1), n represents the integer of 2-50. It is preferable from the viewpoint of solvent resistance that n is 2 or more. n is preferably 50 or less from the viewpoint of solvent resistance, and the industrial production of polycarbonate diol can be carried out satisfactorily. From the viewpoint of availability and ease of handling, a more preferable range of n is 2 to 30, and a more preferable range is 2 to 12.
The polycarbonate diol is produced from HO— (R ₁ —O) n—H, which is a diol compound corresponding to the formula (1), by a known method (for example, Japanese Patent Publication No. 5-29648). Is possible.
Although it does not restrict | limit especially as said polycarbonate diol, The compound represented by following formula (3) is more preferable.

(In the formula, each R ₁ independently represents a straight chain and / or branched hydrocarbon group having 2 to 50 carbon atoms, n represents each independently an integer of 2 to 50, and a represents 1 (It represents the integer above.)
As a method for producing the resin (a) using the polycarbonate diol, it is preferable to produce the resin (a) with formation of a chemical bond between the terminal hydroxyl group and another compound. The type of chemical bond is not particularly limited, but the chemical bond is preferably a urethane bond.
As the resin (a), the terminal hydroxyl group of the polycarbonate diol is chemically bonded to a polyisocyanate compound, a compound having an isocyanate group such as isocyanatoalkyl acrylate and isocyanatoalkyl methacrylate, and a hydroxyalkyl acrylate and hydroxyalkyl methacrylate. It is preferable that it is a polymer manufactured with, and it is preferable that it is a polymer which has polymerizable unsaturated groups, such as an acryl group and a methacryl group.

A preferred first example of the resin (a) is a polycarbonate diol composed of the repeating unit represented by the formula (1), and a polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, Is a polymer in which the terminal hydroxyl group remaining in the polymerized polycarbonate diol and the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate are bonded by a urethane bond.
In the resin (a) of the first example, the terminal hydroxyl group of the polycarbonate diol is a polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, and an isocyanate alkyl acrylate and / or an isocyanate. It is produced by reacting with alkyl methacrylate.

  The polyisocyanate compound in the present embodiment is not limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, when a diisocyanate compound is illustrated, as an aromatic diisocyanate, , Diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or cycloaliphatic diisocyanate As hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate And the like. Examples of triisocyanate compounds include triphenylmethane triisocyanate and tri (isocyanatophenyl) triphosphate. Examples of polyfunctional polyisocyanate compounds include polymeric (diphenylmethane diisocyanate). From the viewpoint of solvent resistance of the printing plate or printing original plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is more preferable.

The isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol means that the equivalent (mol) of the isocyanate group of the polyisocyanate compound is less than the equivalent (mol) of the terminal hydroxyl group of the polycarbonate diol. The isocyanate group equivalent is not limited as long as it is less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, but is preferably 50 to 95% equivalent of the equivalent of the terminal hydroxyl group of the polycarbonate diol, and preferably 60 to 90% equivalent. It is more preferable.
As the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, for example, a compound in which the alkyl portion in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and an alkylene group having 2 or 3 carbon atoms is preferable. Compounds are more preferred. Specific examples of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate include isocyanatoethyl (meth) acrylate and isocyanatopropyl (meth) acrylate.
Among such polymers (a), a polymer represented by the following formula (4) is preferable because it exhibits extremely excellent solvent resistance.

(In the formula, each R _p independently represents a residue obtained by removing both terminal hydroxyl groups from the polycarbonate diol composed of the repeating unit represented by the formula (1), and R _q represents a diisocyanate compound to an isocyanate. Represents a residue excluding a nate group, R _r represents an alkyl moiety of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, and R _S and R _T each independently represents a methyl group or a hydrogen atom. , L represents an integer of 1 or more.)
A preferred second example of the resin (a) is that a polycarbonate diol composed of the repeating unit represented by the formula (1) and a polyisocyanate compound equivalent to the terminal hydroxyl group of the polycarbonate diol are polymerized by a urethane bond. And a polymer in which the remaining isocyanate group of the polymerized polyisocyanate compound and hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate are bonded by a urethane bond.
The resin (a) of the second example includes a polyisocyanate compound having an isocyanate group equivalent of a terminal hydroxyl group of the polycarbonate diol exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol, and a hydroxyalkyl acrylate and / or a hydroxyalkyl methacrylate. It is manufactured by making it react.

  The polyisocyanate compound in the present embodiment is not limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, when a diisocyanate compound is illustrated, as an aromatic diisocyanate, , Diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or cycloaliphatic diisocyanate As hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate And the like. Examples of triisocyanate compounds include triphenylmethane triisocyanate and tri (isocyanatophenyl) triphosphate. Examples of polyfunctional polyisocyanate compounds include polymeric (diphenylmethane diisocyanate). From the viewpoint of solvent resistance of the printing plate or printing original plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is more preferable.

The isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol means that the equivalent (mol) of the isocyanate group of the polyisocyanate compound exceeds the equivalent (mol) of the terminal hydroxyl group of the polycarbonate diol. The isocyanate group equivalent is not limited as long as it exceeds the equivalent of the terminal hydroxyl group of the polycarbonate diol, but is preferably 105 to 150% equivalent of the equivalent of the terminal hydroxyl group of the polycarbonate diol. More preferably.
As the hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, for example, a compound in which the alkyl moiety in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and a compound having an alkylene group having 2 or 3 carbon atoms is preferable. More preferred. Specific examples of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Among such resins (a), a polymer represented by the following formula (5) is preferable because it exhibits extremely excellent solvent resistance.

(In the formula, each R _p independently represents a residue obtained by removing both terminal hydroxyl groups from the polycarbonate diol composed of the repeating unit represented by the formula (1), and R _q represents a diisocyanate compound to an isocyanate. Represents a residue excluding a nate group, R _u represents an alkyl moiety of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, m Represents an arbitrary integer of 1 or more.)
In the formulas (4) and (5), R _r and R _u are preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, and still more preferably It is an ethylene group or a propylene group, more preferably an ethylene group.

Although it does not restrict | limit especially as a manufacturing method of resin (a), For example, resin (a) can be manufactured with the following methods. The polycarbonate diol, a polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol, and the urethanization catalyst are reacted at 50 to 90 ° C. for 1 to 5 hours. ) A resin (a) can be manufactured by adding an acrylate and a urethanization catalyst and making it react at 50-90 degreeC for 1 to 5 hours.
Moreover, after making the said polycarbonate diol, the isocyanate group equivalent polyisocyanate compound exceeding the equivalent of the terminal hydroxyl group of this polycarbonate diol, and a urethanization catalyst react at 50-90 degreeC for 1 to 5 hours, hydroxyalkyl Resin (a) can be manufactured by adding (meth) acrylate and a urethanization catalyst and making it react at 50-90 degreeC for 1 to 5 hours.

  The resin (a) can contain a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a liquid resin having a glass transition temperature of 0 ° C. or lower. Examples of such a liquid resin include compounds having a hydrocarbon chain such as polyethylene, polybutadiene, hydrogenated polybutadiene, and polyisoprene, polyester compounds having an ester bond such as adipate and polycaprolactone, compounds having an aliphatic polycarbonate structure, Examples thereof include compounds having a polydimethylsiloxane skeleton. In particular, unsaturated polyurethanes having a polycarbonate structure are more preferable from the viewpoint of weather resistance. Liquid resin here means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling. When an external force is applied, the liquid resin is instantly deformed according to the external force. However, it is a term corresponding to an elastomer having the property of recovering its original shape in a short time when external force is removed.

[Polyfunctional thiol compound (b)]
The polyfunctional thiol compound (b) is a polyfunctional thiol compound having two or more polymerizable functional groups in one molecule and at least one of the polymerizable functional groups being a thiol group. In the present embodiment, the polymerizable functional group means a polymerizable functional group such as a hydroxyl group, a carboxyl group, an amino group, a phenolic hydroxyl group, a (meth) acryloyl group, a thiol group, and an epoxy group.
The form of the specific polyfunctional thiol compound (b) is not particularly limited. For example, a compound having two or more polymerizable functional groups in which a thiol group is bonded to an alkyl group, or a thioglycol having two or more polymerizable functional groups Examples include acid derivatives and mercaptopropionic acid derivatives having two or more polymerizable functional groups. A thioglycolic acid derivative or a mercaptopropionic acid derivative is obtained by esterifying an arbitrary polyol with thioglycolic acid or mercaptopropionic acid to obtain polyfunctional thiol compounds having various structures. Further, although not particularly limited, the valence (number of thiol groups per molecule) of the polyfunctional thiol compound (b) is preferably 2 or more and more preferably 3 or more from the viewpoint of surface curability.

The molecular weight of the polyfunctional thiol compound (b) is from the viewpoint that the compatibility with the resin (a) is good, and from the viewpoint that the viscosity at the time of resin processing does not increase excessively and cylindrical molding is easy. Preferably it is 10,000 or less, More preferably, it is 1000 or less. The molecular weight referred to here is a value calculated from the molecular structural formula.
A specific example of the polyfunctional thiol compound (b) used in the present invention is not particularly limited as long as it has two or more functional groups in one molecule and at least one of the functional groups is a thiol group.
Thioglycolic acid, ammonium thioglycolate, monoethanolamine thioglycolate, 3-mercaptopropionic acid, methoxybutyl mercaptopropionate, thiomalic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, thiodiglycol, thioglycero- 2-amino-3-mercapto-1-propanol, 4,6-diaminopyrimidine-2-thiol, 2-amino-3-mercaptopropionic acid, 4-aminothiophenol, 3-amino -N- (2-mercaptoethyl) propionamide, 6-amino-2-thiouracil, 2-amino-4-chlorobenzenethiol, 1-amino-2-methyl-2-mercaptopropane-1-carboxylic acid, etc. Two or more polymerizable functional groups, and one of the polymerizable functional groups is thio Compound is a group,

  1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, , 9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3-dimercaptosuccinic acid, 1,2-benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedithiol 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 3,4-dimercaptotoluene, o-, m- or p-xylenedithiol, 4-chloro-1,3-benzenedithiol, 2 , 4,6-trimethyl-1,3-benzenedimethanethiol, 4,4'-thiodiphenol, -Hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino-4,6-dimercapto-1,3,5-triazine, 2-cyclohexylamino-4,6-dimercapto-1,3 , 5-triazine, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, ethylene glycol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis Thioglycolate, ethylene glycol bisthiopropionate, butanediol bisthiopropionate, hexanediol bisthioglycolate, 2,5-dimercapto-1,3,4-thiadiazole, 2,2 ′-(ethylenedithio) Diethanethiol, 2,2-bis (2-hydroxy-3-mercapto (Ropoxyphenylpropane), 1,4-bis (3-mercaptobutyryloxy) butane, 2- (dimethylamino) -1,3-propanebisthiol, 1,3-dimercapto-2-propanol, 2,3- A compound having two or more polymerizable functional groups such as dimercapto-1-propanol and 2,5-diamino-1,4-benzenedithiol, and two of the polymerizable functional groups being a thiol group,

1,2,6-hexanetriol trithioglycolate, 1,3,5-trithiocyanuric acid, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4 , 6, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trihydroxyethyl triisocyanuric acid tristhiopropionate, tris [ 3-mercaptopropionyloxy) -ethyl] isocyanurate and other compounds having three or more polymerizable functional groups, and three of the polymerizable functional groups are thiol groups,
Four or more polymerizable functional groups such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, dipentaerythritol hexakis-3-mercaptopropionate Examples thereof include, but are not limited to, compounds having a group and four or more of the polymerizable functional groups being a thiol group.

These polyfunctional thiol compounds (b) include commercially available ethylene glycol bisthiopropionate (EGTG) (trademark), trimethylolpropane tristhiopropionate (TMTG) (trademark), pentaerythritol tetrakisthiol. Propionate (PETG) (trademark) (all manufactured by Sakai Chemical Co., Ltd.), 1,4-bis (3-mercaptobutyryloxy) butane (Karenz MT BD1) (trademark), pentaerythritol tetrakis (3-mercapto Butyrate) (Karenz MT PE1) (trademark), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion (Karenzu MT NR1) (trademark) (both made by Showa Denko KK)
Trimethylolpropane tris-3-mercaptopropionate (TMMP) (trademark), pentaerythritol tetrakis-3-mercaptopropionate (PEMP) (trademark), dipentaerythritol hexakis-3-mercaptopropionate (DPMP) ( Trademark), tris-[(ethyl-3-mercaptopropionyloxy) -ethyl] isocyanurate (TEMPIC) (trademark) (both manufactured by Sakai Chemical Industry Co., Ltd.), etc., but the polyfunctional thiol compound (b) of the present invention Is not limited.

The content of the polyfunctional thiol compound (b) is 0.1 parts by mass or more and 150 parts by mass or less, preferably 0.2 parts by mass or more and 100 parts by mass or less, particularly 100 parts by mass of the resin (a). Preferably, 0.5 part by mass or more and 50 parts by mass or less are preferable.
When the polyfunctional thiol compound (b) is 0.1 part by mass or more, a cured resin product having excellent surface curability and less surface tack tends to be obtained, and when it is 100 parts by mass or less, storage stability is obtained. A good resin composition tends to be obtained.

[Laser Absorber (c)]
The resin composition of the present embodiment contains a laser absorber (c). In general, an organic compound has a low absorbance corresponding to a laser wavelength in the near infrared region. Therefore, in order to produce a printing original plate with a laser having a wavelength in the near infrared region, a laser absorbent having absorption in the laser wavelength region is required. The laser absorber is not particularly limited as long as it has absorption in the wavelength region, but preferable examples include dyes that absorb strongly in the far infrared spectral region, such as phthalocyanine, naphthalocyanine, cyanine, quinone, metal Complex dyes such as dithiolenes or photochromic dyes. Another suitable laser absorber is an inorganic pigment, particularly a darkly colored inorganic pigment, for example, a carbon material such as chromium oxide, iron oxide, carbon black, carbon nanotube, fullerene, or metal particles. Carbon black is particularly preferred as a laser absorber because of its light absorbency to laser and ease of handling. Moreover, it is described in patent document GB2071574A etc. that carbon black reduces the engraving threshold value at the time of laser engraving.

The average primary particle size of carbon black (c) is preferably 45 nm to 70 nm, more preferably 45 nm to 68 nm. It is 45 nm or more from the viewpoint of dispersibility in the resin composition, and is 70 nm or less from the viewpoint of high-resolution laser engraving. The DBP oil absorption of carbon black (c) is preferably greater than 45 mL / 100 g and less than 150 mL / 100 g, more preferably greater than 45 mL / 100 g and less than 130 mL / 100 g. From the viewpoint of dispersibility in the resin, it is 50 mL / 100 g or more, and from the viewpoint of high-resolution laser engraving, it is 130 mL / 100 g or less.
The pH of the carbon black is preferably 5 or less, more preferably 4 or less from the viewpoint of dispersibility. Setting the pH within the above range is more from the viewpoint of realizing a printing original plate that can further reduce the aggregation of carbon black, can efficiently absorb laser light even with a small amount of carbon black, and can be easily photocured. Is preferred.

The “average primary particle size”, “DBP oil absorption”, and “pH” in the present embodiment can be measured according to the measurement methods in the examples described later.
In the resin composition of the present embodiment, the content of the component (c) is not particularly limited, but is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 100 parts by mass of the resin (a). 3 parts by mass or more and 80 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less. 1 mass part or more is preferable from a viewpoint of laser engraving property. From the viewpoint of production efficiency of the printing original plate, 100 parts by mass or less is preferable. At this time, the component (c) may be used alone or in combination of two or more.

[Thermal polymerization initiator (d)]
In the present embodiment, in order to obtain a printing original plate for laser engraving, the resin layer is thermally cured by a thermal polymerization initiator (d) contained in the resin layer made of the resin composition. Although content in particular of the thermal-polymerization initiator (d) in a resin composition is not restrict | limited, 0.1 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of resin (a), More preferably, it is 0.00. 3 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less. If the content rate of a thermal-polymerization initiator (d) is the said range, a resin composition can fully be hardened and it becomes possible to form the thermosetting material excellent in mechanical strength.
From the viewpoint of keeping a wide temperature range during the molding process, the thermal polymerization initiator (d) preferably has high thermal stability. The thermal stability of the thermal polymerization initiator (d) is usually determined by the method with a 10 hour half-life temperature of 10 h-t1 / 2, ie 50% of the initial amount of thermal polymerization initiator (d) is 10 hours. It is the temperature at which it later decomposes to form free radicals. Further details on this are given in “Encyclopedia of Polymer Science and Engineering”, Vol. 11, page 1 onwards, John Wiley & Sons, New York, 1988.
Particularly suitable thermal polymerization initiators (d) usually have a 10 h-t1 / 2 of preferably at least 60 ° C., more preferably at least 70 ° C. Especially preferably, it is 10 h-t1 / 2 of 80 to 150 degreeC.

  As the thermal polymerization initiator (d), an organic peroxide is particularly preferable from the viewpoint of thermosetting and compatibility with the resin composition. Specific examples of the compound include monoperoxycarbonates such as t-butylperoxy-2-ethylhexyl monocarbonate, peroxyesters such as t-butyl peroctanoate, t-amyl peroctanoate, and peroxyisobutyric acid. t-butyl, t-butyl peroxymaleate, t-amyl perbenzoate, di-t-butyl diperoxyphthalate, t-butyl perbenzoate, t-butyl peracetate and 2,5-di ( Benzoylperoxy) -2,5-dimethylhexane, certain diperoxyketals such as 1,1-di (t-amylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) percyclohexane, 2,2-di (t-butylperoxy) butane and ethyl , 3-di (t-butylperoxy) butyrate, certain dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide and 2,5-di (t- Butylperoxy) -2,5-dimethylhexane, certain diacyl peroxides, such as dibenzoyl peroxide and diacetyl peroxide, certain t-alkyl hydroperoxides, such as t-butyl hydroperoxide, t- Amyl hydroperoxide, pinane hydroperoxide and cumyl hydroperoxide. Moreover, an azo compound can be mentioned as a preferable thing when forming the cushion layer containing a bubble. For example, 1- (t-butylazo) formamide, 2- (t-butylazo) isobutyronitrile, 1- (t-butylazo) cyclohexanecarbonitrile, 2- (t-butylazo) -2-methylbutanenitrile, 2, 2'-azobis (2-acetoxypropane), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutanenitrile), etc. It is a compound of this.

[Monomer (e)]
The resin composition of the present embodiment includes a monomer (e) having a polymerizable unsaturated group and a number average molecular weight of less than 10,000 from the viewpoint of adjusting the viscosity of the resin composition and the hardness of the printing original plate. But it ’s okay. When the resin composition contains the monomer (e), the monomer (e) may be one type, or two or more types may be used in combination. For ease of dilution with the resin (a), the number average molecular weight is preferably less than 10,000, more preferably the number average molecular weight is less than 5000, particularly preferably less than 2000, and is 100 or more from the viewpoint of handling such as low volatility. Is preferred. The definition of a polymerizable unsaturated group is a polymerizable unsaturated group that participates in a radical or addition polymerization reaction as described in the section of the resin (a).

The monomer (e) is a monomer (e) different from (a) having a polymerizable unsaturated group and a number average molecular weight of less than 10,000. In view of ease of dilution with the resin (a), the number average molecular weight of the monomer (e) is less than 10,000, preferably the number average molecular weight is less than 5000, and more preferably less than 2000. Moreover, 100 or more are preferable from a viewpoint of handling, such as low volatility. The definition of a polymerizable unsaturated group is a polymerizable unsaturated group that participates in a radical or addition polymerization reaction as described in the section of the resin (a).
The content of the monomer (e) (the total content when two or more types are used in combination) is preferably 1 part by mass or more and 300 parts by mass or less, more preferably 100 parts by mass of the resin (a). Is 5 parts by weight or more and 250 parts by weight or less, more preferably 10 parts by weight or more and 200 parts by weight or less. When the content of the monomer (e) is 1 part by mass or more, the resin cured product tends to provide sufficient mechanical strength, and when it is 300 parts by mass or less, the curing shrinkage of the resin cured product Is preferable because it tends to be reduced.

  Specific examples of the monomer (e) include radical reactive compounds such as olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, acrylonitrile and the like. Unsaturated nitriles, (meth) acrylamide and derivatives thereof, aryl compounds such as aryl alcohol and aryl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinylpyrrolidone , N-vinylcarbazole and the like. (Meth) acrylic acid and its derivatives are preferable examples from the viewpoints of the abundance of the kind, price, decomposability upon laser light irradiation, and the like. Examples of the derivatives include alicyclic compounds having a cycloalkyl group, a bicycloalkyl group, a cycloalkene group, a bicycloalkene group, an aromatic compound having a benzyl group, a phenyl group, a phenoxy group, a fluorene group, an alkyl group, and a halogenated group. Examples thereof include compounds having an alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, glycidyl group, and the like, and ester compounds with polyhydric alcohols such as alkylene glycol and trimethylolpropane. Specific examples of the derivatives preferably have a (meth) acryloyl group and further an aromatic group from the viewpoint of the strength of the printing plate, the decomposability upon laser irradiation, and the like. Examples thereof include phenoxyethyl acrylate and phenoxyethyl methacrylate.

  In addition, as the compound having an epoxy group that undergoes addition polymerization reaction as the monomer (e), compounds obtained by reacting various diols and polyols such as triol with epichlorohydrin, and peracids in the ethylene bonds in the molecule. An epoxy compound obtained by reacting can be mentioned. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A with ethylene oxide or propylene oxide Epoxy compounds of added compounds such as diglycidyl ether It can be mentioned.

The monomer (e) having a polymerizable unsaturated group is a long-chain aliphatic derivative or alicyclic group from the viewpoint of solvent resistance to an organic solvent such as an aromatic hydrocarbon or an ester which is a solvent for printing ink. It is preferable to have at least one derivative selected from the group consisting of derivatives and aromatic derivatives.
The monomer (e) has at least one bond selected from the group consisting of a carbonate bond, an ester bond and an ether bond in the molecular chain and / or an aliphatic saturated hydrocarbon from the viewpoint of solvent resistance. A compound having at least one molecular chain selected from the group consisting of a chain and an aliphatic unsaturated hydrocarbon chain and having a urethane bond is preferable.

[Fine particles]
Further, fine particles such as inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be added to the resin composition of the present embodiment. Addition of these fine particles improves the mechanical properties of the cured resin obtained by thermosetting, improves the wettability of the surface of the cured resin, or adjusts the viscosity of the resin composition, and improves the viscoelastic properties of the cured resin. Adjustment and the like are possible. The material of the inorganic fine particles or organic fine particles is not particularly limited, and known materials can be used. Examples of the organic / inorganic composite fine particles include fine particles in which an organic layer or organic fine particles are formed on the surface of inorganic fine particles, or fine particles in which an inorganic layer or inorganic fine particles are formed on the surface of organic fine particles.

For the purpose of improving the mechanical properties of the cured resin, inorganic fine particles having high rigidity such as silicon nitride, boron nitride, and silicon carbide, or organic fine particles such as polyimide can be used. Further, for the purpose of improving the solvent resistance of the obtained resin cured product, inorganic fine particles and organic fine particles formed of a material having a good swelling property in the solvent to be used can be added.
In addition, for the purpose of forming a pattern that penetrates the surface of the cured resin layer or the cured resin by the laser engraving method, the number average particle diameter that is excellent in the adsorption removal property of the viscous liquid residue generated at the time of laser engraving is 5 nm or more. You may add the porous fine particle of 10 micrometers or less, or the nonporous fine particle whose number average particle diameter of a primary particle is 5 nm or more and 100 nm or less. Although not particularly limited, for example, porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, porous glass and the like can be mentioned.

The particle shape of the fine particles is not particularly limited, and spherical, flat, needle-like, amorphous, or particles having protrusions on the surface can be used. In particular, spherical particles are preferable from the viewpoint of wear resistance.
Further, the surface of the fine particles can be coated with a silane coupling agent, a titanium coupling agent, or other monomer (e) and subjected to a surface modification treatment to make the particles more hydrophilic or hydrophobic. These fine particles can be selected from one type or two or more types.
Although it does not specifically limit when using microparticles | fine-particles for a resin composition, 1-100 mass parts is preferable with respect to 100 mass parts of resin (a), and the range of 2-50 mass parts is more preferable. A more preferable range is 2 to 20 parts by mass.

[Stabilizer]
As the stabilizer, those usually used in the field of resin materials or rubber materials can be added to the resin composition of the present embodiment. Specific examples thereof include phenolic antioxidants and phosphite antioxidants.
Specific examples of phenolic antioxidants include vitamin E, tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane, 2,5-di- t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6 t-butylphenol), octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis- (6-t-butylphenol), 2-t-butyl -6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, pentaerythritol tetrakis (3-laurylthiopropionate), pentae Thritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,6-di- (t-butyl) -4-methylphenol, 2,2′-methylenebis- ( 6-t-butyl-p-cresol), 1,3,5-tris (3,5-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, and the like.

  Specific examples of the phosphite antioxidant include 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and tris (2,4-di-t-butylphenyl) phosphine. Phyto, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2-ethylhexyl) phosphite, trisdecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite Phyto, didecyl monophenyl phosphite, diphenyl mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) Intererythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyl diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-3-methylphenyl) pentaerythritol diphosphite, and the following formula (1 Phosphite compounds represented by (4) to (4).

These antioxidants may be used alone or in combination of two or more. In particular, the combined use of a hindered phenol antioxidant and a phosphorus antioxidant is preferred.
Although it does not specifically limit when using a stabilizer for a resin composition, 0.01-10 mass parts is preferable with respect to 100 mass parts of resin (a), and the range of 0.05-7.5 mass parts is more preferable. A more preferable range is 0.1 to 5 parts by mass.

[Other additives]
As other additives, an ultraviolet absorber, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the resin composition according to the use and purpose.
Although it does not specifically limit when using another additive for a resin composition, 0.1-20 mass parts is preferable with respect to 100 mass parts of resin (a), and the range of 0.5-15 mass parts is more preferable. A more preferable range is 1 to 10 parts by mass.

[Viscosity of composition]
The viscosity of the resin composition of the present embodiment is not particularly limited, but is preferably 10 Pa · s or more and 10 kPa · s or less at 50 ° C. More preferably, it is 50 Pa · s or more and 5 kPa · s or less at 50 ° C. If the viscosity is 10 Pa · s or higher at 50 ° C., the mechanical strength of the produced printing original plate is sufficient, and it is easy to maintain the shape even when the resin composition is formed into a cylindrical shape and easy to process. . If the viscosity is 10 kPa · s or less at 50 ° C., it is easily deformed and processed easily. . In particular, in order to obtain a printing original plate having high thickness accuracy, the viscosity of the resin composition is 10 Pa · s or more, more preferably 20 Pa · s or more, more preferably 20 Pa · s or more at 50 ° C. so that the resin composition does not cause a phenomenon such as liquid dripping due to gravity. Is desirably a resin composition of 50 Pa · s or more.

[Molding method]
The laser engraving printing original plate obtained from the resin composition for laser engraving original plate according to the present embodiment comprises (i) a step of applying the resin composition on a sheet-like or cylindrical support to form a resin layer, (ii) It is preferably obtained by a method including a step of thermosetting the formed resin layer.
In the step (i), it is preferable not to use a solvent from the viewpoint of being environmentally friendly, simplifying the coating process, and forming a resin layer having no bubbles in the resin.
As a method of applying the resin composition in a sheet shape or a cylindrical shape, an existing resin application method can be used. For example, a casting method, a method of spraying resin using a spray, such as a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, adjusting the thickness by calendaring with a roll, etc. it can. In that case, it is also possible to perform the molding while heating the resin composition within a range that does not cause a reaction. Moreover, you may perform a rolling process, a grinding process, etc. as needed.

At this time, the thickness of the resin composition is preferably 50 μm or more and less than 7 mm. When the thickness is 50 μm or more and less than 7 mm, a pattern having a large unevenness can be obtained during laser engraving. When printing using a printing plate with large irregularities, a large amount of ink can be received and transferred if it is an intaglio plate, the solid density increases, and if it is a relief plate, a printed matter with less filling of white lines can be obtained. .
In gravure printing, there is a step of copper plating on the metallic cylinder after the polishing treatment, and then engraving and hard chrome plating treatment are performed. In the present embodiment, the resin may be applied directly on the metal cylinder, or the resin may be applied after performing copper plating or hard chrome plating.

  Moreover, it is also preferable to apply | coat on the sheet-like support body which consists of raw materials, such as PET and nickel, and to apply | coat directly to a cylindrical support body (sleeve). The cylindrical support is preferably a cylindrical support having at least one material selected from fiber reinforced plastic, film reinforced plastic, metal, and rubber as a constituent component. Specific examples include cylindrical supports such as polyester resins reinforced with fibers such as glass fibers, aramid fibers, and carbon fibers, plastic sleeves such as epoxy resins, and polyester tubes such as polyethylene terephthalate. The cylindrical support is preferably hollow from the viewpoint of weight reduction of the printing plate and ease of handling. The role of the sheet-like support or the cylindrical support is to ensure the dimensional stability of the cured resin. Therefore, it is preferable to select one having high dimensional stability. When evaluated using the linear thermal expansion coefficient, the upper limit value of a preferable material is 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less. Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used.

  Moreover, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as the sheet-like support. When a porous sheet is used as the sheet-like support, high adhesion is obtained because the resin cured product layer and the sheet-like support are integrated by thermosetting after impregnating the resin composition into the pores. be able to. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples thereof include semi-synthetic fibers such as fibers, rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. Further, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material capable of producing a thin nonwoven fabric with high dimensional stability.

In the step (ii), the dimensional stability of the sheet-like support or the cylindrical support, or the liquid dripping in the gravity direction by rotating the cylindrical support when the resin composition is applied on the cylindrical support. It is preferable to have the process heated to 80 to 250 degreeC from a viewpoint which can suppress effectively. More preferably, they are 80 degreeC or more and 200 degrees C or less, More preferably, they are 100 degreeC or more and 150 degrees C or less. These temperatures are the temperatures of the resin layer surface.
In the step (ii), the method for heating the resin layer is at least selected from a method of irradiating with hot rays, a method of blowing hot air, a method of being exposed to an atmosphere in which hot air is convected, and a method of contacting with a heated roll. It is preferred to use one type of method. In particular, from the viewpoint of ease of workability, a method of irradiating with heat rays and a method of contacting with a heated roll are preferable. Examples of the heat rays include near infrared rays and infrared rays.
The thickness of the printing original plate obtained by thermosetting the resin composition of the present embodiment may be arbitrarily set in the range of 20 μm or more and 50 mm or less depending on the purpose of use, but when used as a printing original plate Generally, it is in the range of 50 μm or more and 10 mm or less. In some cases, a plurality of materials having different compositions may be stacked.

[Cushion layer]
A cushion layer can also be provided between the printing original plate and the support. The cushion layer plays a role of absorbing an impact caused by vibration in the printing process. The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees, or an ASKER-C hardness of 20 to 85 degrees as measured with an ASKER-C hardness meter. When the Shore A hardness is 10 degrees or more or the ASKER-C hardness is 20 degrees or more, the print quality can be ensured because the film is appropriately deformed. Moreover, if Shore A hardness is 70 degrees or less or ASKER-C hardness is 85 degrees or less, it can serve as a cushion layer. A more preferable range of Shore A hardness is 20 to 60 degrees, and an ASKER-C hardness is 45 to 75 degrees. The Shore A hardness and the ASKER-C hardness are preferably selected depending on the material used for the cushion layer. The difference between the two types of hardness stems from the difference in the shape of the pushers of the hardness meter used for measurement. In the case of a uniform resin composition, Shore A hardness is preferably used, and in the case of a non-uniform resin composition such as a foamable base material such as foamed polyurethane and foamed polyethylene, ASKER-C hardness is preferably used. ASKER-C hardness is a measurement method based on JIS K7312 standard.

[Solvent resistance]
In the present embodiment, the solvent resistance was evaluated by the mass change rate defined below. The lower the mass change rate, the harder the solvent erodes into the plate, and the smaller the swelling of the plate by the solvent, the better the solvent resistance. The mass change rate of the printing original plate with respect to toluene is preferably 50% by mass or less, and more preferably 40% by mass or less. In these preferable ranges, swelling of the plate is suppressed during printing, and excellent print quality such as no thickening of characters can be reproduced even in long run printing of several hundred thousand meters.
The rate of mass change is as follows: a test piece having a width of 2 cm, a length of 5 cm, and a thickness of 1 mm is immersed in a toluene solvent at a temperature of 20 ° C. for 24 hours. It is defined in 1).
Mass change rate (%) = [mass after immersion (g) / mass before immersion-1] × 100 (formula 1)

[Surface roughness]
Gravure printing includes a step of scraping ink on a printing plate with a doctor. Therefore, the surface roughness of the printing original plate and the printing plate surface in gravure printing is an important factor in image formation. The center line average roughness Ra on the printing surface side of the printing original plate and the printing plate of the present embodiment is preferably 0.01 μm or more and 0.4 μm or less. More preferably, it is 0.02 μm or more and 0.3 μm or less. Within these preferred ranges, the surface roughness is excellent in the ink scraping property by the doctor, the tone expression of the dots is good, and the ink remaining amount in the non-image area can be reduced to the extent that there is no problem.
Here, the centerline average roughness Ra represents a value obtained by dividing the roughness curve from the centerline and dividing the area obtained by the roughness curve and the centerline by the length L in micrometers (μm). As a method for measuring the surface roughness, the measurement is carried out by a method according to JIS B0651.

[Surface adjustment]
When processing the surface, it is preferable to adjust the surface by at least one method selected from cutting, grinding, and polishing. Although it is possible to process the surface using only the cutting process, it is preferable to perform the polishing process after the cutting process or the grinding process because the surface shape of the printing original plate can be adjusted more precisely.
Processing by cutting the surface of the printing original plate is not particularly limited, and examples thereof include processing with a blade such as a lathe, a drilling machine, a milling machine, a shaper, a planer, and an NC machine tool. Examples of the processing by grinding the surface of the printing original plate include processing by a grindstone. The material of the grinding wheel used for grinding is not particularly limited, but examples thereof include alumina-based and silicon carbide-based materials. Examples of the material of the grindstone include brown alumina, white alumina, light red alumina, and pulverized alumina in the case of alumina, and black silicon carbide and green silicon carbide in the case of silicon carbide.
Regarding the particle size of the abrasive grains of the grinding wheel used for grinding, a grinding wheel of 8 or more and 5000 or less is preferably used. Examples of the main component of the binder for bonding abrasive grains include feldspar soluble viscosity / flux, bakelite artificial resin, sodium silicate flux, natural / artificial rubber / sulfur, shellac natural resin, metal foil, and the like.

The polishing body used for polishing the surface of the printing original plate is not particularly limited, and examples thereof include polishing films such as polishing paper, wrapping films, and mirror films, and polishing wheels.
As a material for the abrasive on the surface of the abrasive paper or the abrasive film, at least one kind of fine particles selected from metals, ceramics, and carbon compounds is preferable. As an example of the metal fine particles, a relatively hard material such as chromium, titanium, nickel, and iron is preferable. Specific examples of ceramics include alumina, silica, silicon nitride, boron nitride, zirconia, zirconium silicate, silicon carbide, and the like. Examples of the material quality of the alumina abrasive grains include brown alumina, pulverized alumina abrasive, light red alumina abrasive, white alumina abrasive, and artificial emery abrasive. Examples of the material quality of the silicon carbide abrasive grains include a black silicon carbide abrasive and a green silicon carbide abrasive. Examples of the carbon compound include compounds such as diamond and graphite. In particular, artificial diamond is preferable as an abrasive. Other abrasive materials include glass-based abrasives such as glass beads, resin-based abrasives such as nylon, polycarbonate, polyester, and methyl metal acrylate, plant-based abrasives such as walnut shell, apricot seed, and peach seed. Can also be used. Furthermore, it is also possible to use a polishing cloth in combination with the above abrasive.

The number average particle size of the abrasive is preferably from 0.1 μm to 100 μm. A more preferable particle size is 3 μm or more and 100 μm or less. More preferably, the particle size is 9 μm or more and 30 μm or less. If it is in the range of 100 μm or less, a printing original plate that can be suitably used for printing evaluation can be easily prepared.
In particular, the number average particle size of the abrasive is preferably 20 μm or less from the viewpoint of improving the ink transfer property to the printing medium and the printing quality by reducing the unevenness of the surface of the obtained printing original plate. On the other hand, the number average particle diameter of the abrasive is preferably 12 μm or less from the viewpoint of shortening the time required for surface processing and improving the productivity of the printing original plate.

As the particle size of the grinding wheel surface, 60 to 3000 is preferably used. The material of the polishing wheel is not particularly limited, and examples thereof include iron, alumina, ceramics, carbon compound, grindstone, wood, brush, felt, cork and the like.
The thickness and material of the support such as abrasive paper or abrasive film are not particularly limited, but the thickness is preferably in the range of 1 μm to 1000 μm. More preferably, they are 10 micrometers or more and 500 micrometers, More preferably, they are 25 micrometers-125 micrometers. If it is in the range of 25 μm or more and 125 μm or less, handling such as winding is easy. The shape of the support is not particularly limited, and examples thereof include rolls, disks, sheets, and belts.

In addition, it is possible to polish the printing original plate surface even with dry polishing without interposing liquid when polishing using the polishing body, but the polishing power, uniformity of the printing original plate surface after polishing, less dust generation, polishing In consideration of the removal of heat generated inside, it is preferable to bring the abrasive into contact with the printing original plate while interposing a liquid. Although it does not specifically limit as a liquid to be used, For example, petroleum, machine oil, an alkaline solution, water etc. are mentioned.
In particular, when water is used as a liquid to be interposed during polishing, the printing original plate is less denatured than when other liquids are used, and the waste liquid can be easily treated.
In this embodiment, as another preferable aspect of the surface adjustment, fine particles having a number average particle diameter of at least about 0.1 μm to 100 μm made of at least one substance selected from metals, ceramics, carbon compounds, etc. The method of making it collide with the surface is also mentioned.
The method for causing the fine particles to collide with the printing original plate is not particularly limited, and examples thereof include sand blast, shot blast, air blast, blower blast and the like. The material of the fine particles is not particularly limited. For example, glass particles such as glass beads, resin particles such as nylon, polycarbonate, polyester, and methyl metal acrylate, walnut shell, apricot seed, and peach seed. And plant-based particles.

[laser]
When engraving with a laser on the surface of the printing original plate to form irregularities and using it as a printing plate, the laser engraving method uses a computer as a digital data for the image to be formed and operates the laser device to create the printing original plate. Create a relief image. Any laser used for laser engraving may be used as long as the cured resin layer includes a wavelength having absorption. In order to carry out engraving at a high speed, a high output is desirable, and an infrared ray or infrared emitting solid laser such as a carbon dioxide laser, a fiber laser, a YAG laser, or a semiconductor laser is preferable. However, it is preferable to use a laser having a laser wavelength of 2 μm or less, such as a fiber laser, in order to obtain a high-resolution engraving plate. In addition, the second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser wavelength-converted to the third or fourth harmonic are It can be ablated by cutting the bonds of organic molecules and is suitable for fine processing. The laser may be continuous irradiation or pulse irradiation.
Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by a high-pressure spray or the like. Alternatively, it may be removed using a method of irradiating high-pressure steam.

[Printed version]
The printing plate of the present embodiment can be obtained by forming irregularities on the surface by engraving the printing original plate with a laser. When a high-resolution print pattern is required, it is preferable to engrave with a laser having an oscillation wavelength of 2 μm or less.
Although the printing plate of this Embodiment is not specifically limited, It can be used for uses, such as gravure printing, flexographic printing, letter press printing, dry offset printing, and rotary screen printing. It can also be used in applications where a printing plate is used as a mold and the surface of the printing plate is brought into contact with a thermoplastic resin, thermosetting resin, or photocurable resin, and the concave pattern on the printing plate surface is transferred. .

[surface treatment]
The printing plate of the present embodiment can reduce the tack of the printing plate or improve the ink wettability by forming a modified layer on the surface after polishing or laser engraving. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, and a diamond-like carbon (DLC) film.

In order to describe the present embodiment in more detail, examples and comparative examples are shown below, but these examples specifically illustrate the description of the present embodiment and the effects obtained thereby. Thus, the present embodiment is not limited at all. Various characteristics in the following examples and comparative examples were measured according to the following methods.
<Measurement method>
(1) Average primary particle size of carbon black The average primary particle size of carbon black was observed with a transmission electron microscope HF-2000 manufactured by Hitachi, Ltd., and the average value of 10 points was averaged. The primary particle size was used. The acceleration voltage of the electron beam was measured at 50 kV.
(2) Measuring method of DBP oil absorption of carbon black It measured according to JISK6217-4: 2001.
(3) Measuring method of pH of carbon black It measured according to JISZ8802-1984.

(4) OH value of polycarbonate diol 12.5 g of acetic anhydride was diluted with 50 ml of pyridine to prepare an acetylating reagent. 1.0 g of the sample was precisely weighed into a 100 ml eggplant flask. After adding 2 ml of acetylating reagent and 4 ml of toluene with a whole pipette, a condenser tube was attached, and the mixture was stirred and heated at 100 ° C. for 1 hour. 1 ml of distilled water was added with a whole pipette, and the mixture was further heated and stirred for 10 minutes.
After cooling for 2 to 3 minutes, 5 ml of ethanol was added, and 2 to 3 drops of 1% phenolphthalein / ethanol solution was added as an indicator, followed by titration with 0.5 mol / l ethanolic potassium hydroxide.
As a blank test, 2 ml of an acetylating reagent, 4 ml of toluene, and 1 ml of distilled water were placed in a 100 ml eggplant flask and heated and stirred for 10 minutes, followed by titration in the same manner. Based on this result, the OH value was calculated using the following formula (i).
OH value (mg-KOH / g) = {(ba) × 28.05 × f} / e (i)
a: Titration volume of sample (ml)
b: Titrate of blank test (ml)
e: Sample mass (g)
f: Factor of titrant

(5) Molecular weight of polycarbonate diol The terminals of the polycarbonate diol in Examples and Comparative Examples were substantially all hydroxyl groups as determined by ¹³ C-NMR (270 MHz). Moreover, when the acid value in polycarbonate diol was measured by the titration with KOH, all of the Examples and Comparative Examples were 0.01 or less.
Therefore, the number average molecular weight of the obtained polymer was determined by the following formula (ii).
Number average molecular weight Mn = 2 / (OH value × 10 ⁻³ /56.11) (ii)
(6) Measurement of viscosity The viscosity of the resin composition was measured at 50 ° C. using a B-type viscometer “B8H type” (trademark) manufactured by Tokyo Keiki Co., Ltd.

(7) Measurement of the number average molecular weight of the resin (a) The average molecular weight of the resin (a) was such that the polydispersity (Mw / Mn) obtained by using the GPC method was greater than 1.1. The number average molecular weight Mn obtained in (1) was adopted. Specifically, the number average molecular weight of the resin (a) was obtained by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC device “HLC-8020” (trademark) manufactured by Tosoh Corporation and a polystyrene-filled column “TSKgel GMHXL” (trademark) manufactured by Tosoh Corporation, the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared, and the injection amount was 10 μl. Further, a resin ultraviolet absorption detector was used as a detector, and light at 254 nm was used as monitor light.

(8) Measurement of the number of polymerizable unsaturated groups The average number of polymerizable unsaturated groups present in the molecule of the resin (a) is determined after removing unreacted low molecular components using a liquid chromatographic method. Molecular structure analysis was performed using a nuclear magnetic resonance spectrum method (NMR method, “Avance 600” (trademark) manufactured by Bruker Biospin). For example, “1.7 functionality” means that the average number of polymerizable unsaturated groups present in the molecule is 1.7.
(9) Stickiness of the surface Stickiness of the surface is sticky when touching the surface of the cured resin before polishing, or after touching, or when the touch mark can be visually confirmed, and stickiness when it cannot be visually confirmed. Rated as none.

(10) Surface tack The surface tack was performed using a tack tester “PCIMA TACKYMETER” manufactured by Toyo Seiki Seisakusho. Tack measurement was performed at 20 ° C. by contacting a smooth portion of a sample piece with a portion of an aluminum ring having a radius of 50 mm and a width of 13 mm, applying a load of 0.5 kg to the aluminum ring and leaving it for 4 seconds. The aluminum ring is pulled up at a constant speed of 30 mm and the resistance force when the aluminum ring is separated from the sample piece is read with a push-pull gauge. The larger the value, the greater the stickiness.
(11) Shore A hardness The Shore A hardness was measured using a trademark “GS-710” manufactured by Teclock Corporation for the cured product before polishing. The weight of the weight used for the measurement was 8 kg. The value of Shore A hardness was read 60 seconds after dropping the weight.

(12) Mass change rate The mass change rate was measured by the following method. The laser engraving printing original plate is cut to a width of 2 cm, a length of 5 cm, and a thickness of 1 mm, a test piece is prepared, the mass of the test piece is measured in advance, and the test piece is placed in a sample bottle and placed in a solvent (toluene). The sample bottle was capped and immersed at a temperature of 20 ° C. for 24 hours. Thereafter, the mass of the test piece was measured again, and the mass change rate was calculated by the following equation (iii).
Mass change rate (%) = [mass after immersion (g) / mass before immersion-1] * 100 (iii)
(13) Surface roughness measurement The surface roughness was measured by using a surface roughness measuring machine “SE500” (trademark) manufactured by Kosaka Laboratory Co., Ltd. as a stylus R2 μm, cutoff λc = 0.8 mm. Centerline average roughness Ra was measured and evaluated under the conditions of a measurement length of 4 mm and a feed rate of 0.5 m / s. The centerline average roughness is expressed in micrometer (μm) by dividing the roughness curve from the centerline and dividing the area obtained by the roughness curve and the centerline by the length L.
(14) Sculpture Depth The sculpture depth was measured using an Olympus microscope “BX-61” (trademark) and the difference between the bottom of the engraved gradation shadow cell and the bank (unengraved part). .

<Manufacturing method>
(1) Molding of resin composition A polyester film (PET) was used as a support for the resin composition. A metal frame (inner width 150 mm * 200 mm) having a thickness of 1 mm was used on PET, and the resin composition heated to 50 ° C. was applied, and further maintained at 50 ° C. * 30 min. Thereafter, the resin composition was held at 140 ° C. * 30 min, the resin composition was cured in a gear oven (in the air), and molded to a thickness of 1.1 mm, to prepare a printing original plate for laser engraving.
(2) Surface adjustment The surface of the printing plate precursor for laser engraving was polished using a polishing wheel No. 3000 to prepare a printing plate precursor for laser engraving having a thickness of 1 mm.
(3) Laser Engraving Laser engraving was performed using a fiber laser engraving machine “Spark 4260” (trademark) (wavelength: 1 μm) manufactured by ESKO. As engraving conditions, the rotation speed of the cylinder is 200 rpm, the laser output is 62.952 W, and the energy is 12. J / cm ² . The engraving image was created with a resolution of 2450 dots per inch and a line number of 175 Lines per inch. For the image, a gradation pattern of cells in gravure printing, fine letters 3pt, 5pt, and 7pt were produced in Mincho.

[Production Example 1]
Regular packing Helipak packing No. 3 was charged in a 500 ml four-necked flask equipped with a distillation tower having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head, and diethylene glycol 214 g (2.01 mol) and ethylene carbonate 186 g (2.12 mol) were charged at 70 ° C. Then, the system was purged with nitrogen, and 0.177 g of tetrabutoxy titanium was added as a catalyst. This flask was heated in an oil bath while extracting a part of the reflux liquid from the fractionation head so that the internal temperature of the flask was 145 to 150 ° C. and the pressure was 2.5 to 3.5 kPa, and the reaction was continued for 22 hours. did. Then, remove the packed distillation column, replace it with a simple distillation apparatus, raise the internal temperature of the flask to 170 ° C., drop the pressure to 0.2 kPa, and distill the diethylene glycol and ethylene carbonate remaining in the flask over 1 hour. Left. Thereafter, the reaction was further continued for 5 hours at an internal temperature of the flask of 170 ° C. and a pressure of 0.1 kPa. By this reaction, 174 g of a liquid polycarbonate diol that was viscous at room temperature was obtained. The polycarbonate diol thus obtained had an OH value of 60.9 (number average molecular weight Mn = 1844).

  A 300 ml separable flask equipped with a stirrer was charged with 65.0 g of this polycarbonate diol and 0.05 g of monobutyl phosphate, and stirred at 80 ° C. for 3 hours to deactivate tetrabutoxytitanium. Thereafter, 4.63 g of tolylene diisocyanate, 0.07 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, and 0.001 g of di-n-butyltin dilaurate were added in a dry air atmosphere. Stir at 80 ° C. for 3 hours. Thereafter, 2.77 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it is confirmed by infrared spectroscopic analysis that the terminal hydroxyl group of the polycarbonate diol is linked by a urethane bond and has a double bond, and the terminal is a methacrylic group (one molecule of polymerizable unsaturated group in the molecule). Resin (Lp-A) having a number average molecular weight of about 7000 was prepared.

[Production Example 2]
Into a 2 L separable flask equipped with a thermometer, a stirrer and a reflux condenser, 1318 g of polycarbonate diol “PCDL T4672” (trademark) (number average molecular weight 2059, OH number 54.5) manufactured by Asahi Kasei Co., Ltd. After adding 8 g and reacting at 80 ° C. for about 3 hours, 52.6 g of 2-methacryloyloxyisocyanate was added, and further reacted for about 3 hours, and the terminal was a methacrylic group (polymerizable non-polymerizable in the molecule). A resin (Lp-B) having a number average molecular weight of about 7000 with an average of about 1.7 saturated groups per molecule) was prepared.

[Example 1]
As a polyfunctional thiol (b), trimethylolpropane tris-3-mercaptopropionate “TMMP” (manufactured by Sakai Chemical Industry Co., Ltd.) with respect to 100 parts by mass of Lp-A obtained from Production Example 1 as the resin (a) (Trademark) (trivalent thiol, molecular weight 399) 25 parts by mass, and further, carbon black “TB # A700F” (trademark) manufactured by Tokai Carbon Co., Ltd. as a laser absorber (c) with respect to 100 parts by mass of resin (a) (average) The primary particle size is 62 nm, the DBP oil absorption is 121 mL / 100 g, 12.5 parts by mass, and 1,1-di (t-butylperoxy) percyclohexane “manufactured by NOF Corporation as a thermal polymerization initiator (d)”. While adding 1.25 parts by mass of Perhexa C-75 (EB) "(trademark) and 1.25 parts by mass of triphenyl phosphate as a stabilizer and stirring at 50 ° C, Under reduced pressure to Pa defoamed to give a viscous liquid composition at room temperature. Further, the resin composition was kneaded for 30 minutes with a Laboplast mill manufactured by Toyo Seiki Co., Ltd. Thereafter, the obtained resin composition was coated, molded, polished, laser engraved, and printed on the support by the above method. The molecular weight of the polyfunctional thiol (b) here is a value calculated from the molecular structural formula. (The same applies hereinafter)

[Example 2]
As polyfunctional thiol (b), trimethylolpropane tris-3-mercaptopropionate “TMMP” (trademark) (trivalent thiol, molecular weight 399) 0.8 parts by mass, monomer (e ) Was used in the same manner as Example 1 except that 18.75 parts by mass of phenoxyethyl methacrylate and 5.45 parts by mass of trimethylolpropane trimethacrylate as another monomer (e) were used.
[Example 3]
As polyfunctional thiol compound (b), 6.25 parts by mass of trimethylolpropane tris-3-mercaptopropionate “TMMP” (trademark) (trivalent thiol, molecular weight 399) manufactured by Sakai Chemical Industry Co., Ltd., monomer ( Example 2 was the same as Example 2 except that only 18.75 parts by mass of phenoxyethyl methacrylate was used.
[Example 4]
As a polyfunctional thiol compound (b), Tris-[(ethyl-3-mercaptopropionyloxy) -ethyl] isocyanurate “TEMPIC” (trademark) (trivalent thiol, number average molecular weight 526) 0 manufactured by Sakai Chemical Industry Co., Ltd. The procedure was the same as Example 2 except that the content was 8 parts by mass.

[Example 5]
As the polyfunctional thiol compound (b), Tris-[(ethyl-3-mercaptopropionyloxy) -ethyl] isocyanurate “TEMPIC” (trademark) (trivalent thiol, number average molecular weight 526) 6 manufactured by Sakai Chemical Industry Co., Ltd. 6 The same procedure as in Example 2 was conducted except that the monomer (e) was only 18.75 parts by mass of phenoxyethyl methacrylate.
[Example 6]
As polyfunctional thiol compound (b), except that it was 0.8 parts by mass of Pentaerythritol Tetrakis-3-mercaptopropionate “PEMP” (trademark) (tetravalent thiol, number average molecular weight 489) manufactured by Sakai Chemical Industry Co., Ltd. Same as Example 2.
[Example 7]
As polyfunctional thiol compound (b), except dipentaerythritol hexakis-3-mercaptopropionate “DPMP” (trademark) (hexavalent thiol, number average molecular weight 783) 0.8 parts by mass manufactured by Sakai Chemical Industry Co., Ltd. Was the same as in Example 2.
[Example 8]
The same procedure as in Example 2 was conducted except that Lp-B obtained in Production Example 2 was used as the resin (a).

[Comparative Example 1]
With respect to 100 parts by mass of Lp-A obtained in Production Example 1 as resin (a), 18.75 parts by mass of phenoxyethyl methacrylate as monomer (e) and trimethylolpropane as another monomer (e) 6.25 parts by mass of trimethacrylate was added, and carbon black “TB # A700F” (trademark) (average primary particle diameter) manufactured by Tokai Carbon Co., Ltd. as a laser absorber (c) with respect to 100 parts by mass of resin (a). 62 nm, DBP oil absorption 121 mL / 100 g) 12.5 parts by mass, 1,1-di (t-butylperoxy) percyclohexane “Perhexa C-75 manufactured by NOF Corporation as a thermal polymerization initiator (d) (EB) "(trademark) 1.25 parts by mass, 1.25 parts by mass of triphenyl phosphate as a stabilizer and stirring at 50 ° C, the pressure was reduced to 13 kPa Te defoamed to give a viscous liquid composition at room temperature. Further, the resin composition was kneaded for 30 minutes with a Laboplast mill manufactured by Toyo Seiki Co., Ltd. Thereafter, the obtained resin composition was coated, molded, laser engraved, and printed on the support by the method described above.
The composition of each of the above examples and comparative examples, the viscosity of the resin composition at 50 ° C., the surface tackiness of the printing original plate, tack, mass change rate, Shore A hardness, centerline average roughness Ra, and engraving depth of the printing plate The measurement results are summarized in Table 1.

  Comparing the results of surface tackiness and tack measurement of Examples and Comparative Examples, it can be seen that the printing original plate of the present invention has an extremely excellent surface tackiness reducing effect.

  The present invention is most suitable for forming relief images for printing plates such as high-definition gravure, flexo, and dry offset by laser engraving. In addition, conductors for electronic components, semiconductors, insulators, pattern formation, antireflection films for optical components, color filters, pattern formation of functional materials such as (near) infrared cut filters, and liquid crystal displays or organic electroluminescence displays Ideal as a cylindrical printing plate that can be used as a laser-engravable printing plate suitable for forming coating films and patterns for alignment films, underlayers, light-emitting layers, electron transport layers, and sealing material layers is there.

Claims (17)

  Polyfunctional thiol having two or more polymerizable functional groups in one molecule and at least one of the functional groups being a thiol group with respect to 100 parts by mass of the resin (a) having a number average molecular weight of 300 to 300,000 A resin layer comprising a resin composition containing 0.1 to 150 parts by mass of the compound (b), 1 to 100 parts by mass of the laser absorber (c), and 0.1 to 10 parts by mass of the thermal polymerization initiator (d). Printing master plate for laser engraving obtained by heat curing.   The printing original plate for laser engraving according to claim 1, wherein the polyfunctional thiol compound (b) is a thioglycolic acid derivative and / or a mercaptopropionic acid derivative.   The printing original plate for laser engraving according to claim 1 or 2, wherein the resin composition further comprises 1 to 300 parts by mass of a monomer (e) having a polymerizable unsaturated group and a number average molecular weight of 10,000 or less.   The printing original plate for laser engraving according to claim 1, wherein the resin composition further comprises 0.01 to 10 parts by mass of a stabilizer.   The printing original plate for laser engraving according to claim 1, wherein the component (a) has a urethane bond and / or an ester bond.   (D) A component is an organic peroxide, The printing original plate for laser engravings as described in any one of Claims 1-5.   The printing original plate for laser engraving according to any one of claims 1 to 7, wherein the center line average roughness Ra of the surface of the printing original plate is 0.01 µm or more and 0.4 µm or less.   A printing plate obtained by engraving the printing plate precursor for laser engraving according to any one of claims 1 to 7 with a laser having a wavelength of 2 µm or less.   Polyfunctional having two or more polymerizable functional groups in one molecule and at least one of the functional groups is a thiol group with respect to 100 parts by mass of the resin (a) having a number average molecular weight of 300 to 300,000 Resin composition for printing original plate containing 0.1 to 150 parts by mass of thiol compound (b), 1 to 100 parts by mass of laser absorber (c), and 0.1 to 10 parts by mass of thermal polymerization initiator (d). .   The resin composition for printing original plates according to claim 9, wherein the resin composition further comprises 1 to 300 parts by mass of a monomer (e) having a polymerizable unsaturated group and a number average molecular weight of 10,000 or less.   The resin composition for printing original plate according to claim 9 or 10, wherein the resin composition further comprises 0.01 to 10 parts by mass of a stabilizer.   The resin composition for printing original plate as described in any one of Claims 9-11 in which (a) component has a urethane bond and / or an ester bond.   The resin composition for a printing original plate according to any one of claims 9 to 12, wherein the component (d) is an organic peroxide.   Applying the resin composition according to any one of claims 9 to 13 on a cylindrical support so as to have a thickness of 50 μm or more and less than 7 mm, and molding a resin layer; The manufacturing method of the printing original plate for laser engravings including the process of heating and hardening the shape | molded resin layer.   The method for producing a printing plate precursor for laser engraving according to claim 14, further comprising a step of adjusting the surface roughness after the step of heating and curing.   The method for producing a printing plate precursor for laser engraving according to claim 15, wherein the step of adjusting the surface roughness includes at least one step selected from the group consisting of cutting, grinding, and polishing.   The manufacturing method of a printing plate including the process of engraving the printing original plate for laser engraving as described in any one of Claims 1-7 with a laser with an oscillation wavelength of 2 micrometers or less.