JP2011032378A - Polycarbonate diol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate diol composition and a polymer that are excellent in solvent resistance against such organic solvents as ethyl acetate etc. used in the field of general printing and as anisole and methyl benzoate, etc. used in the field of electronic material, and are suitable for a printing plate or a printing original plate suitable for resin printing, and are suitable also for producing the printing plates. <P>SOLUTION: The polycarbonate diol composition comprises a polycarbonate diol (a1), and the polycarbonate diol (a1) is represented by formula (1) and has a number average molecular weight of 100-50,000, wherein R<SB>1</SB>are each independently a 3-50C linear, branched and/or cyclic hydrocarbon group that may contain in the carbon skeleton at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polycarbonate diol composition, a polymer, a printing plate or a curable resin composition for a printing plate, a printing plate, a printing plate, a printing plate production method, and a printing plate production method.

  In recent years, resin printing plates are often used in the general printing field. In particular, a flexographic printing plate characterized by using a flexible printing plate, and in flexographic printing whose specific gravity is increasing among various printing methods, a resin printing plate is exclusively used. The ink often contains an organic solvent.

  Further, as a pattern forming method in the field of electronic materials, a direct printing method, which is a method of printing an electronic material as ink, has attracted attention. Among various printing methods, flexographic printing is letterpress printing, and therefore, it is expected to be particularly suitable for the direct printing method because it is non-contact except for the printed portion and high-definition printing is possible. In the direct printing method, various organic solvents are used in order to dissolve the material into ink.

  However, in the case of a resin printing plate, durability against organic solvents is often insufficient, printing accuracy is insufficient, durability of the printing plate itself is insufficient, or organic solvents that can be used for ink are limited. Problems arise. This is because the resin printing plate swells with an organic solvent, and the dimensions change, the mechanical strength decreases, or cracks and breakage occur. Therefore, excellent solvent resistance against various solvents is desired for resin printing plates and printing original plates.

By the way, it is already known that a polymer produced from polycarbonate diol can be applied to a resin composition for producing a printing original plate.
For example, Patent Document 1 discloses a curable resin composition for a printing original plate and a printing original plate, which can be engraved with a laser, comprising a resin produced from polycarbonate diol and inorganic fine particles.
Patent Document 2 discloses a solvent-resistant photosensitive resin composition for a printing original plate and a printing original plate.

International Publication No. 2003/022594 Pamphlet International Publication No. 2008/078699 Pamphlet

At present, a printing plate and a printing original plate having further excellent solvent resistance with respect to the organic solvent contained in the ink are desired.
The problem to be solved by the present invention is excellent in solvent resistance to organic solvents such as ethyl acetate used in the general printing field, and organic solvents such as anisole and methyl benzoate used in the field of electronic materials, and is suitable for resin printing. It is to provide a suitable printing plate or printing original plate, and to provide a polycarbonate diol composition and a polymer suitable for their production.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a printing plate and a printing original plate obtained by using a polycarbonate diol composition containing a polycarbonate diol having a specific structure and a monomer as a raw material. Was found to exhibit excellent durability against various solvents used in inks and the like, and the present invention was completed.

That is, the present invention is as follows.
[1]
A polycarbonate diol composition comprising a polycarbonate diol (a1) and a monomer (a2),
The polycarbonate diol (a1) is a polycarbonate diol represented by the following formula (1) and having a number average molecular weight of 100 to 50,000,
Formula (1):

(In the formula, each R ₁ is independently a straight chain having 3 to 50 carbon atoms, which may contain at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton; Represents a branched and / or cyclic hydrocarbon group.)
The monomer (a2) is a monomer having a number average molecular weight of 60 to 600 represented by the following formula (2):
Formula (2):

(In the formula, each R ₂ is independently a straight chain having 1 to 50 carbon atoms which may contain at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, Represents a branched chain and / or a cyclic hydrocarbon group, and each X independently represents a group containing active hydrogen.)
A polycarbonate diol composition having a number average molecular weight of 60 to 1,000.
[2]
The polycarbonate diol composition according to [1], wherein R ₁ contains at least one ether bond.
[3]
The polycarbonate diol composition according to [1] or [2], wherein R ₁ is a group derived from diethylene glycol.
[4]
The polycarbonate diol composition according to any one of [1] to [3] and a polyisocyanate compound (b) having an isocyanate group equivalent less than the equivalent of the terminal group of the polycarbonate diol composition are polymerized,
A polymer in which the remaining terminal group of the polymerized polycarbonate diol composition is bonded to isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate.
[5]
The polycarbonate diol composition according to any one of [1] to [3] and an isocyanate group equivalent polyisocyanate compound (b) exceeding the equivalent of the terminal group of the polycarbonate diol composition are polymerized,
A polymer in which a remaining isocyanate group of the polymerized polyisocyanate compound (b) is bonded to a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate by a urethane bond.
[6]
The polymer according to [4] or [5], wherein the polyisocyanate compound (b) is a diisocyanate compound.
[7]
A curable resin composition for a printing plate or printing original plate, comprising a polymer (B1) produced from the polycarbonate diol composition according to any one of [1] to [3].
[8]
[7] The polymer (B1) is a polymer having a chemical bond formed between a terminal hydroxyl group of the polycarbonate diol composition and another compound and having a polymerizable unsaturated group. Curable resin composition for printing plate or printing original plate.
[9]
The curable resin composition for a printing plate or printing original plate according to [8], wherein the chemical bond is a urethane bond.
[10]
The curable resin composition for printing plates or printing plate precursors according to [8] or [9], wherein the polymerizable unsaturated group is a double bond.
[11]
The curable resin composition for a printing plate or printing original plate according to any one of [7] to [10], wherein the polymer (B1) has a number average molecular weight of 400 to 100,000.
[12]
[4] A curable resin composition for printing plates or printing original plates, comprising the polymer according to any one of [6].
[13]
Curability for printing plate or printing original plate according to any one of [7] to [12], further comprising an organic compound (C) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000. Resin composition.
[14]
The curable resin composition for printing plates or printing original plates according to any one of [7] to [13], further comprising inorganic fine particles (D).
[15]
The curable resin composition for a printing plate or printing original plate according to any one of [7] to [14], further comprising a photopolymerization initiator (E).
[16]
The curable resin composition for a printing plate or printing original plate according to any one of [7] to [15], further comprising a thermal polymerization initiator (F).
[17]
The terminal group X of the monomer (a2) having a molecular weight of 60 to 600 represented by the following formula (2), and the polyisocyanate compound (b) having an isocyanate group equivalent less than the terminal group equivalent of the monomer (a2) Polymerized,
The polymer which the terminal group X of the monomer (a2) which has superposed | polymerized and the isocyanatoalkyl acrylate and / or isocyanatoalkylmethacrylate couple | bond together.
Formula (2):

(In the formula, each R ₂ independently contains at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, and a straight chain having 2 to 50 carbon atoms and And / or a branched hydrocarbon group, each X independently represents a group containing active hydrogen.)
[18]
The end group X of the monomer (a2) having a molecular weight of 60 to 600 represented by the following formula (2), and an isocyanate group equivalent polyisocyanate compound (b) exceeding the end group equivalent of the monomer (a2) are: Polymerized,
A polymer in which the remaining isocyanate group of the polymerized polyisocyanate compound (b) is bonded to a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate by a urethane bond.
Formula (2):

(In the formula, each R ₂ independently contains at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, and a straight chain having 2 to 50 carbon atoms and And / or a branched hydrocarbon group, each X independently represents a group containing active hydrogen.)
[19]
[17] A curable resin composition for a printing plate or printing original plate, comprising the polymer (B2) according to [18].
[20]
The curable resin composition for printing plates or printing plate precursors according to [19], wherein the polymer (B2) has a number average molecular weight of 400 to 100,000.
[21]
The curable resin composition for a printing plate or printing original plate according to [19] or [20], further comprising an organic compound (C) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000. .
[22]
The curable resin composition for printing plates or printing original plates according to any one of [19] to [21], further comprising inorganic fine particles (D).
[23]
The curable resin composition for printing plates or printing original plates according to any one of [19] to [22], further comprising a photopolymerization initiator (E).
[24]
The curable resin composition for printing plates or printing original plates according to any one of [19] to [23], further comprising a thermal polymerization initiator (F).
[25]
[7]-[16] and printing original plate manufactured using the curable resin composition for printing plates or printing original plates in any one of [19]-[24].
[26]
A printing plate obtained by laser engraving the printing original plate according to [25].
[27]
[7] to [16] and a step of molding the curable resin composition for a printing plate or printing original plate according to any one of [19] to [24] into a sheet shape or a cylindrical shape;
The manufacturing method of a printing original plate including the process of hardening | curing the shape | molded printing plate or curable resin composition for printing original plates.
[28]
The manufacturing method of a printing plate including the process of carrying out laser engraving of the printing original plate as described in [25], or the printing original plate obtained by the manufacturing method as described in [27].
[29]
[7] to [16] and a step of molding the curable resin composition for a printing plate or printing original plate according to any one of [19] to [24] into a sheet shape or a cylindrical shape;
Placing a mask layer on the surface of the curable resin composition for a printing plate or printing original plate formed into the sheet or cylinder; and
Irradiating actinic rays from the surface side where the mask layer is disposed;
A method for producing a printing plate, comprising: removing an unirradiated portion.

  ADVANTAGE OF THE INVENTION According to this invention, the printing plate and printing original plate which are excellent in solvent resistance can be provided.

  Hereinafter, a 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.

<Polycarbonate diol composition (A)>
The polycarbonate diol composition of the present embodiment is a composition comprising a polycarbonate diol (a1) and a monomer (a2),
The polycarbonate diol (a1) is a polycarbonate diol represented by the following formula (1) and having a number average molecular weight of 100 to 50,000,
Formula (1):

(In the formula, each R ₁ is independently a straight chain having 3 to 50 carbon atoms, which may contain at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton; Represents a branched and / or cyclic hydrocarbon group.)
The monomer (a2) is a monomer having a number average molecular weight of 60 to 600 represented by the following formula (2):
Formula (2):

(In the formula, each R ₂ is independently a straight chain having 2 to 50 carbon atoms, which may contain at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton; Represents a branched chain and / or a cyclic hydrocarbon group, and each X independently represents a group containing active hydrogen.)
The number average molecular weight of the polycarbonate diol composition is 60 to 1,000.

The number average molecular weight of the polycarbonate diol composition is 60 to 1,000, preferably 80 to 900, more preferably 100 to 800.
By using a polymer (B1) produced from a polycarbonate diol composition (A) having a number average molecular weight within the above range for a curable resin composition, a printing plate and a printing original plate exhibiting excellent solvent resistance can be obtained. it can.

In the present embodiment, the “number average molecular weight of the polycarbonate diol composition (A)” is a number average molecular weight determined by the following formulas 1 to 4.
・ Formula 1
Number average molecular weight of polycarbonate diol composition (A) = 112200 / (total active hydrogen group number of polycarbonate diol composition (A))
・ Formula 2
Total active hydrogen value of the polycarbonate diol composition (A) [mg-KOH / g]
= 56.11 × (total number of active hydroxyl groups) / [(weight of polycarbonate diol (a1)) + (weight of monomer (a2))]
・ Formula 3
Total number of moles of active hydrogen groups = [(Total number of moles of active hydrogen groups in polycarbonate diol (a1)) + (Total number of moles of active hydrogen groups in monomer (a2))]
= [(Active hydrogen group value of polycarbonate diol (a1)) × (Weight of polycarbonate diol composition (a1)) + (Active hydrogen group value of monomer (a2)) × (Weight of monomer (a2))] / 56 .11
・ Formula 4
Active hydrogen group of monomer (a2) = 112200 / (Number average molecular weight of monomer (a2))

<Polycarbonate diol (a1)>
The polycarbonate diol used in the present embodiment is a polycarbonate diol represented by the formula (1). In the formula (1), each R ₁ independently represents an oxygen atom or the like (nitrogen, R ₁ represents a linear, branched, and / or cyclic hydrocarbon group having 3 to 50 carbon atoms, which may contain at least one atom selected from the group consisting of sulfur and oxygen. It may be a single component or a plurality of components.
n is preferably an integer of 1 to 500.

In the present embodiment, the “hydrocarbon group” may be a saturated or unsaturated hydrocarbon group.
In the present embodiment, the “carbon skeleton” means a structural part having 3 to 50 carbon atoms constituting a hydrocarbon group, and “the carbon skeleton may contain an oxygen atom or the like” means a main chain. Or it means a structure in which an oxygen atom or the like is inserted between the carbon-carbon bonds of the side chain. Moreover, the substituent which has an oxygen atom couple | bonded with the carbon atom of a main chain or a side chain may be sufficient.

Examples of the linear hydrocarbon group as R ₁ include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3-8 carbon atoms such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16-hexadecanediol, 1,20-eicosanediol And hydrocarbon groups derived from linear aliphatic diols.

Examples of the branched hydrocarbon group as R ₁ include 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, and 2,2-diethyl-1,3. -Propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl-1,3-propanediol, 1,2 -Butanediol, 2-ethyl-1,4-butanediol, 2-isopropyl-1,4-butanediol, 2,3-dimethyl-1,4-butanediol, 2,3-diethyl-1,4-butane Diol, 3,3-dimethyl-1,2-butanediol, pinacol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2-methyl -2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 3-ethyl-1,5-pentanediol, 2-isopropyl-1,5-pentane Diol, 3-isopropyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,3-dimethyl-1,5-pentane Diol, 2,2,3-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 2-ethyl-1 , 6-hexanediol, 2-ethyl-1,3-hexanediol, 2-isopropyl-1,6-hexanediol, 2,4-diethyl-1,6-hexene Diol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,8-octanediol, 2,6-dimethyl-1,8-octanediol, And hydrocarbon groups derived from branched aliphatic diols having 3 to 30 carbon atoms such as 1,2-decanediol and 8,13-dimethyl-1,20-eicosanediol.

Examples of the cyclic hydrocarbon group as R ₁ include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, and 1,3-cyclohexanedimethyl. Methanol, 1,4-cyclohexanedimethanol, m-xylene-α, α'-diol, p-xylene-α, α'-diol, 2,2-bis (4-hydroxycyclohexyl) -propane, 2,2- And hydrocarbon groups derived from cyclic aliphatic diols having 3 to 30 carbon atoms such as bis (4-hydroxyphenyl) -propane and dimer diol.

  Explaining as an example a hydrocarbon group derived from a linear aliphatic diol having 3 to 50 carbon atoms, in the present embodiment, the “hydrocarbon group derived from a linear aliphatic diol having 3 to 50 carbon atoms” This means a group having a partial structure other than the diol hydroxyl group of a linear aliphatic diol having 3 to 50 carbon atoms.

Examples of the hydrocarbon group containing at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen as R ₁ include diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, 1,2,6-hexanetriol, Trimethylolethane, trimethylolpropane, pentaerythritol, dihydroxyacetone, 1,4: 3,6-dianhydroglucitol, diethanolamine, N-methyldiethanolamine, dihydroxyethylacetamide, 2,2'-dithiodiethanol, 2,5 Examples include hydrocarbon groups derived from -dihydroxy-1,4-dithiane, and groups represented by the following formula (3).
Formula (3):

Since the polycarbonate diol (a1) is a hydroxyl group at both terminal groups, the polycarbonate diol (a1) can be chemically bonded to other functional molecules when producing a printing original plate or the like.
The number average molecular weight of the polycarbonate diol (a1) is 100 to 50,000.
The number average molecular weight of the polycarbonate diol (a1) can be measured by the method described in the following examples.

The polycarbonate diol (a1) can be produced by a conventionally known method as described in, for example, Japanese Patent Publication No. 5-29648. Specifically, the polycarbonate diol (a1) is produced by a transesterification reaction between a diol and a carbonate ester. can do.
When considering that the polycarbonate diol (a1) has a molecular weight distribution, the number average molecular weight 100 is the lower limit. Moreover, when a number average molecular weight is 50,000 or less, a viscosity increase can be suppressed and industrial manufacture of polycarbonate diol (a1) is enabled.
In general, it is difficult to produce the corresponding polycarbonate diol (a1) from a diol having 2 carbon atoms because it is a competitive reaction with the formation of a cyclic carbonate. This is because the cyclic carbonate having 2 carbon atoms is chemically stable. Therefore, it is necessary to use a diol having 3 or more carbon atoms.

In the formula (1), from the viewpoint of solvent resistance, R ₁ preferably contains at least one ether bond. From the viewpoint of solvent resistance and durability, R ₁ is a group derived from diethylene glycol (— (CH ₂ ) ₂ —O— (CH ₂ ) ₂ — is preferred).

In this embodiment, the polycarbonate diol (a1) can be used singly or in combination of two or more depending on the purpose, but it is preferable to use one kind of polycarbonate diol.
The two or more polycarbonate diol (a1), may be two or more polycarbonate diol R ₁ are different, R ₁ is the same, for example, a mixture of two or more polycarbonate diols having different number-average molecular weight May be.

<Monomer (a2)>
The monomer (a2) used in the present embodiment is a monomer represented by the formula (2). In the formula (2), each R ₂ independently represents nitrogen, sulfur, and Represents a linear, branched and / or cyclic hydrocarbon group having 1 to 50 carbon atoms which may contain at least one atom selected from the group consisting of oxygen, and R ₂ is a single component. It may be composed of a plurality of components.
Each X independently represents a group containing active hydrogen.

In the present embodiment, the “group containing active hydrogen” is a group containing nitrogen, sulfur, or oxygen and hydrogen, and means a group capable of liberating hydrogen.
Examples of the group containing active hydrogen include a hydroxyl group, a thiol group, a carboxyl group, an unsubstituted or 1-2-substituted amino group, and a hydroxyl group is preferable.
When the monomer (a2) has a group containing active hydrogen, a reaction such as condensation or addition can occur with another molecule.

  Examples of the monomer (a2) include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -C2-C50 straight chain such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16-hexadecanediol, 1,20-eicosanediol Compounds having a hydrocarbon structure; 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl- 2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-dibutyl 1 3-propanediol, 1,2-butanediol, 2-ethyl-1,4-butanediol, 2-isopropyl-1,4-butanediol, 2,3-dimethyl-1,4-butanediol, 2,3 -Diethyl-1,4-butanediol, 3,3-dimethyl-1,2-butanediol, pinacol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2-methyl- 2,4-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,5-pentanediol, 3-ethyl-1,5-pentanediol, 2-isopropyl-1,5-pentanediol 3-isopropyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol 2,3-dimethyl-1,5-pentanediol, 2,2,3-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 2-ethyl-1,6-hexanediol, 2-ethyl-1,3-hexanediol, 2-isopropyl-1,6-hexanediol, 2,4-diethyl-1,6 -Hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,8-octanediol, 2,6-dimethyl-1,8-octane Compounds having a branched hydrocarbon structure of 3 to 50 carbon atoms such as diol, 1,2-decanediol, 8,13-dimethyl-1,20-eicosanediol; Cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, m-xylene-α, α'- C 3-50 such as diol, p-xylene-α, α′-diol, 2,2-bis (4-hydroxycyclohexyl) -propane, 2,2-bis (4-hydroxyphenyl) -propane, dimer diol, etc. And compounds having a cyclic hydrocarbon structure.

  The monomer (a2) may be a compound having a hydrocarbon structure in which the hydroxyl portion of the compound is substituted with a thiol group or an amino group, or a compound having a hydrocarbon structure substituted with an amino group. As an example, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, hexamethylenediamine and the like can be mentioned.

  The monomer (a2) may be a compound having a hydrocarbon structure in which the hydroxyl portion of the above compound is substituted with a carboxyl group, and a compound having a hydrocarbon structure substituted with a carboxyl group is shown as an example. And glycolic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, isophthalic acid, terephthalic acid and the like.

  Examples of the monomer (a2) include compounds having a hydrocarbon structure containing at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen. For example, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, dihydroxyacetone, 1,4: 3,6-dianhydroglucitol, diethanolamine, triethanolamine, N-methyldiethanolamine, dihydroxyethyl Acetamide, dimethylolurea, urea, 1,3-dimethylurea, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, diethylenetriamine, isophoronediamine, 2,2 - dithiodiethanol, 2,5-dihydroxy-1,4-dithiane and the like.

The hydrocarbon group as R ₂ is preferably a group derived from the above compound.
The monomer (a2) has active hydrogen at both terminal groups, and thus can be chemically bonded to other functional molecules when producing a printing original plate or the like.
The monomer (a2) preferably has a number average molecular weight of 60 to 600 from the viewpoint of availability. When the monomer (a2) is a single compound, the number average molecular weight means the molecular weight.

In this embodiment, a monomer (a2) can be used 1 type or in combination of 2 or more types according to the objective.
The two or more monomers (a2), may be two or more monomers R ₂ are different, R ₂ may be the same two or more monomers.

(Curable resin composition for printing plate or printing original plate)
The curable resin composition for a printing plate or printing original plate of the present embodiment (hereinafter sometimes simply referred to as “curable resin composition”) is a polymer produced from the polycarbonate diol composition (A). (B1) and / or polymer (B2).
The number average molecular weight of the polymer (B1) is preferably 400 to 100,000 from the viewpoint of easy handling and hardness after curing, and the number average molecular weight of the polymer (B2) is easy to handle and hardened. From the viewpoint of the later hardness, it is preferably 400 to 100,000.

<Polymer (B1)>
The polymer (B1) is not particularly limited as long as it is a polymer produced from the polycarbonate diol composition (A), but as the polymer (B1), the terminal hydroxyl group of the polycarbonate diol composition (A), other compounds and It is preferably a polymer produced with the formation of a chemical bond between and containing a polymerizable unsaturated group.
In the polymer (B1), the number average molecular weight can be obtained as a polymer composition obtained by randomly polymerizing the polycarbonate diol (a1) and the monomer (a2) of the polycarbonate diol composition (A) of 60 to 1,000.
When the polymer (B1) has a polymerizable unsaturated group, it is suitable for linking with various molecules when producing a printing original plate or the like.
Although there is no restriction | limiting in particular as a chemical bond and a polymerizable unsaturated group, As a chemical bond, a urethane bond is preferable and a double bond is preferable as a polymerizable unsaturated group.

As the polymer (B1), from the viewpoint of adjusting the viscosity or adjusting the properties of a printing plate or printing original plate obtained by curing, the terminal group of the polycarbonate diol composition (A) and the terminal of the polycarbonate diol composition (A) are used. An isocyanate group equivalent polyisocyanate compound (b) less than the group equivalent, and the remaining terminal group of the polymerized polycarbonate diol composition (A), isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, Is preferably a polymer to which are bound.
As the polymer (B1), the terminal group X of the monomer (a2) contained in the polycarbonate diol composition (A) is preferably a hydroxyl group. In this case, the polycarbonate diol composition (A) and the polyisocyanate compound (b) The polymerization with is preferably performed by polyurethane bonding. Moreover, it is preferable that the bond between the terminal hydroxyl group remaining in the polycarbonate diol composition (A) and the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate is bonded by a polyurethane bond.
As the polymer (B1), the end group of the polycarbonate diol composition (A) and the polyisocyanate compound (b) having an isocyanate group equivalent exceeding the end group equivalent of the polycarbonate diol composition (A) are polymerized. The polymer group in which the remaining isocyanate group of the polymerized polyisocyanate compound (b) is bonded to the hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate by a urethane bond is preferable.

  When the polyisocyanate compound (b) is reacted with an isocyanate group equivalent less than the terminal group equivalent of the polycarbonate diol composition (A), the equivalent ratio is particularly limited as long as (A) / (b) exceeds 1. However, it is preferably 1.01 or more and 3 or less. Further, when the polyisocyanate compound (b) is reacted with an isocyanate group equivalent exceeding the terminal group equivalent of the polycarbonate diol composition (A), the equivalent ratio (b) / (A) is particularly preferably greater than 1. Although not limited, it is preferably 1.01 or more and 3 or less.

<Polymer (B2)>
As the polymer (B2), from the viewpoints of adjusting the viscosity and adjusting the properties of the printing plate or printing original plate obtained by curing, the terminal group of the monomer (a2) and the isocyanate group less than the terminal group equivalent of the monomer (a2) An equivalent amount of the polyisocyanate compound (b) is polymerized, and the remaining terminal group of the polymerized monomer (a2) is bonded to the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate. .
As the polymer (B2), it is preferable that the terminal group X of the monomer (a2) is a hydroxyl group, and in this case, the polymerization of the monomer (a2) and the polyisocyanate compound (b) is performed by a polyurethane bond. Is preferred. Moreover, it is preferable that the coupling | bonding of the terminal hydroxyl group which the monomer (a2) remains, and isocyanato alkyl acrylate and / or isocyanato alkyl methacrylate is couple | bonded by the urethane bond.
Further, as the polymer (B2), a terminal group of the monomer (a2) and a polyisocyanate compound (b) having an isocyanate group equivalent exceeding the terminal group equivalent of the monomer (a2) are polymerized and polymerized. It is a polymer in which the remaining isocyanate group of the isocyanate compound (b) and a hydroxyalkyl acrylate and / or a hydroxyalkyl methacrylate are urethane-bonded.

  When the polyisocyanate compound (b) is reacted using an isocyanate group equivalent less than the terminal group equivalent of the monomer (a2), the equivalent ratio is particularly limited as long as (a2) / (b) exceeds 1. However, it is preferably 1.01 or more and 3 or less. Further, when the polyisocyanate compound (b) is reacted with an isocyanate group equivalent exceeding the terminal group equivalent of the monomer (a2), the equivalent ratio is not particularly limited as long as (b) / (a2) exceeds 1. Although not intended, it is preferably 1.01 or more and 3 or less.

For example, the reaction temperature in the polymerization step of the polycarbonate diol composition (A) or the monomer (a2) and the polyisocyanate compound (b) when producing the polymer (B1) and the polymer (B2) is not particularly limited. The temperature is preferably 20 ° C. or higher and 200 ° C. or lower, more preferably 30 ° C. or higher and 150 ° C. or lower, and further preferably 40 ° C. or higher and 120 ° C. or lower.
When the reaction temperature in the polymerization step is 20 ° C. or higher and 200 ° C. or lower, productivity of the polymer is improved and quality deterioration due to side reaction can be suppressed.
The reaction time in the polymerization step is not particularly limited, but is preferably 1 hour to 20 hours, more preferably 2 hours to 10 hours, and further preferably 2 hours to 8 hours.
When the reaction time in the polymerization step is 1 hour or more and 20 hours or less, the productivity of the polymer can be improved and the quality deterioration due to the side reaction can be suppressed.

<Polyisocyanate compound (b)>
In the present embodiment, the polyisocyanate compound (b) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. Examples of the polyisocyanate compound (b) include diisocyanate compounds such as aromatic diisocyanates and aliphatic or alicyclic diisocyanates, and one or more can be used in combination. In this Embodiment, the isocyanate group equivalent of a polyisocyanate compound (b) can be calculated | required as a theoretical value of a polyisocyanate compound (b).
Examples of the aromatic diisocyanate include diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like.
Examples of the aliphatic or alicyclic diisocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and hydrogenated xylylene diisocyanate.
Examples of the polyisocyanate compound (b) include triisocyanate compounds, such as triphenylmethane triisocyanate and tri (isocyanatophenyl) triphosphate. Examples of the other polyisocyanate compound (b) include polymeric (diphenylmethane diisocyanate), but from the viewpoint of solvent resistance, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is more preferable.

In this embodiment, as isocyanatoalkyl acrylate and isocyanatoalkyl methacrylate, for example, isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, and the like are used alone or in combination of two or more. be able to.
Examples of the hydroxyalkyl acrylate and hydroxyalkyl methacrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like, and one or more of them can be used in combination.

<Organic compound (C)>
The curable resin composition of the present embodiment has a polymerizable unsaturated group and has a number average molecular weight of less than 5,000 in terms of adjusting the viscosity and adjusting the properties of the printing plate or printing original plate obtained by curing. It is preferable to further contain an organic compound (C) (hereinafter sometimes simply referred to as “organic compound (C)”).
In the present embodiment, the “number average molecular weight of the organic compound (C)” means a molecular weight when it is a single compound, and it is measured by a GPC method (gel filtration chromatography method) when it is not a single compound. Means a value that can be
In this embodiment, “polymerizable unsaturated group” means an unsaturated group involved in radical polymerization or addition reaction.
Examples of the polymerizable unsaturated group involved in the radical polymerization reaction include an acrylic group and a methacryl group. Examples of the polymerizable unsaturated group involved in the addition reaction include an epoxy group, an oxetane group, and a vinyl ether group. Is mentioned.

  Examples of the organic compound (C) include olefins such as ethylene, propylene, styrene, and divinylbenzene; (meth) acrylic acid and derivatives thereof; unsaturated nitriles such as haloolefins and acrylonitrile; (meth) acrylamide and Derivatives thereof; allyl compounds such as allyl alcohol and allyl 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 or derivatives thereof are preferred.

Examples of the derivatives include aliphatic such as alkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, allyl-, cycloalkyl-, bicycloalkyl-, cycloalkenyl-, and bicycloarnyl-. Or a compound having an alicyclic skeleton; a compound having an aromatic skeleton such as benzyl-, phenyl-, phenoxy- or fluorenyl-; containing oxygen, nitrogen, sulfur or the like as a heteroatom such as tetrahydrofurfuryl- It may be a compound having a heteroaromatic skeleton.
Examples of the derivatives include glycidol, alkylene glycol, polyoxyalkylene glycol, (alkyl / allyloxy) polyalkylene glycol, and esters of alcohol such as trimethylolpropane.

  Examples of the organic compound (C) include phenoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylene glycol butyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, trimethylolpropane (meth) acrylate, lauryl ( Such as (meth) acrylate

Examples of the organic compound (C) include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S propylene oxide diglycidyl ether , Hydrogenated bisphenol A diglycidyl -Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (ethylene oxide or propylene oxide added to bisphenol A) (Caprolactone) diol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1-methyl-3,4-epoxycyclohexylmethyl-1′-methyl-3 ′, 4′- Epoxy cyclohexyl carboxylate, bis [1-methyl-3,4-epoxy cyclohexyl] ester adipate, vinyl cyclohexene diepoxide, polybutadiene and poly Also included are polyepoxy compounds obtained by reacting polyacenes such as lyisoprene with peracetic acid, epoxidized soybean oil, and the like.
The organic compound (C) can be used alone or in combination of two or more depending on the purpose.

<Inorganic fine particles (D)>
When the curable resin composition of the present embodiment is a printing original plate, in addition to flexibility, it preferably has a feature that it is excellent in laser engraving property, which is an important characteristic in a method of directly forming a relief image with a laser, In order to further improve the laser engraving property, it is preferable to further contain inorganic fine particles (D).

  Although there is no restriction | limiting in the material and form of inorganic type microparticles | fine-particles (D), What has a micropore or a micro space | gap in a particle is preferable. When the curable resin composition is used as a printing original plate, the inorganic fine particles (D) have a function of effectively absorbing and removing liquid waste generated when the original plate is decomposed by a laser. By containing the fine particles (D), not only the accuracy of the relief image by laser engraving is improved, but also the cleaning operation after laser engraving becomes extremely simple.

Although there is no restriction | limiting in the magnitude | size of inorganic type microparticles | fine-particles (D), it is preferable that a number average particle diameter is 0.01-100 micrometers, More preferably, it is 0.1-20 micrometers, More preferably, it is 1-10 micrometers. is there.
Although there is no restriction | limiting in the average pore diameter of inorganic type microparticles | fine-particles (D), Preferably it is 1-1000 nm, More preferably, it is 2-200 nm, More preferably, it is 2-50 nm.
Although there is no restriction | limiting in the pore volume of inorganic type microparticles | fine-particles (D), 0.01-10 mL / g is preferable, More preferably, it is 0.1-5 mL / g.
Although there is no restriction | limiting in the specific surface area of inorganic type microparticles | fine-particles (D), 1-1,500m < ² > / g is preferable, More preferably, it is 10-800m < ² > / g.
Although there is no restriction | limiting in the shape of inorganic type microparticles | fine-particles (D), A spherical shape, flat shape, needle shape, an amorphous shape, or the particle | grains with a processus | protrusion on the surface can be used. In addition, particles in which the inside of the particles are hollow, spherical granules having a uniform pore diameter such as silica sponge, and the like can also be used. For example, porous silica, mesoporous silica, silica-zirconia porous gel, mesoporous molecular sieve, porous alumina, porous glass and the like can be used. Moreover, what has a space | gap of several nm-100 nm between layers like a layered clay compound can also be used as inorganic type fine particles.
The inorganic fine particles (D) can be used alone or in combination of two or more according to the purpose.

<Photopolymerization initiator (E)>
It is preferable that the curable resin composition of this embodiment further contains a photopolymerization initiator (E).
The photopolymerization initiator (E) may be appropriately selected from known ones. For example, radical polymerization exemplified in “Polymer Data Handbook-Fundamental” edited by the Society of Polymer Science (1986, published by Baifukan). Initiators for cationic polymerization and anionic polymerization can be used.
Crosslinking of a curable resin composition by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing original plate with high productivity while maintaining storage stability.

Examples of the photopolymerization initiator (E) include benzoin alkyl ethers such as benzoin and benzoin ethyl ether; 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone , Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone and diethoxyacetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- Photo-radical polymerization initiators such as ON, methyl phenylglyoxylate, benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine, anthraquinones; aromatic diazonium salts, aromatic iodonium salts that generate light by absorbing light, aromatic Photocationic polymerization initiators such as group sulfonium salts; photoanionic polymerization initiators that absorb light and generate bases.
A photoinitiator (E) can be used 1 type or in combination of 2 or more types according to the objective.

<Thermal polymerization initiator (F)>
It is preferable that the curable resin composition of this embodiment further contains a thermal polymerization initiator (F).
It does not restrict | limit especially as a thermal-polymerization initiator (F), All the thermal-polymerization initiators which can be used for radical polymerization reaction and ring-opening polymerization reaction are mentioned.
Examples of the thermal polymerization initiator used in the radical polymerization reaction include organic peroxides, inorganic peroxides, organic silicon peroxides, hydroperoxides, azo compounds, thiol compounds, quinones, and quinone dioxime derivatives.
As a thermal polymerization initiator used in the ring-opening polymerization reaction, for example, a polymerization initiator containing an acid or a base is placed in the microcapsule, and the microcapsule is destroyed by heating, so that the internal polymerization initiator flows out. It is preferable to select a latent thermal polymerization initiator of a type that initiates curing.
Specifically, it is preferable to use NovaCure (registered trademark) manufactured by Asahi Kasei Chemicals Corporation.
The thermal polymerization initiator (F) can be used alone or in combination of two or more depending on the purpose.

The thermal polymerization initiator (F) is preferably liquid at 20 ° C. from the viewpoint of easy mixing.
The thermal stability of the thermal polymerization initiator (F) is usually determined by the method with a 10-hour half-life temperature of 10 h-t _1/2 , that is, 50% of the initial amount of the thermal polymerization initiator (F) is 10 It is shown at the temperature at which it decomposes after time 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 (F) preferably have 10 h-t _1/2 of at least 60 ° C., more preferably at least 70 ° C. More preferably, it is 10h-t _1/2 of 80 degreeC-150 degreeC.
As the thermal polymerization initiator (F), an organic peroxide is preferable from the viewpoints of securing thermosetting in the atmosphere, handling, reducing the hardness of the thermoset, and compatibility with the thermosetting resin composition. .

  Examples of the organic peroxide include peroxyesters, diperoxyketals, dialkyl peroxides, diacyl peroxides, and t-alkyl hydroperoxides.

Examples of peroxyesters include t-butyl peroctanoate, t-amyl peroctanoate, t-butyl peroxyisobutyrate, t-butyl peroxymaleate, t-amyl perbenzoate, di-peroxyphthalate di- Examples include t-butyl, t-butyl perbenzoate, t-butyl peracetate, and 2,5-di (benzoylperoxy) -2,5-dimethylhexane.
Examples of diperoxyketals include 1,1-di (t-amylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane and ethyl 3 , 3-di (t-butylperoxy) butyrate and the like.
Examples of the dialkyl peroxides include di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide and 2,5-di (t-butylperoxy) -2,5-dimethylhexane.
Examples of diacyl peroxides include dibenzoyl peroxide and diacetyl peroxide.
Examples of t-alkyl hydroperoxides include t-butyl hydroperoxide, t-amyl hydroperoxide, pinane hydroperoxide and cumyl hydroperoxide.

Examples of the inorganic peroxide include peroxides such as Ba, Ca, Mg, and Zn.
Examples of the organosilicon peroxide include Si—O—O—Si type, Si—O—O—C type, and Si—O—O—R (alkyl) type compounds.
Examples of the thiol compound include 6-dibutylamino-1,3,5-triazine-2,4-dithiol, mercaptobenzothiazole, 2-mercaptoimidazoline, and the like.
Examples of quinone and quinonedioxime derivatives include p-quinone and p-quinonedioxime.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, and the like. It is done.
Examples of the hydroperoxide include aliphatic and alicyclic saturated hydroperoxides, and hydroperoxides having an OOH group in the aromatic side chain. Examples of the hydroperoxide include methyl hydroperoxide, ethyl hydroperoxide, propyl hydroperoxide, butyl hydroperoxide, isopropyl hydroperoxide, isobutyl hydroperoxide, hexyl hydroperoxide, octyl hydroperoxide, decyl hydroperoxide, cyclopentyl hydroperoxide, and cyclohexyl hydroperoxide. Benzyl hydroperoxide, 1-phenylethyl hydroperoxide, diphenylmethyl hydroperoxide, triphenylmethyl hydroperoxide, tetralin hydroperoxide, 9-fluorenyl hydroperoxide and the like.

The method for producing a curable resin composition in the present embodiment includes an organic compound (C) having a polymerizable unsaturated group and a number average molecular weight of less than 5,000 in the polymer (B1) and / or (B2), It is preferable to include a step of adding at least one selected from the group consisting of inorganic fine particles (D), a photopolymerization initiator (E), and a thermal polymerization initiator (F).
Although it does not specifically limit in the manufacturing method of a curable resin composition, It mixes following a process (2) on the temperature conditions similar to manufacturing a polymer (B1) and / or a polymer (B2). Thus, a curable resin composition can be produced.

  In the present embodiment, the composition of the curable resin composition is not limited, but is organic with respect to 100 parts by mass of the polymer (B1) and / or polymer (B2) produced from the polycarbonate diol composition (A). The compound (C) is 5 to 200 parts by mass, the inorganic fine particles (D) are 1 to 100 parts by mass, the photopolymerization initiator (E) is 1 to 100 parts by mass, and the thermal polymerization initiator (F) is 1 to 100 parts by mass. Part.

  A polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the curable resin composition depending on the application and purpose. The addition amount is preferably in the range of 10% by mass or less with respect to the curable resin composition.

  By using the curable resin composition containing the polymer (B1) and / or the polymer (B2) produced from the polycarbonate diol composition (A), a printing plate or printing original plate excellent in solvent resistance can be obtained. it can. Moreover, the printing plate excellent in solvent resistance can be obtained by carrying out the laser engraving of this printing original plate.

<Printing master>
In the method for producing a printing original plate according to the present embodiment, a polymer (B1) produced from the polycarbonate diol composition (A) and / or a curable resin composition containing the polymer (B2) is formed into a sheet shape or a cylindrical shape. And a step of curing the curable resin composition formed into a sheet shape or a cylindrical shape.
By using the curable resin composition containing the polymer (B1) and / or the polymer (B2) produced from the polycarbonate diol composition (A), a printing original plate excellent in solvent resistance can be produced.

There is no restriction | limiting in the method of shape | molding curable resin composition in a sheet | seat or cylindrical shape, The existing molding method of resin can be used. For example, a method of extruding resin from a nozzle or a die with a machine such as a pump or an extruder and adjusting the thickness with a blade (casting method); a method of adjusting the thickness by calendaring with a roll, and the like.
It is also possible to perform molding while heating within a range that does not deteriorate the performance of the curable resin composition. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, a curable resin composition can be formed on an underlay called a back film made of a material such as PET (polyethylene terephthalate) or nickel.

  The forming step in the method for producing the printing original plate may be a step of directly forming the curable resin composition on the cylinder of the printing press. In that case, a seamless seamless sleeve can be formed.

There is no restriction | limiting in the method of hardening | curing the curable resin composition shape | molded by the sheet form or the cylindrical form, The hardening method of the existing resin can be used.
The curing step in the method for producing a printing original plate is preferably a step of curing with actinic rays, and examples of the actinic rays include at least one selected from the group consisting of light, electron beams, and heat.

<Printed version>
The method for producing a printing plate according to the present embodiment includes a step of laser engraving the printing original plate, and it is preferable to form irregularities on the surface of the printing original plate by laser engraving.
By using a printing original plate excellent in solvent resistance, a printing plate excellent in solvent resistance can be produced.
The method of laser engraving is not particularly limited. For example, a printing plate having irregularities on the surface can be formed by attaching a printing original plate to a laser processing machine and performing laser engraving.
Since the curable resin composition of the present embodiment has good laser engraving properties when cured, it is particularly suitable for producing a printing plate by a laser engraving method.

  Sleeve molding / engraving device (a liquid curable resin composition is applied onto a cylindrical support and the liquid curable resin composition is cured by at least one means selected from the group consisting of light, electron beam, and heat) The printing plate can be formed using a laser light source for laser engraving incorporated in the apparatus. When such an apparatus is used, the printing plate can be formed by laser engraving immediately after forming the sleeve, so a short time that cannot be considered with a conventional rubber sleeve that required several weeks for the forming process. Time machining can be realized.

As a method for producing the printing plate of the present embodiment, there is a so-called photolithography method, a step of forming a curable resin composition into a sheet or cylinder, and a curable resin formed into the sheet or cylinder. It includes a step of disposing a negative mask layer on the surface of the composition, a step of irradiating actinic rays from the surface side where the negative mask layer is disposed (exposure step), and a step of removing unirradiated portions (development step).
Examples of the actinic ray include at least one selected from the group consisting of light, electron beam, and heat, and the curable resin composition formed into a sheet shape or a cylindrical shape is partially cured by the exposure process. .
By using the curable resin composition of this embodiment, a printing plate excellent in solvent resistance can be produced.

<Application>
The printing plate of this embodiment can be suitably used for at least one printing application selected from flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing. In addition, the printing plate can be used as a mold, and the printing plate surface can be used in contact with the thermoplastic resin, thermosetting resin, or photocurable resin to transfer the concave pattern on the printing plate surface.

  Hereinafter, the present embodiment will be described in detail with reference to examples and reference examples, but the present embodiment is not limited to the following examples. Various characteristics in the following Examples and Reference Examples were measured according to the following methods.

<Measurement method>
1. Active hydrogen group value of polycarbonate diol 12.5 g of acetic anhydride was made up to 50 mL with pyridine to prepare an acetylating reagent. In a 100 mL eggplant flask, 0.1 to 1.0 g of the sample was precisely weighed. 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 (titration solution).
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, and then titrated in the same manner. Based on this result, the active hydrogen group value was calculated using the following formula (i) as the terminal hydroxyl group equivalent of polycarbonate diol.
Formula (i):
Active hydrogen group value (mg-KOH / g) = {(ba) × 28.05 × f} / e
a: Titration volume of sample (mL)
b: Titration volume of blank test (mL)
e: Sample weight (g)
f: Factor of titrant

2. Measurement of number average molecular weight of polycarbonate diol The terminals of the polycarbonate diol in Examples and Reference 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 Reference Examples were 0.01 or less.
Therefore, the number average molecular weight of the obtained polycarbonate diol was determined by the following mathematical formula (ii).
Formula (ii):
Number average molecular weight Mn = 2 / (active hydrogen group value × 10 ⁻³ /56.11)

3. Measurement of number average molecular weight of polymer (calculation by GPC method)
The number average molecular weights of the polymers in Examples and Reference Examples were determined by conversion with polystyrene having a known molecular weight using gel permeation chromatography (GPC method). Using a high-speed GPC device “HLC-8220GPC” manufactured by Tosoh Corporation and a polystyrene-filled column “TSKgel GMHXL” manufactured by Tosoh Corporation (inner diameter 7.8 mm, length 300 mm × 3), 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 polymer concentration of 1% by mass was prepared, and the injection amount was 10 μL. A differential refractive index detector was used as the detector.

4). Swelling rate of printing original plate About swelling rate with respect to various solvents, a printing original plate having a thickness of 3 mm was cut into 2 cm × 1 cm, immersed at 23 ° C. for 24 hours, and the swelling rate was obtained using the following formula (iii).
Formula (iii):
Swelling rate (mass%) = {(mass after immersion−mass before immersion) / mass before immersion} × 100

5). Laser engraving of the printing original plate Laser engraving of the original printing plate was performed using a carbon dioxide laser engraving machine (output: 12 watts, trademark Laser Pro Venus, manufactured by GCC). The engraving was performed by creating a pattern including a line drawing with a convex line having a width of 200 μm. The engraving depth (relief depth) was 400 μm. The presence or absence of viscous liquid residue generated by laser engraving and the sharpness of the line drawing were visually determined.

[Example 1]
Diethylene glycol (30.04 g, 0.283 mol) (molecular weight Mw = 106) is placed in a 300 mL separable flask equipped with a stirrer, and tolylene diisocyanate (36.66 g, 0.210 mol) is added in three divided portions every 30 minutes. It was. Under a dry air atmosphere, tolylene diisocyanate was first added, and the mixture was stirred at 40 ° C. for 30 minutes and then at 80 ° C. for 2 hours. Thereafter, 22.96 g of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at 80 ° C. for 3 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of diethylene glycol was linked by a urethane bond and a polymer having a double bond (number average molecular weight Mn by GPC method = 1601) was obtained. Thereafter, 13.33 g of ethylene glycol phenyl ether methacrylate, 7.40 g of trimethylolpropane trimethacrylate, 6.88 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.50 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 0.90 g, benzophenone 1.50 g, 2,6-di-tert-butyl-4-methylphenol 0.90 g, Sanol (registered trademark) LS-785 (Sankyo Corporation) ) 1.50 g was added and stirred at 80 ° C. for 2 hours to mix, and then depressurized to 13 kPa for defoaming to obtain a viscous liquid curable resin composition at 80 ° C.

[Example 2]
Regular packing Helipak packing No. Into a 20 L reaction kettle equipped with a distillation tower having a packing height of 400 mm and an inner diameter of 60 mm, and a fractionation head, 1225 g (120.9 mol) of diethylene glycol and 11175 g (126.9 mol) of ethylene carbonate were charged at 70 ° C. After stirring and dissolving and replacing the system with nitrogen, 9.6 g of tetrabutoxy titanium was added as a catalyst. This reaction kettle was heated while extracting a part of the reflux liquid from the fractionation head so that the internal temperature was 160 to 165 ° C. and the pressure was 8 to 11 kPa, and reacted for 55 hours. Then, remove the packed distillation column, replace it with a simple distillation device, raise the internal temperature to 170-180 ° C, drop the pressure to 0.2 kPa, and distill off the raw materials (diethylene glycol, ethylene carbonate) remaining in the reaction kettle did. Then, it reacted for 10 hours, distilling the diethylene glycol produced | generated by reaction with an internal temperature of 175-190 degreeC and the pressure of 0.1 kPa with a single distillation apparatus. By this reaction, 10020 g of a liquid polycarbonate diol that was viscous at room temperature was obtained. The active hydrogen group value of the obtained polycarbonate diol was 69.5 (number average molecular weight Mn = 1614).
A 300 mL separable flask equipped with a stirrer was charged with 48.04 g of polycarbonate diol having the above number average molecular weight Mn = 1614 and 12.00 g of diethylene glycol (molecular weight Mw = 106), and a polycarbonate diol composition (calculated value of number average molecular weight Mn). = 420) and 22.12 g of tolylene diisocyanate were added in half portions every 30 minutes. Under a dry air atmosphere, tolylene diisocyanate was first added, followed by stirring at 40 ° C. for 30 minutes and then at 80 ° C. for 3 hours. Thereafter, 5.04 g of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of the polycarbonate diol composition was linked by a urethane bond and a polymer having a double bond (number average molecular weight Mn = 7108 by GPC method) was obtained. .
Thereafter, 12.93 g of ethylene glycol phenyl ether methacrylate, 7.18 g of trimethylolpropane trimethacrylate, 6.68 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.45 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 0.87 g, benzophenone 1.46 g, 2,6-di-tert-butyl-4-methylphenol 0.88 g, Sanol (registered trademark) LS-785 (Sankyo Corporation) ) 1.45 g was added and stirred for 2 hours at 80 ° C., followed by mixing and degassing under reduced pressure to 13 kPa to obtain a viscous liquid curable resin composition at 80 ° C.

Example 3
Diethylene glycol was charged into a 3m3SUS reactor with a heating jacket equipped with a regular packing, a distillation column with a packing height of 5m, a diameter of 0.45m, a theoretical plate number of 10, a condenser, a pot, a reflux pump, and a stirrer. 1298.4 kg (12.235 kmol) and 1131.3 kg (12.847 kmol) of ethylene carbonate were charged, and 0.97 kg of tetrabutoxy titanium was added as a catalyst. The operation of reducing the pressure of the reactor to 1 kPa, introducing nitrogen and returning to atmospheric pressure was repeated three times, and the inside of the reactor was replaced with nitrogen.
Heating was started by flowing a heat medium at 250 ° C. through the jacket, the tower top pressure was adjusted to 7-8 kPa, and the reactor was heated at 150 ° C. for 2 hours. At this time, extraction from the distillation column was not performed.
Thereafter, the reflux ratio of the distillation column is set to 8 to 12, the top pressure is adjusted to 7 to 3 kPa so that the extraction amount is 35 to 55 kg / hour, and a heating medium at 25 ° C. is passed through the jacket. Heated at a temperature of 160-165 ° C. for 15 hours.
Thereafter, the entire amount was withdrawn from the distillation column, the top pressure was adjusted to 0.5 kPa, and a heating medium at 210 ° C. was passed through the jacket to heat the reactor at 160 to 175 ° C. for 3 hours.
Thereafter, the pressure at the top of the column is adjusted to 0.2 to 0.3 kPa, and the temperature inside the reactor is 175 ° C. by flowing a heating medium at 180 ° C. through the jacket. While extracting, it was heated for 3 hours and 20 minutes.
By this reaction, 1002 kg of a viscous polycarbonate diol at room temperature was obtained. The active hydrogen group value of the obtained polycarbonate diol was 54.8 (number average molecular weight Mn = 2047).
A 300 mL separable flask equipped with a stirrer was charged with 89.45 g of the polycarbonate diol having the above number average molecular weight Mn = 2047 and 10.52 g of diethylene glycol (molecular weight Mw = 106), and a polycarbonate diol composition (calculation of the number average molecular weight Mn). Value = 700), and 21.40 g of tolylene diisocyanate was added in half portions every 30 minutes. Under a dry air atmosphere, tolylene diisocyanate was first added, followed by stirring at 40 ° C. for 30 minutes and then at 80 ° C. for 3 hours. Thereafter, 6.41 g of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a polymer having a terminal hydroxyl group of diethylene glycol linked by a urethane bond and having a double bond (number average molecular weight Mn by GPC method = 8399) was obtained.
Then, ethylene glycol phenyl ether methacrylate 18.97g, trimethylolpropane trimethacrylate 10.53g, silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.) 9.80g, silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2.13g 2,2-dimethoxy-2-phenylacetophenone 1.28 g, benzophenone 2.13 g, 2,6-di-tert-butyl-4-methylphenol 1.29 g, SANOL (registered trademark) LS-785 (Sankyo Corporation) 2.14 g was added and mixed by stirring at 80 ° C. for 2 hours, and then degassed by reducing the pressure to 13 kPa to obtain a viscous liquid curable resin composition at 80 ° C.

Example 4
A 300 mL separable flask equipped with a stirrer was charged with 93.98 g of the polycarbonate diol of Example 7 having a number average molecular weight Mn = 2047 and 6.02 g of ethylene glycol (molecular weight Mw = 62), and a polycarbonate diol composition (number average molecular weight). The calculated value of Mn was 700), and 21.38 g of tolylene diisocyanate was added in 30 portions every 30 minutes. Under a dry air atmosphere, tolylene diisocyanate was first added, followed by stirring at 40 ° C. for 30 minutes and then at 80 ° C. for 4 hours. Thereafter, 6.40 g of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of diethylene glycol was linked by a urethane bond and a polymer having a double bond (number average molecular weight Mn by GPC method = 7700) was obtained.
Thereafter, 18.96 g of ethylene glycol phenyl ether methacrylate, 10.52 g of trimethylolpropane trimethacrylate, 9.81 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 2.12 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 1.28 g, benzophenone 2.14 g, 2,6-di-tert-butyl-4-methylphenol 1.29 g, SANOL (registered trademark) LS-785 (Sankyo Corporation) ) 2.13 g was added and stirred at 80 ° C. for 2 hours to mix, and then depressurized to 13 kPa for defoaming to obtain a viscous liquid curable resin composition at 80 ° C.

Example 5
A viscous liquid curable resin composition was obtained at 80 ° C. in the same manner as in Example 2 except that silica gel C-1504 was not added.

[Reference Example 1]
Regular packing Helipak packing No. 3, a 2 L flask equipped with a distillation tower having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head was charged with 587.8 g (5.54 mol) of diethylene glycol and 512.2 g (5.82 mol) of ethylene carbonate, After stirring and dissolving at 70 ° C. and replacing the system with nitrogen, 0.44 g of tetrabutoxy titanium was added as a catalyst. This flask was heated while extracting a part of the reflux liquid from the fractionation head so that the internal temperature was 160 to 165 ° C. and the pressure was 8 to 10 kPa, and reacted for 25 hours. After that, remove the packed distillation column, replace it with a simple distillation device, raise the internal temperature to 170-175 ° C, drop the pressure to 0.2 kPa, and distill off the raw materials (diethylene glycol, ethylene carbonate) remaining in the reaction kettle did. By this reaction, 1100.0 g of a liquid polycarbonate diol viscous at room temperature was obtained. The active hydrogen group value of the obtained polycarbonate diol was 100.0 (number average molecular weight Mn = 1122).
The polycarbonate diol 65.0 g and the monobutyl phosphate 0.06 g were put into a 300 mL separable flask equipped with a stirrer, and tetrabutoxytitanium was deactivated by stirring at 95 ° C. for 3 hours.
Thereafter, 0.08 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, 8.49 g of tolylene diisocyanate, and 0.001 g of di-n-butyltin dilaurate were added. In a dry air atmosphere, tolylene diisocyanate was added, and the mixture was stirred at 40 ° C. for 30 minutes and then at 80 ° C. for 3 hours. Thereafter, 2.92 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 was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of diethylene glycol was linked by a urethane bond and a polymer having a double bond (number average molecular weight Mn by GPC method = 7250) was obtained.
Thereafter, 11.34 g of ethylene glycol phenyl ether methacrylate, 6.29 g of trimethylolpropane trimethacrylate, 5.86 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.28 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 2.04 g, benzophenone 0.51 g, 2,6-di-tert-butyl-4-methylphenol 0.77 g, SANOL (registered trademark) LS-785 (Sankyo Corporation) 1.28 g was added and stirred at 80 ° C. for 2 hours to mix, and then depressurized to 13 kPa and defoamed to obtain a viscous liquid curable resin composition at 80 ° C.

[Reference Example 2]
Regular packing Helipak packing No. 3, a 2 L flask equipped with a distillation tower having a packing height of 300 mm and an inner diameter of 30 mm, and a fractionation head was charged with 534.8 g (5.04 mol) of diethylene glycol and 465.8 g (5.29 mol) of ethylene carbonate, After stirring and dissolving at 70 ° C. and replacing the system with nitrogen, 0.40 g of tetrabutoxy titanium was added as a catalyst. This flask was heated while extracting a part of the reflux liquid from the fractionation head so that the internal temperature was 155 to 160 ° C. and the pressure was 5 to 10 kPa, and reacted for 27 hours. Then, remove the packed distillation column, replace it with a simple distillation device, raise the internal temperature to 160-170 ° C, drop the pressure to 0.2 kPa, and distill off the raw materials (diethylene glycol, ethylene carbonate) remaining in the reaction kettle did. Then, it reacted for 11 hours, distilling the diethylene glycol produced | generated by reaction with an internal temperature of 160-170 degreeC and a pressure of 0.1 kPa with a single distillation apparatus. Thereafter, 0.27 g of monobutyl phosphate was added and the mixture was stirred at 95 ° C. for 3 hours to deactivate tetrabutoxy titanium. By this reaction, 326.8 g of a polycarbonate diol that was viscous at room temperature was obtained. The active hydrogen group value of the obtained polycarbonate diol was 54.4 (number average molecular weight Mn = 2063).
In a 300 mL separable flask equipped with a stirrer, 200.0 g of the above polycarbonate diol, 0.22 g of 2,6-di-tert-butyl-4-methylphenol, 0.04 g of adipic acid, 12.26 g of tolylene diisocyanate, 0.02 g of di-n-butyltin dilaurate was added. In a dry air atmosphere, tolylene diisocyanate was added, and the mixture was stirred at 40 ° C. for 30 minutes and then at 80 ° C. for 3 hours. Thereafter, 8.44 g of 2-methacryloyloxyethyl isocyanate and 0.01 g of di-n-butyltin dilaurate were added and stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of diethylene glycol was connected by a urethane bond and a polymer having a double bond (number average molecular weight Mn by GPC method = 7470) was obtained.
Thereafter, ethylene glycol phenyl ether methacrylate 32.76 g, trimethylolpropane trimethacrylate 18.18 g, silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.) 16.93 g, silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 3.68 g 2,2-dimethoxy-2-phenylacetophenone 5.91 g, benzophenone 1.47 g, 2,6-di-tert-butyl-4-methylphenol 2.22 g, Sanol (registered trademark) LS-785 (Sankyo Corporation) 3.69 g was added and mixed by stirring at 80 ° C. for 2 hours, and then degassed by reducing the pressure to 13 kPa to obtain a viscous liquid curable resin composition at 80 ° C.

[Reference Example 3]
Polycarbonate diol “T4672” (active hydrogen group number = 53.7, number average molecular weight Mn = 2089, copolymer polycarbonate of 1,4-butanediol and 1,6-hexanediol in a 300 mL separable flask equipped with a stirrer Diol, Asahi Kasei Chemicals Corporation) 65.46 g, 2,6-di-tert-butyl-4-methylphenol 0.08 g, adipic acid 0.01 g, tolylene diisocyanate 3.91 g, di-n-butyltin dilaurate 001 g was added. In a dry air atmosphere, tolylene diisocyanate was added, and the mixture was stirred at 40 ° C. for 30 minutes and then at 80 ° C. for 3 hours. Thereafter, 2.75 g of 2-methacryloyloxyethyl isocyanate and 0.002 g of di-n-butyltin dilaurate were added and stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of diethylene glycol was linked by a urethane bond and a polymer having a double bond (number average molecular weight Mn by GPC method = 15033) was obtained.
Thereafter, 23.85 g of ethylene glycol phenyl ether methacrylate, 7.15 g of diethylene glycol butyl ether methacrylate, 0.13 g of trimethylolpropane trimethacrylate, 5.50 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), silicone oil KF-410 (Shin-Etsu Chemical) 1.20 g, 2,2-dimethoxy-2-phenylacetophenone 0.72 g, benzophenone 1.20 g, 2,6-di-tert-butyl-4-methylphenol 0.73 g, Sanol (registered trademark) 1.16 g of LS-785 (Sankyo Co., Ltd.) was added and stirred and mixed at 80 ° C. for 2 hours, then degassed by reducing the pressure to 13 kPa, and a viscous liquid curable resin composition at 80 ° C. Obtained.

Using each of the curable resin compositions obtained in Examples 1 to 5 and Reference Examples 1 to 3, printing original plates were produced by the following method.
After thinly applying diethylene glycol to a 15′14′0.5 cm glass plate, a PET film was placed thereon and rubbed closely with a spatula. A square frame with a side of 10 cm made of a sponge frame fixed by double-sided sealing on the film and an aluminum spacer with a thickness of 3 mm were placed at the four corners outside the frame. The prepared jig was placed on a hot plate at about 90 ° C.
After pouring the curable resin composition of Examples 1 to 5 or Reference Examples 1 to 3 into the frame of the jig, the PET film surface is a curable resin composition with a PET film surface coated with diethylene glycol. Covered to touch. Thereafter, the upper and lower glass plates were clamped and fixed.
The jig surface was exposed to 500 mJ / cm ² (illuminance 33.7 mW / cm ² , time 14.8 seconds) using a high-pressure mercury lamp (trade name: HC-98) manufactured by Sen Engineering Co., Ltd. On the other hand, exposure was further performed at 500 mJ / cm ² . Irradiation to each surface was performed 12 times in total, and a total of 6000 mJ / cm ² exposure was performed to prepare a printing original plate.

[Example 6]
Instead of 2,2-dimethoxy-2-phenylacetophenone, benzophenone and 2,6-di-tert-butyl-4-methylphenol used in Example 1, t-butyl peroxy-2-ethylhexyl carbonate (“perbutyl ( A curable resin composition was obtained in the same manner as in Example 1 except that (registered trademark) E ”, Nippon Oil & Fat Co., Ltd., and 10-hour half-life of 100 ° C. were used.

[Example 7]
Instead of 2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2,6-di-tert-butyl-4-methylphenol, t-butylperoxy-2-ethylhexyl carbonate (“Perbutyl® E”, A curable resin composition was obtained in the same manner as in Example 2 except that Nippon Oil & Fat Co., Ltd. was used.

Each of the curable resin compositions obtained in Examples 6 and 7 was sandwiched with a 100 μm polyester film, and a pressure of 10 kg / cm ² for 60 minutes at 130 ° C. with a press using a 3 mm thick spacer. To prepare a printing original plate having a thickness of 3.0 mm.

  Table 1 shows the results of measuring the swelling ratio and laser engraving property of the printing original plates of each Example and Reference Example.

The polycarbonate diol composition of the present invention, the polymer, and the curable resin composition containing these are suitable for printing using an ink containing an organic solvent, and have excellent solvent resistance characterized by greatly improving printing accuracy. The printing plate and the printing original plate can be manufactured.
Further, the polycarbonate diol composition, the polymer, and the curable resin composition containing these are also suitable for the production of a printing plate precursor for laser engraving in which a printing plate is formed by image formation by laser engraving.
The present invention can be suitably used in at least one printing application selected from flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing.

Claims (29)

A polycarbonate diol composition comprising a polycarbonate diol (a1) and a monomer (a2),
The polycarbonate diol (a1) is a polycarbonate diol represented by the following formula (1) and having a number average molecular weight of 100 to 50,000,
Formula (1):

(In the formula, each R ₁ is independently a straight chain having 3 to 50 carbon atoms, which may contain at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton; Represents a branched and / or cyclic hydrocarbon group.)
The monomer (a2) is a monomer having a number average molecular weight of 60 to 600 represented by the following formula (2):
Formula (2):

(In the formula, each R ₂ is independently a straight chain having 1 to 50 carbon atoms which may contain at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, Represents a branched chain and / or a cyclic hydrocarbon group, and each X independently represents a group containing active hydrogen.)
A polycarbonate diol composition having a number average molecular weight of 60 to 1,000. The polycarbonate diol composition according to claim 1, wherein R ₁ contains at least one ether bond. The polycarbonate diol composition according to claim 1 or 2, wherein R ₁ is a group derived from diethylene glycol. The polycarbonate diol composition according to any one of claims 1 to 3, and a polyisocyanate compound (b) having an isocyanate group equivalent less than the equivalent of the terminal group of the polycarbonate diol composition are polymerized,
A polymer in which the remaining terminal group of the polymerized polycarbonate diol composition is bonded to isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate. The polycarbonate diol composition according to any one of claims 1 to 3 and an isocyanate group equivalent polyisocyanate compound (b) exceeding the equivalent of the terminal group of the polycarbonate diol composition are polymerized,
A polymer in which a remaining isocyanate group of the polymerized polyisocyanate compound (b) is bonded to a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate by a urethane bond.   The polymer according to claim 4 or 5, wherein the polyisocyanate compound (b) is a diisocyanate compound.   A curable resin composition for a printing plate or a printing original plate, comprising a polymer (B1) produced from the polycarbonate diol composition according to any one of claims 1 to 3.   The polymer (B1) is a polymer having a chemical bond formed between a terminal hydroxyl group of the polycarbonate diol composition and another compound and having a polymerizable unsaturated group. Curable resin composition for printing plate or printing original plate.   The curable resin composition for a printing plate or a printing original plate according to claim 8, wherein the chemical bond is a urethane bond.   The curable resin composition for a printing plate or a printing original plate according to claim 8 or 9, wherein the polymerizable unsaturated group is a double bond.   The curable resin composition for printing plates or printing original plates according to any one of claims 7 to 10, wherein the number average molecular weight of the polymer (B1) is 400 to 100,000.   A curable resin composition for a printing plate or printing original plate, comprising the polymer according to any one of claims 4 to 6.   The curable composition for printing plate or printing plate precursor according to any one of claims 7 to 12, further comprising an organic compound (C) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000. Resin composition.   The curable resin composition for printing plates or printing plate precursors according to any one of claims 7 to 13, further comprising inorganic fine particles (D).   The curable resin composition for a printing plate or printing original plate according to any one of claims 7 to 14, further comprising a photopolymerization initiator (E).   The curable resin composition for a printing plate or a printing original plate according to any one of claims 7 to 15, further comprising a thermal polymerization initiator (F). The terminal group X of the monomer (a2) having a molecular weight of 60 to 600 represented by the following formula (2), and the polyisocyanate compound (b) having an isocyanate group equivalent less than the terminal group equivalent of the monomer (a2) Polymerized,
The polymer which the terminal group X of the monomer (a2) which has superposed | polymerized and the isocyanatoalkyl acrylate and / or isocyanatoalkylmethacrylate couple | bond together.
Formula (2):

(In the formula, each R ₂ independently contains at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, and a straight chain having 2 to 50 carbon atoms and And / or a branched hydrocarbon group, each X independently represents a group containing active hydrogen.) The end group X of the monomer (a2) having a molecular weight of 60 to 600 represented by the following formula (2), and an isocyanate group equivalent polyisocyanate compound (b) exceeding the end group equivalent of the monomer (a2) are: Polymerized,
A polymer in which the remaining isocyanate group of the polymerized polyisocyanate compound (b) is bonded to a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate by a urethane bond.
Formula (2):

(In the formula, each R ₂ independently contains at least one atom selected from the group consisting of nitrogen, sulfur and oxygen in the carbon skeleton, and a straight chain having 2 to 50 carbon atoms and And / or a branched hydrocarbon group, each X independently represents a group containing active hydrogen.)   A curable resin composition for a printing plate or printing original plate comprising the polymer (B2) according to claim 17 or 18.   The curable resin composition for printing plates or printing plate precursors according to claim 19, wherein the polymer (B2) has a number average molecular weight of 400 to 100,000.   21. The curable resin composition for a printing plate or printing plate precursor according to claim 19 or 20, further comprising an organic compound (C) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000.   The curable resin composition for a printing plate or printing original plate according to any one of claims 19 to 21, further comprising inorganic fine particles (D).   The curable resin composition for a printing plate or printing original plate according to any one of claims 19 to 22, further comprising a photopolymerization initiator (E).   The curable resin composition for a printing plate or printing original plate according to any one of claims 19 to 23, further comprising a thermal polymerization initiator (F).   The printing original plate manufactured using the curable resin composition for printing plates or printing original plates of any one of Claims 7-16 and Claims 19-24.   A printing plate obtained by laser engraving the printing original plate according to claim 25. A step of molding the curable resin composition for a printing plate or a printing original plate according to any one of claims 7 to 16 and claims 19 to 24 into a sheet shape or a cylindrical shape,
The manufacturing method of a printing original plate including the process of hardening | curing the shape | molded printing plate or the curable resin composition for printing original plates.   A method for producing a printing plate, comprising a step of laser engraving the printing original plate according to claim 25 or the printing original plate obtained by the production method according to claim 27. A step of molding the curable resin composition for a printing plate or a printing original plate according to any one of claims 7 to 16 and 19 to 24 into a sheet shape or a cylindrical shape,
Placing a mask layer on the surface of the curable resin composition for a printing plate or printing original plate formed into the sheet or cylinder; and
Irradiating actinic rays from the surface side where the mask layer is disposed;
A method for producing a printing plate, comprising: removing an unirradiated portion.