JP5425556B2 - Method for producing polymer for printing original plate - Google Patents

Description

  The present invention relates to a method for producing a polymer for a printing original plate, a method for producing a resin composition, a method for producing a printing original plate, and a method for producing a printing plate.

  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 a printing original plate.
For example, Patent Document 1 discloses a resin composition for a printing original plate and a printing original plate, which are capable of laser engraving, made of 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 an object of the present invention to provide a method for producing a printing plate polymer that can provide a suitable printing plate or printing plate.

  As a result of diligent studies to solve the above problems, the present inventors have used a polycarbonate diol that has been subjected to a depolymerization step, thereby making it possible to produce a printing plate or printing plate precursor that is excellent in solvent resistance. The present invention has been completed by finding that a polymer can be produced.

That is, the present invention is as follows.
[1]
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
The manufacturing method of the polymer for printing original plates containing.
[2]
In the step (2), the polyisocyanate compound (b) is reacted with an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′). .
[3]
The method for producing a printing plate polymer according to [2], further comprising a step of reacting an isocyanatoalkyl acrylate and / or an isocyanatoalkyl methacrylate after the step (2).
[4]
In the step (2), the polyisocyanate compound (b) is reacted with an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′). .
[5]
The method for producing a printing original plate polymer according to [4], further comprising a step of reacting the hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate after the step (2).
[6]
The manufacturing method of the polymer for printing original plates in any one of [1]-[5] whose reaction temperature of the said process (1) is 100 degreeC or more and 250 degrees C or less.
[7]
The method for producing a printing original plate polymer according to any one of [1] to [6], wherein the reaction temperature in the step (2) is 20 ° C or higher and 200 ° C or lower.
[8]
The method for producing a printing original plate polymer according to any one of [1] to [7], wherein the polycarbonate diol (a ′) has a number average molecular weight of 100 or more and less than 1,000.
[9]
The method for producing a printing original plate polymer according to any one of [1] to [8], wherein the polycarbonate diol (a) is represented by the following formula (I).
Formula (I):

(In the formula, each R ₁ independently contains at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton, and is a straight chain or branched chain having 3 to 50 carbon atoms. Represents a chain and / or a cyclic hydrocarbon group.)
[10]
The method for producing a printing original plate polymer according to [9], wherein R ₁ includes one or more ether bonds.
[11]
The method for producing a printing original plate polymer according to [9] or [10], wherein R ₁ is a group represented by — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —.
[12]
The method for producing a printing original plate polymer according to any one of [1] to [11], wherein the polyisocyanate compound (b) is a diisocyanate compound.
[13]
A method for producing a resin composition, comprising:
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 to 50.000,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
The manufacturing method of the resin composition containing this.
[14]
A method for producing a printing original plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(5) A step of curing the resin composition formed into the sheet shape or the cylindrical shape,
A method for producing a printing original plate containing
[15]
A method for producing a printing plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(5) A step of curing the resin composition formed into the sheet shape or the cylindrical shape,
(6) A step of laser engraving the printing original plate obtained by the step (5),
A method for producing a printing plate, comprising:
[16]
A method for producing a printing plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(7) A step of disposing a mask layer on the surface of the resin composition molded into the sheet or cylinder,
(8) A step of irradiating actinic rays from the surface side on which the mask layer is disposed,
(9) removing unirradiated portions;
A method for producing a printing plate, comprising:

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the polymer for printing original plates which enables manufacture of the printing plate or printing original plate 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.

<Method for producing polymer for printing original plate>
The method for producing the printing original plate polymer of the present embodiment (hereinafter sometimes referred to as “polymer (A)”) is as follows:
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) A step of reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b) is included.
Since the printing original plate polymer obtained by the production method of the present embodiment is excellent in solvent resistance, the printing plate and the printing original plate polymer (hereinafter sometimes simply referred to as “printing original plate polymer”). Can be suitably used.

In the production method of the polymer (A), as the step (2), the polyisocyanate compound (b) can be reacted with an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′). It is preferable to further include the step of reacting isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate after step (2).
As the step (2), the polyisocyanate compound (b) can be reacted with an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′). It is preferable that the process further includes the step of reacting hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate after step (2). Alternatively, the polyisocyanate compound (b) can be reacted with an isocyanate group equivalent of the terminal hydroxyl equivalent of the polycarbonate diol (a ′), and then hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate and isocyanatoalkyl acrylate and / Or Isocyanatoalkyl methacrylate may be reacted.

The equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′) can be measured by the method described in the following examples. The isocyanate group equivalent can be determined as a theoretical value of the polyisocyanate compound (b).
When the polyisocyanate compound (b) is reacted using an isocyanate group equivalent less than the terminal hydroxyl group equivalent of the polycarbonate diol (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 hydroxyl group equivalent of the polycarbonate diol (a ′), if the equivalent ratio (b) / (a ′) exceeds 1, Although not particularly limited, it is preferably 1.01 or more and 3 or less.

<Polycarbonate diol (a)>
The number average molecular weight of the polycarbonate diol (a) is 1,000 or more and 50,000 or less.
In the present embodiment, the “number average molecular weight” can be measured by the method described in the following examples.

The polycarbonate diol (a) can be produced by a conventionally known method as described in, for example, Japanese Patent Publication No. 5-29648. Specifically, the polycarbonate diol (a) is produced by a transesterification reaction between a diol and a carbonate ester. can do.
The polycarbonate diol (a) is preferably a polycarbonate diol represented by the following formula (I) because the solvent resistance is improved.
Formula (I):

(In the formula, each R ₁ independently contains at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton, and is a straight chain or branched chain having 3 to 50 carbon atoms. Represents a chain and / or a cyclic hydrocarbon group.)

In the formula (I), each R ₁ independently contains an oxygen atom or the like (at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen) in the carbon skeleton. 3 to 50 linear, branched and / or cyclic hydrocarbon groups are represented. R ₁ 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.

The linear hydrocarbon group as R ₁ is, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16-hexadecanediol, 1,20-eicosanediol, etc. Examples include hydrocarbon groups derived from chain aliphatic diols.

Examples of the branched hydrocarbon group as R ₁ include 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, , 2,3-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-hexanedi 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 50 carbon atoms such as 1,2-decanediol and 8,13-dimethyl-1,20-eicosanediol.

The cyclic hydrocarbon group as R ₁ is, for example, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol. 1,4-cyclohexanedimethanol, m-xylene-α, α'-diol, p-xylene-α, α'-diol, 2,2-bis (4-hydroxycyclohexyl) -propane, 2,2-bis Examples include hydrocarbon groups derived from cyclic diols having 3 to 50 carbon atoms such as (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.

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

In the formula (I), from the viewpoint of solvent resistance, R ₁ preferably contains one or more ether bonds. 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 the present embodiment, the polycarbonate diol (a) can be used alone or in combination of two or more depending on the purpose.
The two or more polycarbonate diol (a), 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.

<Process (1): Depolymerization process>
The depolymerized polycarbonate diol (a ′) can be obtained from the polycarbonate diol (a) by the depolymerization step in the method for producing the printing original plate polymer of the present embodiment.
The depolymerization step in the present embodiment is not particularly limited as long as the molecular chain of the polycarbonate diol (a) is cleaved at any position, but in addition to the polycarbonate diol (a), a straight chain having 3 to 50 carbon atoms. In view of improving the productivity of the polycarbonate diol (a ′), the reaction is preferably performed in the presence of a diol having a branched chain and / or a cyclic hydrocarbon group, and the same diol as the raw material of the polycarbonate diol (a) It is more preferable to make it react in presence of.
The reaction temperature in the depolymerization step is not particularly limited, but is preferably 100 ° C to 250 ° C, more preferably 120 ° C to 220 ° C, and further preferably 130 ° C to 200 ° C.
When the reaction temperature in the depolymerization step is 100 ° C. or more and 250 ° C. or less, the productivity of the polycarbonate diol (a ′) can be improved and the quality deterioration due to the side reaction can be suppressed.
The reaction time in the depolymerization step is not particularly limited, but is preferably 1 hour or more and 20 hours or less, more preferably 1 hour or more and 12 hours or less, and further preferably 2 hours or more and 8 hours or less.
When the reaction time in the depolymerization step is 1 hour or more and 20 hours or less, the productivity of the polycarbonate diol (a ′) can be improved and the quality deterioration due to the side reaction can be suppressed.

In the depolymerization step, a catalyst can be used to accelerate the reaction. Examples of the catalyst include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, cobalt, zinc, aluminum, germanium, tin, lead, antimony, arsenic, and cerium. And compounds thereof. Examples of the metal compound include oxides, hydroxides, salts, alkoxides, and organic compounds.
Examples of the catalyst include titanium compounds such as tetraisopropoxy titanium and tetra-n-butoxy titanium, tin compounds such as di-n-butyltin dilaurate, di-n-butyltin oxide and dibutyltin diacetate, lead acetate, and lead stearate. Lead compounds are preferred.

<Polycarbonate diol (a ')>
The polycarbonate diol (a ′) is not particularly limited as long as it is obtained by depolymerizing the polycarbonate diol (a), but the number average molecular weight of the polycarbonate diol (a ′) is preferably 100 or more and less than 1,000. More preferably, it is 200 or more and 900 or less, More preferably, it is 300 or more and 800 or less.
By using the polycarbonate diol (a ′) having a number average molecular weight of 100 or more and less than 1,000 for the production of the polymer (A), a printing plate or printing original plate exhibiting a particularly excellent solvent resistance can be obtained. Therefore, it is preferable.

In the present embodiment, the polycarbonate diol (a ′) can be used alone or in combination of two or more depending on the purpose.
The two or more kinds of polycarbonate diols (a ′) may be two or more kinds of polycarbonate diols having different R ₁ in the polycarbonate diol (a), and R ₁ is the same, for example, two or more kinds having different number average molecular weights. The polycarbonate diol may be used.

<Polyisocyanate compound (b)>
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.
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.

<Process (2): Polymerization process>
The polymer (A) obtained by polymerizing the polycarbonate diol (a ′) and the polyisocyanate compound (b) can be obtained by the polymerization step in the method for producing a printing original plate polymer according to this embodiment.

The reaction temperature in the polymerization step is not particularly limited, but 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, the productivity of the polymer (A) can be improved and quality deterioration due to side reactions 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 (A) can be improved and quality deterioration due to side reactions can be suppressed.

In the production method of the polymer (A), in the step (2), when the polyisocyanate compound (b) is polymerized by using an isocyanate group equivalent less than the terminal hydroxyl group equivalent of the polycarbonate diol (a ′), the step (2) ) Isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate is preferably reacted.
In the step (2), when the polyisocyanate compound (b) is polymerized using an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol (a ′), after the step (2), the hydroxyalkyl acrylate and / or Alternatively, it is preferable to react with hydroxyalkyl methacrylate.
In the reaction, the reaction can be performed under the same conditions as in the polymerization step.

Examples of the isocyanatoalkyl acrylate and isocyanatoalkyl methacrylate include isocyanatoethyl (meth) acrylate and isocyanatopropyl (meth) acrylate, which can be used alone or in combination of two or more.
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.

  By reacting the (meth) acrylate compound as described above, a double bond as a polymerizable unsaturated group can be introduced to the molecular chain terminal of the polymer (A).

As another aspect of the present embodiment, a polycarbonate diol (a ′) obtained by depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less, and the polycarbonate diol (a ′) This is a printing original plate polymer obtained by polymerizing a polyisocyanate compound (b) having an isocyanate group equivalent less than the terminal hydroxyl group by a urethane bond.
The printing original plate polymer is preferably a polymer in which the terminal hydroxyl group remaining in the polymerized polycarbonate diol (a) is bonded to the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate by a urethane bond. .
As another aspect of the present embodiment, a polycarbonate diol (a ′) obtained by depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less, and the polycarbonate diol (a ′ And a polyisocyanate compound (b) having an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group is a printing original plate polymer polymerized by a urethane bond.
The printing original plate polymer is preferably a polymer 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.

  These printing original plate polymers are preferably polymers produced by the production method of the present embodiment.

<Method for producing resin composition>
In the method for producing a resin composition of the present embodiment, the polymer (A) obtained by the steps (1) and (2) has an organic group having a polymerizable unsaturated group and a number average molecular weight of less than 5,000. A step of adding at least one selected from the group consisting of the compound (B), the inorganic fine particles (C), the photopolymerization initiator (D), and the thermal polymerization initiator (E) is included.
In the method for producing a resin composition, although not particularly limited, the resin composition can be produced by mixing following step (2) under the same temperature conditions as in step (2). it can.

<Organic compound having a polymerizable unsaturated group and a number average molecular weight of less than 5,000>
The method for producing the 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 include a step of adding an organic compound (hereinafter sometimes referred to as “organic compound (B)”).
In the present embodiment, the “number average molecular weight of the organic compound (B)” means a molecular weight when it is a single compound, and is measured by a GPC method (gel filtration chromatography method) when it is not a single compound. Means a value that can be

In the present 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 (B) 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 their derivatives; 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 (B) 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 (B) 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 glycol or propylene oxide) added to ether, 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 (B) can be used alone or in combination of two or more depending on the purpose.

<Inorganic fine particles>
The method for producing a resin composition of the present embodiment may be further described as inorganic fine particles (hereinafter referred to as “inorganic fine particles (C)”) in order to further improve the laser engraving property when it is used as a printing original plate. It is preferable to include a step of adding.

  The material and form of the inorganic fine particles (C) are not limited, but those having fine pores or fine voids in the particles are preferable. The inorganic fine particles (C) have a function of effectively absorbing and removing liquid debris generated when the original resin is decomposed by a laser when the resin composition is used as a printing original plate. The inorganic fine particles ( Inclusion of C) not only improves the accuracy of the relief image by laser engraving, but also makes the cleaning operation after laser engraving extremely simple.

Although there is no restriction | limiting in the magnitude | size of inorganic type microparticles | fine-particles (C), 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 (C), 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 (C), Preferably it is 0.01-10 mL / g, 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 (C), 1-1,500m < ² > / g is preferable, More preferably, it is 10-800m < ² > / g.
There is no restriction | limiting in the shape of inorganic type microparticles | fine-particles (C), A spherical shape, flat shape, needle shape, amorphous, or a particle | grain with a processus | protrusion on the surface etc. 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 (C) can be used alone or in combination of two or more according to the purpose.

<Photopolymerization initiator>
It is preferable that the manufacturing method of the resin composition of this embodiment includes the process of adding a photoinitiator (Hereinafter, it may describe as a "photoinitiator (D).").
The photopolymerization initiator (D) may be appropriately selected from known ones. For example, radical polymerization exemplified in “Polymer Data Handbook-Fundamentals” edited by the Society of Polymer Science, Japan (1986, published by Baifukan). Initiators for cationic polymerization and anionic polymerization can be used.
Crosslinking of the 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 (D) 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 (D) can be used combining 1 type (s) or 2 or more types according to the objective.

<Thermal polymerization initiator>
It is preferable that the manufacturing method of the resin composition of this embodiment includes the process of adding a thermal polymerization initiator (Hereinafter, it may be described as a thermal polymerization initiator (E).).
The thermal polymerization initiator (E) is not particularly limited, and examples thereof include all thermal polymerization initiators that can be used for radical polymerization reactions and ring-opening polymerization reactions.
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, whereby 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 (E) can be used alone or in combination of two or more depending on the purpose.

The thermal polymerization initiator (E) is preferably liquid at 20 ° C. from the viewpoint of easy mixing.
The thermal stability of the thermal polymerization initiator (E) is usually determined by a 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 (E) 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 (E) usually have a 10 h-t _1/2 of preferably 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 compounds such as Si—O—O—Si type, Si—O—O—C type, and Si—O—O—R (alkyl) type.
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 thermal polymerization initiator (E) can be used alone or in combination of two or more depending on the purpose.

In the method for producing a resin composition of the present embodiment, the amount of the organic compound (B), inorganic fine particles (C), photopolymerization initiator (D), and thermal polymerization initiator (E) is not limited, but the polymer (A) The organic compound (B) is 5 to 200 parts by mass, the inorganic fine particles (C) are 1 to 100 parts by mass, the photopolymerization initiator (D) is 1 to 100 parts by mass, and heat is 100 parts by mass. It is preferable to add 1-100 mass parts of polymerization initiators (E).
The method for producing a resin composition of the present embodiment may include a step of adding a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like depending on applications and purposes. The addition amount is preferably in the range of 10% by mass or less with respect to the resin composition.

  The resin composition obtained by the method for producing a resin composition of the present embodiment is a curable resin composition and is suitably used for printing original plates or printing plate applications.

<Printing master>
The method for producing a printing original plate according to the present embodiment comprises a step of molding the resin composition obtained by the method for producing a resin composition into a sheet or cylinder, and a resin composition molded into the sheet or cylinder. A step of curing.
By using the resin composition, it is possible to produce a printing original plate excellent in solvent resistance.

There is no restriction | limiting in the method of shape | molding a resin composition in a sheet | seat or cylindrical shape, The shaping | molding method of the existing 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 degrade the performance of the resin composition. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, the resin composition can be molded on an underlay called a back film made of a material such as PET (polyethylene terephthalate) or nickel.
The molding step in the method for producing the printing original plate may be a step of directly molding the 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 resin composition shape | molded by the sheet form or the cylindrical form, The existing hardening method of 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 this embodiment includes a step of laser engraving a printing original plate obtained by the method for producing a printing original plate, and forms 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 resin composition in 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 (inside of a device in which a liquid 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) In addition, a printing plate can be formed by using a laser light source for laser engraving). 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.

A so-called photolithography method can be cited as a method for producing a printing plate of the present embodiment. A resin composition obtained by a method for producing a printing original plate is formed into a sheet shape or a cylindrical shape, and the sheet shape or the cylindrical shape is obtained. A step of disposing a negative mask layer on the surface of the molded resin 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) including.
Examples of the actinic ray include at least one selected from the group consisting of light, electron beam, and heat, and the resin composition molded into a sheet shape or a cylindrical shape is partially cured by the exposure process.
By using the resin composition in the present embodiment, a printing plate having excellent solvent resistance can be produced.

<Application>
The printing plate obtained by the production method of the present 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, although an embodiment and a reference example explain this embodiment in detail, this embodiment is not limited only to the following examples. Various characteristics in the following Examples and Reference Examples were measured according to the following methods.

<Measurement method>
1. OH value of polycarbonate diol 12.5 g of acetic anhydride was diluted with 50 mL of 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 OH value was calculated using the following formula (i) as the terminal hydroxyl group equivalent of polycarbonate diol.
Formula (i):
OH 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. Number average molecular weight of polycarbonate diol The terminals of the polycarbonate diol in Examples and Reference Examples were substantially all hydroxyl groups as measured 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.
The number average molecular weight of the obtained polycarbonate diol was determined by the following formula (ii).
Formula (ii):
Number average molecular weight Mn = 2 / (OH value × 10 ⁻³ /56.11)

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

4). 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]
Regular packing Helipak packing No. Into a 20 L reaction kettle equipped with 3 and having a distillation height of 400 mm and an inner diameter of 60 mm, and a fractionation head, 12,825 g (120.9 mol) of diethylene glycol and 11,175 g (126.9 mol) of ethylene carbonate were charged. After stirring and dissolving at 70 ° C. 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. This reaction yielded 10,020 g of a viscous liquid polycarbonate diol at room temperature. The polycarbonate diol thus obtained had an OH value of 69.5 (number average molecular weight Mn = 1,614).
99.79 g of the above polycarbonate diol and 57.03 g of diethylene glycol were placed in a 500 mL flask equipped with a stirrer, and depolymerized by stirring at 150 ° C. for 5 hours. The polycarbonate diol obtained here had an OH value of 436.6 (number average molecular weight Mn = 257).
Into a 300 mL separable flask equipped with a stirrer, 50.05 g of the polycarbonate diol having the above number average molecular weight Mn = 257 was added, and 27.23 g of tolylene diisocyanate was added in 30 portions every 30 minutes. In a dry air atmosphere, tolylene diisocyanate was first added, and the mixture was stirred at 40 ° C. for 1 hour and then at 80 ° C. for 2 hours and 30 minutes. Thereafter, 12.30 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 was obtained. Thereafter, 13.27 g of ethylene glycol phenyl ether methacrylate, 7.36 g of trimethylolpropane trimethacrylate, 6.86 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.49 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 0.89 g, benzophenone 1.49 g, 2,6-di-tert-butyl-4-methylphenol 0.90 g, SANOL (registered trademark) LS-785 (Sankyo Corporation) ) 1.49 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 resin composition at 80 ° C.

[Example 2]
A 500 mL flask equipped with a stirrer was charged with 120.21 g of polycarbonate diol of Example 1 having a number average molecular weight Mn = 1,614 and 30.07 g of diethylene glycol, and depolymerized by stirring at 150 ° C. for 4 hours. The polycarbonate diol obtained here had an OH value of 262.5 (number average molecular weight Mn = 427).
Into a 300 mL separable flask equipped with a stirrer, 70.05 g of the polycarbonate diol having the number average molecular weight Mn = 427 was added, and 25.34 g of tolylene diisocyanate was added in 30 portions every 30 minutes. 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 3 hours and 30 minutes. Thereafter, 5.86 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 was obtained. Thereafter, 15.01 g of ethylene glycol phenyl ether methacrylate, 8.33 g of trimethylolpropane trimethacrylate, 7.76 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), 1.69 g of silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 2,2-dimethoxy-2-phenylacetophenone 1.01 g, benzophenone 1.69 g, 2,6-di-tert-butyl-4-methylphenol 1.02 g, Sanol (registered trademark) LS-785 (Sankyo Corporation) 1.69 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 resin composition at 80 ° C.

Example 3
A 500 mL flask equipped with a stirrer was charged with 120.17 g of polycarbonate diol of Example 1 having a number average molecular weight Mn = 1,614 and 19.15 g of diethylene glycol, and depolymerized by stirring at 150 ° C. for 4 hours. The polycarbonate diol obtained here had an OH value of 204.7 (number average molecular weight Mn = 548).
In a 300 mL separable flask equipped with a stirrer, 75.03 g of the polycarbonate diol having the number average molecular weight Mn = 548 was added, and 21.03 g of tolylene diisocyanate was added in 30 portions every 30 minutes. 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 and 30 minutes. Thereafter, 5.10 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 was obtained. 40.06 g was taken out of the obtained polymer, 5.94 g of ethylene glycol phenyl ether methacrylate, 3.29 g of trimethylolpropane trimethacrylate, 3.07 g of silica gel C-1504 (Fuji Silysia Chemical Ltd.), silicone oil KF- 410 (Shin-Etsu Chemical Co., Ltd.) 0.66 g, 2,2-dimethoxy-2-phenylacetophenone 0.40 g, benzophenone 0.66 g, 2,6-di-tert-butyl-4-methylphenol 0.40 g, sanol (Registered trademark) LS-785 (Sankyo Co., Ltd.) 0.69 g was added and mixed by stirring at 80 ° C. for 2 hours, then degassed by depressurizing to 13 kPa, and a viscous liquid resin composition at 80 ° C. I got a thing.

Example 4
In a 300 mL separable flask equipped with a stirrer, 40.21 g of the polymer obtained in Example 4, 5.94 g of 2-hydroxyethyl methacrylate, 3.29 g of trimethylolpropane trimethacrylate, silica gel C-1504 (Fuji Silysia Chemical) Co., Ltd.) 3.07 g, silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) 0.67 g, 2,2-dimethoxy-2-phenylacetophenone 0.40 g, benzophenone 0.67 g, 2,6-di-tert- After adding 0.40 g of butyl-4-methylphenol and 0.66 g of SANOL (registered trademark) LS-785 (Sankyo Co., Ltd.) and stirring and mixing at 80 ° C. for 2 hours, the mixture was degassed by reducing the pressure to 13 kPa, A viscous liquid resin composition was obtained at 80 ° C.

Example 5
A viscous liquid curable resin composition was obtained at 80 ° C. in the same manner as in Example 1 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 OH number of the obtained polycarbonate diol was 100.0 (number average molecular weight Mn = 1,122).
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 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 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 for defoaming to obtain a viscous liquid 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 obtained polycarbonate diol had an OH value of 54.4 (number average molecular weight Mn = 2,063).
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 linked by a urethane bond and a polymer having a double bond 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 resin composition at 80 ° C.

[Reference Example 3]
Polycarbonate diol “T4672” (OH number = 53.7, number average molecular weight Mn = 2,089, 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 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) After adding 1.16 g of LS-785 (Sankyo Co., Ltd.) and stirring for 2 hours at 80 ° C., the mixture was degassed by reducing the pressure to 13 kPa to obtain a viscous liquid resin composition at 80 ° C. .

Using each resin composition 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 each said curable resin composition in the flame | frame of a jig | tool, it covered with the glass plate which apply | coated diethylene glycol and put PET film so that a PET film surface might contact a curable resin composition. Thereafter, the upper and lower glass plates were clamped and fixed.
This jig was exposed to 500 mJ / cm ² (illuminance 33.7 mW / cm ² , time 14.8 seconds) using a high pressure mercury lamp (HC-98) manufactured by Sen Engineering Co., Ltd., and then the jig surface was reversed. Further, exposure was performed at 500 mJ / cm ² . Irradiation to each surface was performed 12 times in total, and a total of 6,000 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 resin composition was obtained in the same manner except that (registered trademark) E ”, manufactured by NOF Corporation and having a half-life of 10 hours at 100 ° C. was used.

[Example 7]
Instead of 2,2-dimethoxy-2-phenylacetophenone, benzophenone, and 2,6-di-tert-butyl-4-methylphenol used in Example 3, t-butyl peroxy-2-ethylhexyl carbonate (“perbutyl ( A resin composition was obtained in the same manner except that (registered trademark) E ”, manufactured by NOF Corporation) was used.

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

Suitable for printing using an ink containing an organic solvent by the polymer for printing original plate, resin composition, printing original plate and printing plate manufacturing method of the present invention, and having a solvent resistance characterized by greatly improving printing accuracy It was possible to produce excellent printing plates and printing original plates.
In addition, according to the printing original plate polymer, the resin composition, and the printing original plate manufacturing method of the present invention, it is also possible to provide a printing original plate for laser engraving which forms an image by forming an image 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 (16)

(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
The manufacturing method of the polymer for printing original plates containing.   2. The method for producing a printing original plate polymer according to claim 1, wherein in the step (2), the polyisocyanate compound (b) is reacted with an isocyanate group equivalent less than an equivalent of a terminal hydroxyl group of the polycarbonate diol (a ′). .   The method for producing a printing original plate polymer according to claim 2, further comprising, after the step (2), a step of reacting isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate.   The method for producing a printing original plate polymer according to claim 1, wherein, in the step (2), the polyisocyanate compound (b) is reacted with an isocyanate group equivalent exceeding the equivalent of the terminal hydroxyl group of the polycarbonate diol (a '). .   The method for producing a printing original plate polymer according to claim 4, further comprising, after the step (2), a step of reacting a hydroxyalkyl acrylate and / or a hydroxyalkyl methacrylate.   The manufacturing method of the polymer for printing original plates as described in any one of Claims 1-5 whose reaction temperature of the said process (1) is 100 degreeC or more and 250 degrees C or less.   The manufacturing method of the polymer for printing original plates as described in any one of Claims 1-6 whose reaction temperature of the said process (2) is 20 to 200 degreeC.   The method for producing a printing original plate polymer according to any one of claims 1 to 7, wherein the number average molecular weight of the polycarbonate diol (a ') is 100 or more and less than 1,000. The manufacturing method of the polymer for printing original plates as described in any one of Claims 1-8 by which the said polycarbonate diol (a) is represented by following formula (I).
Formula (I):

(In the formula, each R ₁ independently contains at least one atom selected from the group consisting of nitrogen, sulfur, and oxygen in the carbon skeleton, and is a straight chain or branched chain having 3 to 50 carbon atoms. Represents a chain and / or a cyclic hydrocarbon group.) The method for producing a printing original plate polymer according to claim 9, wherein R ₁ includes one or more ether bonds. The method for producing a printing original plate polymer according to claim 9 or 10, wherein R ₁ is a group represented by-(CH ₂ ) ₂ -O- (CH ₂ ) _2- . The manufacturing method of the polymer for printing original plates as described in any one of Claims 1-11 whose said polyisocyanate compound (b) is a diisocyanate compound.
Manufacturing method. A method for producing a resin composition, comprising:
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 to 50.000,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
The manufacturing method of the resin composition containing this. A method for producing a printing original plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(5) A step of curing the resin composition formed into the sheet shape or the cylindrical shape,
A method for producing a printing original plate containing A method for producing a printing plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(5) A step of curing the resin composition formed into the sheet shape or the cylindrical shape,
(6) A step of laser engraving the printing original plate obtained by the step (5),
A method for producing a printing plate, comprising: A method for producing a printing plate,
(1) a step of depolymerizing a polycarbonate diol (a) having a number average molecular weight of 1,000 or more and 50,000 or less,
(2) reacting the polycarbonate diol (a ′) obtained by the step (1) with the polyisocyanate compound (b),
(3) The printing original plate polymer obtained by the step (2) is selected from the group consisting of an organic compound having a number average molecular weight of less than 5,000, inorganic fine particles, a photopolymerization initiator, and a thermal polymerization initiator. Adding at least one of
(4) A step of molding the resin composition obtained by the step (3) into a sheet shape or a cylindrical shape,
(7) A step of disposing a mask layer on the surface of the resin composition molded into the sheet or cylinder,
(8) A step of irradiating actinic rays from the surface side on which the mask layer is disposed,
(9) removing unirradiated portions;
A method for producing a printing plate, comprising: