WO2009084682A1

WO2009084682A1 - Heat-curable resin composition for laser engraved original printing plates

Info

Publication number: WO2009084682A1
Application number: PCT/JP2008/073851
Authority: WO
Inventors: Yoko Tomita; Hiroshi Yamada
Original assignee: Asahi Kasei E-Materials Corporation
Priority date: 2007-12-27
Filing date: 2008-12-26
Publication date: 2009-07-09
Also published as: JP5134012B2; JPWO2009084682A1

Abstract

Disclosed is a heat-curable resin composition for laser engraved original printing plates that contains a resin composition (A) that includes (a) a resin with a number-average molecular weight of at least 1000 and no more than 300,000, (b) an organic compound with a number-average molecular weight of less than 1000 and possessing a polymerizable unsaturated group in the molecule, and (c) a thermal polymerization initiator. Here, the aforementioned resin (a) and/or the aforementioned organic compound (b) contains at least one compound with a carbonate bond in the molecule, and the aforementioned resin composition (A) is liquid at 20ºC.

Description

Thermosetting resin composition for laser engraving printing master

The present invention relates to a thermosetting resin composition for a laser engraving printing original plate. The present invention also relates to a laser engraving printing original plate for forming a concave pattern on the surface by a laser engraving method, a method for producing the same, and a printing plate.

In recent years, surface printing such as flexographic printing, dry offset printing, and letterpress printing using resin relief printing, or surface processing such as embossing, removes the resin on the surface irradiated with laser light. A laser engraving method for forming an uneven pattern has been used. As materials applied to the laser engraving method, vulcanized rubber and a cured photosensitive resin obtained by photocuring a photosensitive resin composition are mainly used. In particular, in recent years, from the viewpoint of shortening the processing time, a technique for laser engraving a photosensitive resin cured product obtained by photocuring a photosensitive resin composition has increased.

Patent Document 1 discloses a method for producing a flexographic printing original plate in which a solid resin composition is thermochemically reinforced at 20 ° C. using a thermoplastic elastomer.
Patent Document 2 discloses that a thermal polymerization initiator is added to an elastomer layer to be laser engraved, and this layer is thermally crosslinked. In the method disclosed in Patent Document 2, a photocrosslinkable flexible printing plate based on a thermoplastic elastomer is produced in a smart manner by extrusion and rolling at an elevated temperature using a thermostable photoinitiator. To do.
Patent Document 3 discloses a laser engraving printing original plate that can be mixed and molded and thermally crosslinked by treating an elastomeric binder, a laser irradiation absorbent, and a thermal polymerization initiator in a solvent.
Patent Document 4 discloses a photosensitive resin composition that is liquid at 20 ° C.

Japanese Patent No. 2846954 European Patent Application Publication No. 0640044 Special table 2004-506551 gazette Japanese Patent No. 3801592

However, in laser engraving printing plates, especially when a large amount of materials such as pigments that reduce light transmittance are added or when a thick film is required, thermosetting laser engraving printing plates have been craved. However, there is no material in the prior art that has excellent manufacturing and storage stability, high productivity of printing plates, and does not use volatile components such as solvents and can form thermosetting laser engraving printing plates. It is. Further, there is no known laser engraving printing plate that can be cured in the air, has a low tack on the surface of the printing plate, and has a low hardness of the thermoset, and can be printed on low-quality paper or corrugated paper with high surface roughness.

In the technique disclosed in Patent Document 1, a thermoplastic polymerization initiator and a monomer having a polymerizable unsaturated group undergo a process of heating over 100 ° C. when mixing, and therefore a thermal polymerization initiator that can be added. It is necessary to select a compound that does not react at the heating temperature during mixing. Therefore, since the resin composition is heated to a very high temperature to be strengthened thermochemically, the support is deformed by heat and the dimensional stability cannot be ensured.

In the technique disclosed in US Pat. No. 6,053,086, premature crosslinking can occur due to high working temperatures during the production of the thermal crosslinking mixture in the extruder and due to high shear stress, so thermal polymerization in the production process. It is difficult to use an initiator. Also, due to such temperature sensitivity of the crosslinkable mixture, an operating temperature significantly lower than 100 ° C. is required, and as a result, processing with a twin screw extruder is not possible. The photocrosslinkable flexible printing plate used in Patent Document 2 is also solid at 20 ° C.

In the technique disclosed in Patent Document 3, a process for evaporating the solvent is required, and foaming is performed in the solvent removal process. Therefore, it is indispensable to mold very slowly so as not to foam, and thus productivity is reduced. Absent. Further, depending on the balance between the temperature for evaporating the solvent and the temperature for thermal crosslinking, there is a problem that the solvent component remains in the resin. Furthermore, Patent Document 3 also describes that a large amount of carbon black is added to a photosensitive resin composition that is solid at 20 ° C., the main component of which is a thermoplastic elastomer. However, the photocuring is insufficient due to the strong light absorption, and the mechanical properties of the resulting cured product are low.

In the technique described in Patent Document 4, when a compound having a strong light absorption property in the ultraviolet region such as carbon black or an additive having a large light scattering property is mixed in a large amount, only a very thin cured product can be obtained. There is a big problem. In addition, there is no effective technique for setting the hardness low while maintaining laser engraving property and solvent resistance, and there remains a problem in printing applications on low-quality paper and corrugated paper with high surface roughness.

The problems to be solved by the present invention are a thermosetting resin composition for a laser engraving printing original plate, which has excellent manufacturing and storage stability, high plate productivity, and can be cured in the atmosphere, and surface roughness It is an object of the present invention to provide a laser engraving printing plate capable of printing on high-quality low-grade paper or cardboard paper.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin (a) having a polymerizable unsaturated group having a number average molecular weight of 1,000 or more and 300,000 or less, a number average molecular weight of less than 1,000 and a polymerizable non-polymerizable group in the molecule. A resin composition (A) containing an organic compound (b) having a saturated group and a thermal polymerization initiator (c) is contained, and the resin (a) and / or the organic compound (b) is carbonated in the molecule. It has been found that the above-mentioned problems can be solved by using a thermosetting resin composition for a laser engraving printing original plate, which contains at least one compound having a bond and the resin composition (A) is liquid at 20 ° C. The invention has been completed.

That is, the present invention is as follows.
1.
A thermosetting resin composition for a laser engraving printing original plate,
A resin composition (a) having a number average molecular weight of 1,000 or more and 300,000 or less, an organic compound (b) having a number average molecular weight of less than 1,000 and having a polymerizable unsaturated group in the molecule, and a thermal polymerization initiator (c) ( A) containing
The resin (a) and / or the organic compound (b) includes at least one compound having a carbonate bond in the molecule,
A thermosetting resin composition for a laser engraving printing original plate, wherein the resin composition (A) is liquid at 20 ° C.
2.
The thermal polymerization initiator (c) is an organic peroxide, and the content of the thermal polymerization initiator (c) is 0.1 wt% or more and 10 wt% with respect to the total amount of the thermosetting resin composition for the laser engraving printing original plate. % Or less, A thermosetting resin composition for a laser engraving printing original plate as described in 1.
3.
1. A pigment having a primary particle number average particle diameter of 5 nm to 10 μm is further contained in an amount of 0.1 wt% to 30 wt% of the total amount of the thermosetting resin composition for laser engraving printing original plate. Or 2. A thermosetting resin composition for a laser engraving printing original plate as described in 1.
4).
1. further containing porous fine particles having a number average particle diameter of 5 nm to 10 μm, or nonporous fine particles having a number average particle diameter of 5 nm to 100 nm. To 3. The thermosetting resin composition for laser engraving printing original plate of any one of these.
5).
The thermal polymerization initiator (c) is liquid at 20 ° C. To 4. The thermosetting resin composition for laser engraving printing original plate of any one of these.
6).
A laser engraving printing original plate comprising a support and a cured resin layer laminated on the support,
The cured resin layer is 1. To 5. The laser-engraving printing original plate obtained by thermosetting the thermosetting resin composition for laser-engraving printing original plates of any one of these.
7).
5. The thickness of the cured resin layer is 50 μm or more and 50 mm or less. The laser engraving printing original plate described in 1.
8).
5. It is a sheet shape or a cylindrical shape. Or 7. The laser engraving printing original plate described in 1.
9.
5. The support is at least one selected from the group consisting of a fiber reinforced plastic sleeve, a metal sleeve, a metal cylinder, and a rubber cylinder. To 8. The manufacturing method of the laser engraving printing original plate of any one of these.
10.
The laser engraving printing original plate according to any one of claims 6 to 9, further comprising a cushion layer between the resin cured product layer and the support.
11.
9. The cushion layer has hollow fine particles having a number average particle diameter of 100 nm to 500 μm, or bubbles having a number average particle diameter of 100 nm to 500 μm. The laser engraving printing original plate described in 1.
12
6). To 11. A printing plate obtained by laser engraving the laser engraving printing original plate according to any one of the above.
13.
The printing plate according to 12., which is a cylindrical printing plate.
14
13. A printing plate having the concave pattern on the surface of the cylindrical printing plate as a convex portion using the cylindrical printing plate described in 1 above as a mold.
15.
12. Used in at least one printing application selected from the group consisting of flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing; A cylindrical printing plate as described in 1.
16.
A method for producing a laser engraving printing original plate comprising a support and a cured resin layer laminated on the support,
(I) 1. To 5. A step of applying the thermosetting resin composition for laser engraving printing original plate according to any one of the above to the support to form a resin layer;
(Ii) A method for producing a laser engraving printing original plate, comprising the step of heating the resin layer.
17.
In the step (i), no solvent is used; 16. 18. Method for producing the laser engraving printing original plate described
In the step (ii), the resin layer is heated at 80 ° C. or higher and 250 ° C. or lower. Or 17. The manufacturing method of the laser-engraving printing original plate as described in 1 above.
19.
In the step (ii), at least one method selected from the group consisting of a method of irradiating hot rays, a method of blowing hot air, a method of exposing to a hot air convection atmosphere, and a method of contacting with a heated roll Heating the resin layer, 16. To 18. The manufacturing method of the laser engraving printing original plate of any one of these.
20.
In the step (ii), the resin layer is heated in a state where the resin layer is exposed to the atmosphere. To 19. The manufacturing method of the laser engraving printing original plate of any one of these.

According to the present invention, there is provided a thermosetting resin composition for a laser engraving printing original plate that is excellent in production and storage stability, has high productivity of the printing original plate, and can form an environmentally friendly thermosetting laser engraving printing plate. can do.

Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The thermosetting resin composition for laser engraving printing original plate of the present embodiment is a resin (a) having a polymerizable unsaturated group having a number average molecular weight of 1000 or more and 300,000 or less, and having a number average molecular weight of less than 1000 and is polymerizable in the molecule. An organic compound (b) having an unsaturated group and a resin composition (A) containing a thermal polymerization initiator (c) are contained, and the resin (a) and / or the organic compound (b) are contained in the molecule. A thermosetting resin composition for a laser engraving printing original plate, comprising at least one compound having a carbonate bond, wherein the resin composition (A) is liquid at 20 ° C.
Hereinafter, "a resin (a) having a polymerizable unsaturated group having a number average molecular weight of 1000 or more and 300,000 or less", "an organic compound (b) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule", Each may be simply referred to as “resin (a)” or “organic compound (b)”.

The resin composition (A) is a composition containing a resin (a), an organic compound (b), and a thermal polymerization initiator (c).
The thermosetting resin composition for a laser engraving printing original plate according to the present embodiment preferably does not contain a solvent component from the viewpoints of simplification and shortening of the process, suppression of bubble generation, and environmental friendliness.
When the thermal polymerization initiator (c) is solid at 20 ° C., a thermal polymerization initiator solution dissolved in some solvent may be used.
In the case where the thermosetting resin for laser engraving printing original plate contains a solvent component, the content of the solvent component is from the viewpoint of suppressing the generation of bubbles to the printing original plate, shortening the drying time, and environmentally friendly, etc. 1 wt% or less of the total amount of the thermosetting resin composition for laser engraving printing original plate is preferable, more preferably 0.5 wt% or less, and still more preferably 0.1 wt% or less.

In the present embodiment, the thermosetting resin composition for a laser engraving printing original plate includes a resin composition (A), and the other components are compositions including components other than the resin composition (A). .
In the thermosetting resin composition for a laser engraving printing original plate of the present embodiment, including a component other than the resin composition (A) means that the component that polymerizes when thermally cured as the other component is a resin composition. It means that it is not contained other than the product (A).
In the present embodiment, the resin composition (A) is preferably a composition comprising, as its components, a resin (a), an organic compound (b), and a thermal polymerization initiator (c).

At least one of the resin (a) and the organic compound (b) in the resin composition (A) contains at least one compound having a carbonate bond in the molecule.
When the resin (a) contains at least one compound having a carbonate bond in the molecule, the organic compound (b) can be appropriately selected from the organic compounds described below as the organic compound (b).
When the organic compound (b) contains at least one compound having a carbonate bond in the molecule, the resin (a) can be appropriately selected from the resins described below as the resin (a).
Both the resin (a) and the organic compound (b) may contain at least one compound having a carbonate bond in the molecule, and the resin (a) contains at least one compound having a carbonate bond in the molecule. Is preferred.

The resin composition (A) is liquid at 20 ° C.
In the present embodiment, the “liquid resin composition” means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling, and when an external force is applied. It means an elastomer that has the property of recovering its original shape in a short time when it is deformed instantaneously according to its external force and the external force is removed.
When the resin (a) is liquid at 20 ° C., the resin composition (A) is liquid at 20 ° C., and when the resin (a) is solid at 20 ° C., the organic compound (b) or The resin composition (A) can be made liquid at 20 ° C. by appropriately selecting the thermal polymerization initiator (c).

The viscosity at 20 ° C. of the thermosetting resin composition for laser engraving printing original plate is 10 Pa · s or more and 10 kPa · s or less from the viewpoint of obtaining good thickness accuracy and dimensional accuracy when forming into a sheet shape or a cylindrical shape. It is preferably 50 Pa · s or more and 5 kPa · s or less.
When the viscosity is 10 Pa · s or more, the mechanical strength of the produced resin cured product is sufficient, and the shape can be easily maintained and processed even when molded into a cylindrical shape.
When the viscosity is 10 kPa · s or less, it is easily deformed even at room temperature and is easy to process. Moreover, it is easy to shape | mold into a sheet-like or cylindrical resin cured material, and a process is also simple.
In the present embodiment, in order to obtain a cylindrical resin cured product with high thickness accuracy, when the liquid resin layer is formed on the cylindrical support, the thermosetting resin composition for the laser engraving printing original plate is subjected to gravity. It is preferable that the composition has a relatively high viscosity so as not to cause a phenomenon such as liquid dripping, and the viscosity is preferably 100 Pa · s or more, more preferably 200 Pa · s or more, and still more preferably Is 500 Pa · s or more.

The number average molecular weight of the resin (a) is from 1,000 to 300,000, preferably from 2,000 to 150,000, more preferably from 5,000 to 50,000.
When the number average molecular weight of the resin (a) is 1000 or more, a cured resin obtained by crosslinking later maintains strength, and can withstand repeated use when used as a printing substrate.
If the number average molecular weight of the resin (a) is 300,000 or less, the viscosity of the thermosetting resin composition for laser engraving printing original plate does not increase excessively, and a sheet-shaped or cylindrical photosensitive resin cured product is obtained. There is no need for a complicated processing method such as heat extrusion when producing.
In the present embodiment, the “number average molecular weight” is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

The blending amount of the resin (a) is preferably 10 wt% or more and 90 wt% or less, more preferably 30 wt% or more and 80 wt% or less, and still more preferably, with respect to the total amount of the thermosetting resin composition for laser engraving printing original plate. Is 40 wt% or more and 75 wt% or less.
If the content rate of resin (a) is in the said range, the mechanical physical property as a printing plate can be ensured.

Examples of the resin (a) include polyolefins such as polyethylene and polypropylene; polydienes such as polybutadiene and polyisoprene; polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride; polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, Polyvinyl acetal, polyacrylic acid, poly (meth) acrylic acid esters, poly (meth) acrylamide; group consisting of polymers having hetero atoms in the main chain such as polyester, polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyimide, etc. Examples thereof include polymer compounds having one or more selected ones as a polymer skeleton.
In the case of using a plurality of polymer compounds, either a copolymer or a blend may be used.
As the resin (a), a compound having a carbonate bond in the molecule is preferable, and an unsaturated polyurethane is preferable as the compound having a carbonate bond in the molecule.
By using a compound having a carbonate bond as the resin (a), it is possible to significantly reduce the tack of the surface of the thermoset that has been thermoset in the atmosphere.

As a specific example of a particularly effective compound as the resin (a), a compound having a polycarbonate polyurethane obtained by reacting an aliphatic polycarbonate diol and a diisocyanate compound in the molecular skeleton, and a (meth) acrylate group at the molecular terminal is mentioned. The compound which further has polymerizable unsaturated groups, such as, is more preferable.
Examples of the aliphatic polycarbonate diol include poly (polymethylene (C = 2, 4, 5, 6) carbonate, poly ((1,9-nonanediol; 2-methyl-1,8-octanediol) carbonate, And compounds such as 3-dioxan-2-on, polymer with 1,6-hexane diol, carbonic acid, dimethyl ester, polymer with 1,6-hexandiol and 2-oxepone.
As a commercial product of a compound having a carbonate bond in the molecule as the resin (a), manufactured by Asahi Kasei Chemicals Corporation, PCDL (registered trademark) “T4672”, “T5651”, “T6002”, “T5652”, “T5650J”, “T "T4671", manufactured by Kuraray Co., Ltd., Kuraray Polyol (registered trademark) "C-2015N", manufactured by Daicel Chemical Industries, Plaxel CD (registered trademark) "CD205", "CD205PL", "CD205HL", "CD210", "CD210PL", “CD220”, “CD220PL”, Ube Industries, Ltd., ETERNACOLL (registered trademark) “UH”, “UHC”, “UC”, “UM”, and the like can be obtained.
Examples of the diisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylenebis (cyclohexane-1,4-diyl) diisocyanate, m -Phenylenebis (1-methylethane-1,1-diyl) diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, naphthalene-1,5-diyl diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, cyclohexane-1,3- Yl isocyanate, cyclohexane-1,4-diyl diisocyanate, dimer acid diisocyanate, cyclohexane-1,3-diylbis (methyl isocyanate), 2-methyl-1,4-phenylene diisocyanate, 4-[(2-isocyanatophenyl) oxy ] Phenyl isocyanate, 4,4'-oxybis (phenyl isocyanate), naphthalene-1,4-diisocyanate, naphthalene-2,6-diyl diisocyanate, naphthalene-2,7-diyl isocyanate, 1-methylcyclohexane-2,4- Diisocyanate, 2,2′-dimethoxybiphenyl-4,4′-diyl diisocyanate, methyl 2,6-diisocyanatohexanoate, 5-methyl-1,3-phenylene diisocyanate, methylene bis (2,1-phenol Nylene) diisocyanate, 4-[(2-isocyanatophenyl) methyl] phenyl isocyanate, dimethyldiisocyanatosilane, 2,4,6-triisopropylbenzene-1,3-diyl diisocyanate, 2,2-dimethylpentane-1 , 5-diyl diisocyanate, 4-[(2-isocyanatophenyl) thio] phenyl isocyanate, undecamethylene diisocyanate, methylene bis (2-methyl-4,1-phenylene) diisocyanate, adipoyl isocyanate, 4,4'- Ethylenebis (1-isocyanatobenzene), 1- (trifluoromethyl) -2,2,2-trifluoroethylidenebis (4,1-phenylene) diisocyanate, tetramethylene diisocyanate, 1,4-phenylenebis (ethylene) Diisocyanate 1,4-phenylenebis (ethylene) diisocyanate, 1-methylethylene diisocyanate, methylene diisocyanate, sulfonyl bis (3,1-phenylene) diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, pentanemethylene diisocyanate, heptane-1,7 -Diyl diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate and the like.
As a compound for introducing a polymerizable unsaturated group such as a (meth) acrylate group at the molecular end, a functional group such as a (meth) acrylate group or a vinyl group as a polymerizable unsaturated group in the molecule, a hydroxyl group, an isocyanate And compounds having both functional groups such as a group, amino group, and carboxyl group.
As such a compound, for example, 2- (meth) acryloyloxyisocyanate, 2-hydroxyethyl (meth) acrylate and the like are preferable from the viewpoint of reactivity.

When a flexible relief image is required as in flexographic printing plate applications, a part of the resin (a) is a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a liquid resin having a glass transition temperature of 0 ° C. or lower. Can also be added. Examples of such liquid resins include hydrocarbons such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene; polyesters such as adipate and polycaprolactone; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Polyethers of the following: silicones such as aliphatic polycarbonates and polydimethylsiloxanes; polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof.
The content of the liquid resin is preferably 30 wt% or more and 100 wt% or less with respect to the entire resin (a).

As the resin (a), it is preferable to use a compound having high thermal decomposability. For example, a compound having α-methylstyrene, methacrylic acid ester, acrylic acid ester, carbonate bond, carbamate bond and the like in the molecule is known as a compound having high thermal decomposability. As an index of thermal decomposability, thermogravimetric data obtained by measuring weight loss when a sample is heated in an inert gas atmosphere can be used. As a preferred resin, the temperature at which the weight is reduced by half is preferably in the range of 150 ° C. or higher and 450 ° C. or lower. A more preferable range is 250 ° C. or higher and 400 ° C. or lower, and further preferably 250 ° C. or higher and 380 ° C. or lower. Also preferred are compounds that undergo thermal decomposition in a narrow temperature range. As the index, in the thermogravimetric analysis, the difference between the temperature at which the weight is reduced to 80% of the initial weight and the temperature at which the weight is reduced to 20% of the initial weight is preferably 100 ° C. or less. More preferably, it is 80 degrees C or less, More preferably, it is 60 degrees C or less.

The resin (a) preferably has a polymerizable unsaturated group in the molecule.
Examples of the resin (a) include polymer compounds having an average of 0.7 or more polymerizable unsaturated groups per molecule as preferable compounds.
If the average number of polymerizable unsaturated groups is 0.7 or more, the cured resin has excellent mechanical strength and durability, and can withstand repeated use, particularly as a printing substrate. Therefore, it is preferable.
Considering the mechanical strength of the cured resin, the polymerizable unsaturated group of the resin (a) is preferably 0.7 or more per molecule, and more preferably 1 or more.
The upper limit of the number of polymerizable unsaturated groups per molecule is not particularly limited, but is preferably 20 or less because shrinkage during thermosetting can be suppressed to a low level and the occurrence of cracks in the vicinity of the surface can be suppressed. .
In the present embodiment, “having a polymerizable unsaturated group in the molecule” means that the terminal of the polymer main chain, the terminal of the polymer side chain, the polymer main chain or the side chain directly, It means the case with a polymerizable unsaturated group.

Examples of the method of introducing a polymerizable unsaturated group into the polymer compound constituting the resin (a) include a method of directly introducing a polymerizable unsaturated group into the molecular end or molecular chain of the polymer compound. It is done.
Alternatively, a compound having a plurality of reactive groups such as hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone group, hydrazine residue, isocyanate group, isothiocyanate group, cyclic carbonate group, ester group, etc. After reacting a binder having a plurality of functional groups capable of binding to the reactive group (for example, polyisocyanate in the case of a hydroxyl group or an amino group), adjusting the molecular weight and converting to a terminal binding group And a method of introducing a polymerizable unsaturated group at the terminal by reacting the compound obtained by the reaction with a compound having a functional group and a polymerizable unsaturated group that reacts with the terminal binding group of the compound. It is done.

The organic compound (b) is a compound having a polymerizable unsaturated group in the molecule, and the number average molecular weight is less than 1000 from the viewpoint of easy dilution with the resin (a).
The compounding amount of the organic compound (b) is to secure a three-dimensional cross-linked structure or a three-dimensional network structure, to prevent the thermosetting resin composition from increasing in viscosity, and to cure, with respect to the total amount of the thermosetting resin composition for laser engraving printing original plate. From the viewpoint of suppressing curing shrinkage of the product and ensuring the mechanical properties and solvent resistance of the cured product, it is preferably 1 wt% or more and 60 wt% or less, more preferably 5 wt% or more and 50 wt% or less, and even more preferably 10 wt%. % To 40 wt%.

Examples of the organic compound (b) include olefins such as ethylene, propylene, styrene, divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, unsaturated nitriles such as acrylonitrile, (meth) Acrylamide and its derivatives, allyl compounds such as allyl alcohol and allyl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid and their derivatives, vinyl acetates, N-vinylpyrrolidone, N-vinyl Examples thereof include carbazole and cyanate esters.
The organic compound (b) is preferably a derivative such as (meth) acrylic acid and (meth) acrylic acid ester from the viewpoints of variety and price.
Examples of (meth) acrylic acid ester derivatives include alicyclic compounds that may have a functional group such as a cycloalkyl group, a bicycloalkyl group, a cycloalkene group, and a bicycloalkene group, a benzyl group, a phenyl group, and a phenoxy group. Group, methylstyryl group, aromatic compound which may have a functional group such as styryl group, alkyl group, halogenated alkyl group, alkoxyalkyl group, hydroxyalkyl group, aminoalkyl group, tetrahydrofurfuryl group, glycidyl group And ester derivatives of compounds that may have other functional groups.
Examples of (meth) acrylic acid ester derivatives include ester compounds of (meth) acrylic acid with polyhydric alcohols such as alkylene glycol, polyoxyalkylene glycol, (alkyl / allyloxy) polyalkylene glycol and trimethylolpropane. .
Specific examples include phenoxyethyl methacrylate, polypropylene glycol monomethacrylate, lauryl methacrylate, 2-ethylhexyl diethylene glycol monoacrylate, and isobornyl mono (meth) acrylate.

In the present embodiment, one or more organic compounds (b) can be selected depending on the purpose.
The organic compound (b) contains at least one long-chain aliphatic, alicyclic or aromatic ester derivative in order to suppress swelling with respect to an organic solvent such as alcohol or ester which is a solvent for printing ink. Is preferred.
In order to increase the mechanical strength of the cured resin, the organic compound (b) preferably has at least one alicyclic or aromatic ester derivative, and contains an alicyclic or aromatic ester derivative. The amount is preferably 20 wt% or more and 100 wt% or less, more preferably 50 wt% or more and 100 wt% or less of the total amount of the organic compound (b).

It is preferable to use a compound having a carbonate bond in the molecule as the organic compound (b). In the range where the number average molecular weight of the organic compound (b) is less than 1000, for example, polymerization is performed at the terminal of a polycarbonate diol or polycarbonate polyol having a number average molecular weight of 800 or less, or a polycarbonate diamine or polycarbonate polyamine. And compounds having an unsaturated group bonded thereto. In particular, from the viewpoint of reactivity, a compound in which 2-methacryloyloxyisocyanate or 2-acryloyloxyisocyanate is reacted with the hydroxyl group of polycarbonate diol or polycarbonate polyol is preferable. By using a compound having a carbonate bond by using these compounds, tack of the surface of the thermoset cured by thermosetting in the air can be greatly reduced.

In the organic compound (b), the organic compound having 3 or more polymerizable unsaturated groups in the molecule is preferably contained in an amount of 5 wt% to 100%, more preferably 15 wt% or more of the total amount of the organic compound (b). It is 100 wt% or less, More preferably, it is 30 wt% or more and 100 wt% or less.
If the content of the organic compound having 3 or more polymerizable unsaturated groups in the molecule is within the above range, the resistance of the printing plate obtained by curing the curable resin composition for laser engraving printing original plate is greatly improved. Can be improved.
The organic compound (b) is more preferably a compound having 3 to 6 polymerizable unsaturated groups in the molecule, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meta). ) Acrylate, PO modified trimethylolpropane tri (meth) acrylate, ECH modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) acrylate, caprolactone Modified trimethylolpropane (tri) acrylate, HPA modified trimethylolpropane tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) a Relate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxy penta (meth) acrylate, dimethylol propane tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate.

Examples of the thermal polymerization initiator (c) used in the present embodiment 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 quinonedioxime 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 (c) is preferably liquid at 20 ° C. from the viewpoint of easy mixing with the resin (a) or the organic compound (b).
The content of the thermal polymerization initiator (c) is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% with respect to the total amount of the thermosetting resin composition for the laser engraving printing original plate. % Or less, and more preferably 1 wt% or more and 5 wt% or less.
When the content of the thermal polymerization initiator (c) is within the above range, the thermosetting resin composition for laser engraving printing original plate can be sufficiently cured, and the adhesiveness of the surface of the thermosetting product can be reduced. Is possible.

The selection of a suitable thermal polymerization initiator (c) is particularly important for carrying out the process of the present invention. The thermal stability of the thermal polymerization initiator (c) is usually determined by a method with a 10 hour half-life temperature of 10 h-t _1/2 , ie 50% of the initial amount of the thermal polymerization initiator (c) 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 (c) usually have a 10 h-t _1/2 of preferably at least 60 ° C., more preferably at least 70 ° C. Particularly preferred is 10 h-t _1/2 at 80 ° C. to 150 ° C.

As the thermal polymerization initiator (c), an organic peroxide is preferable from the viewpoints of securing and handling thermosetting in the atmosphere, handling, reducing the hardness of the thermoset, and compatibility with the thermosetting resin composition. . The cured product of the thermosetting resin composition using the organic peroxide as the thermal polymerization initiator is remarkably different from the cured product of the photosensitive resin composition in which only the thermal polymerization initiator is replaced with the photopolymerization initiator. Hardness can be lowered. Further, it is possible to set the hardness in a wide range by controlling the temperature condition at the time of thermosetting. By reducing the hardness of the thermosetting product, it is possible to obtain a printed material of good quality in printing on low-quality paper with high surface roughness and in printing on corrugated cardboard.

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 thereof 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.
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 the t-alkyl hydroperoxides include t-butyl hydroperoxide, t-amyl hydroperoxide, pinane hydroperoxide and cumyl hydroperoxide.

In the present embodiment, when the cushion layer containing bubbles is formed, an azo compound can be preferably used as the thermal polymerization initiator.
Examples of the azo compound include 1- (t-butylazo) formamide, 2- (t-butylazo) isobutyronitrile, 1- (t-butylazo) cyclohexanecarbonitrile, 2- (t-butylazo) -2-methyl. Butanenitrile, 2,2'-azobis (2-acetoxypropane), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2- Methylbutanenitrile) and the like.

Examples of inorganic peroxides 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.
Hydroperoxides include aliphatic and alicyclic saturated hydroperoxides, and hydroperoxides having OOH groups 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.

Fine particles such as inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles can be added to the thermosetting resin composition for a laser engraving printing original plate of the present embodiment. Improvement of mechanical properties of cured resin obtained by thermosetting by adding these fine particles, improvement of wettability of the surface of cured resin, and adjustment of viscosity of thermosetting resin composition for laser engraving printing original plate, It becomes possible to adjust the viscoelastic properties of the cured resin.
The material of the inorganic fine particles or organic fine particles is not particularly limited, and known materials can be used.
Examples of the organic-inorganic composite fine particles include fine particles in which an organic layer or organic fine particles are formed on the surface of the inorganic fine particles, or fine particles in which an inorganic layer or inorganic fine particles are formed on the surface of the organic fine particles.
For the purpose of improving the mechanical properties of the cured resin, inorganic fine particles having high rigidity such as silicon nitride, boron nitride, and silicon carbide, or organic fine particles such as polyimide can be used.
In order to improve the solvent resistance of the obtained resin cured product, inorganic fine particles or organic fine particles formed of a material having a good swelling property in the solvent to be used can be added.

For the purpose of forming a pattern that penetrates the surface of the resin cured product layer or the resin cured product by the laser engraving method, the number average particle diameter excellent in the adsorption removal property of the viscous liquid residue generated during laser engraving is 5 nm or more and 10 μm or less. It is preferable to add non-porous fine particles having a number average particle diameter of 5 nm to 100 nm.

In the present embodiment, “porous fine particles” means fine particles having a pore volume of 0.1 ml / g or more.
In the present embodiment, the pore volume is determined from an adsorption isotherm of nitrogen at −196 ° C. using a nitrogen adsorption method.

The preferable range of the pore volume of the porous fine particles is 0.1 ml / g or more and 10 ml / g or less, and more preferably 0.2 ml / g or more and 5 ml / g or less.
By using porous fine particles having a pore volume of 0.1 ml / g or more, the absorption amount of the viscous liquid residue generated during laser engraving becomes sufficient.
When the pore volume is 10 ml / g or less, the mechanical strength of the porous fine particles can be ensured.
The number average particle diameter of the porous fine particles is preferably 100 nm or more and 10 μm or less, and more preferably 300 nm or more and 5 μm or less.
When fine particles having a number average particle diameter within the above range are used, problems such as increase in viscosity, entrainment of bubbles, and generation of a large amount of dust occur when mixing with the resin (a) and the organic compound (b). Without unevenness on the surface of the cured resin product. The average particle size of the fine particles is a value measured using a laser scattering type particle size distribution measuring device.
In the present embodiment, the number average particle size can be measured using a laser scattering type particle size distribution measuring apparatus.

The porous particles are not particularly limited, and examples thereof include porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, and porous glass.

In the present embodiment, “nonporous fine particles” mean fine particles having a pore volume of less than 0.1 ml / g.
The number average particle diameter of the nonporous fine particles is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 50 nm or less.
When fine particles having a number average particle diameter within the above range are used, problems such as increase in viscosity, entrainment of bubbles, and generation of a large amount of dust occur when mixing with the resin (a) and the organic compound (b). Without unevenness on the surface of the cured resin product.
As the material of the nonporous fine particles, for example, alumina, silica, zirconium oxide, barium titanate, strontium titanate, titanium oxide, silicon nitride, boron nitride, silicon carbide, chromium oxide, vanadium oxide, tin oxide, bismuth oxide, It is preferably a fine particle mainly composed of at least one selected from germanium oxide, aluminum borate, nickel oxide, molybdenum oxide, tungsten oxide, iron oxide, and cerium oxide.
The nonporous fine particles are preferably fine particles produced by any one of the flame hydrolysis method, the arc method, the plasma method, the sedimentation method, the gelation method, and the molten solid method using the above materials. The flame hydrolysis method, the arc method, and the plasma method are also called a thermal decomposition method or a high heat method (dry method). The sedimentation method and the gelation method are also called wet methods. Of these, a dry method, particularly a flame hydrolysis method is preferred.
One kind or two or more kinds of inorganic fine particles can be used in combination.

The particle shape of the fine particles is not particularly limited, and spherical, flat, needle-like, amorphous, or particles having protrusions on the surface can be used. In particular, spherical particles are preferable from the viewpoint of wear resistance.
The surface of the fine particles may be coated with a silane coupling agent, a titanium coupling agent, or other organic compound and subjected to a surface modification treatment to make the particles more hydrophilic or hydrophobic. These fine particles can be selected from one type or two or more types.
When using microparticles | fine-particles for a thermosetting resin composition, it is preferable that they are 1 mass part or more and 100 mass parts or less with respect to 100 mass parts of resin (a), More preferably, they are 2 mass parts or more and 50 mass parts or less. More preferably, it is 2 parts by mass or more and 20 parts by mass or less.

A polymerization inhibitor, an ultraviolet absorber, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the thermosetting resin composition for a laser engraving printing original plate according to the present embodiment, depending on the application and purpose. it can.

In the present embodiment, the cured resin obtained by thermosetting the thermosetting resin composition for laser engraving printing original plate is a polymerizable unsaturated group of organic compound (b), or resin (a) and organic compound. By reacting the polymerizable unsaturated group (b), a three-dimensional cross-linked structure is formed and insolubilized in a commonly used ester-based, ketone-based, aromatic-based, ether-based, alcohol-based or halogen-based solvent.
In the reaction for forming a three-dimensional crosslinked structure, it occurs between the organic compounds (b), between the resins (a), or between the resin (a) and the organic compound (b), and the polymerizable unsaturated group is consumed. . In this embodiment, since thermosetting is performed using a thermal polymerization initiator, the thermal polymerization initiator is decomposed by heat. Therefore, the resin cured product is extracted with a solvent and separated by GC-MS (gas chromatography). LC-MS method (method for mass spectrometry of those separated by liquid chromatography), GPC-MS method (method of mass spectrometry by separation by gel permeation chromatography), LC-NMR method An unreacted thermal polymerization initiator and a decomposition product can be identified by analysis using a method (analysis of a component separated by liquid chromatography using a nuclear magnetic resonance spectrum).
By using the GPC-MS method, the LC-MS method, and the GPC-NMR method, the unreacted resin (a), the unreacted organic compound (b), and the polymerizable unsaturated group in the solvent extract are reacted. The relatively low molecular weight product obtained in this way can also be identified from the analysis of the solvent extract. For high molecular weight components that are insoluble in solvents and that form a three-dimensional cross-linked structure, the site formed by the reaction of a polymerizable unsaturated group as a component constituting the high molecular weight body by using the pyrolysis GC-MS method Can be verified. By the pyrolysis GC-MS method, it can be estimated from the mass spectrometry spectrum pattern that there is a site where a polymerizable unsaturated group such as a methacrylate group, an acrylate group, or a vinyl group has reacted.
The pyrolysis GC-MS method is a method in which a sample is thermally decomposed and a gas component to be generated is separated by gas chromatography and then mass spectrometry is performed. In addition to the unreacted polymerizable unsaturated group or the site obtained by reacting the polymerizable unsaturated group in the cured resin, the decomposition product derived from the thermal polymerization initiator and the unreacted thermal polymerization initiator are detected. Then, it can be concluded that it was obtained by thermosetting the thermosetting resin composition for laser engraving printing original plate of the present embodiment.
The resin (a) or the thermal polymerization initiator (c) in the thermosetting resin composition for laser engraving printing original plate is separated and purified using liquid chromatography such as GPC method or LC method, followed by nuclear magnetic resonance spectroscopy ( NMR method) can be used to identify the molecular structure. By analyzing the chemical shift peculiar to a functional group using an NMR method focusing on hydrogen atoms ( ¹ H-NMR method), it is possible to identify what functional group exists in the molecule, The amount of a specific bond or functional group present can be quantified. The carbonate bond is preferably present in the resin (a) or the organic compound (b), but can be quantitatively identified from these methods.

The laser engraving printing original plate of the present embodiment is composed of a support and a cured resin layer laminated on the support, and the cured resin layer is a thermosetting resin for the laser engraving printing original plate of the present embodiment. It is a printing original plate which is a layer obtained by thermosetting the composition.
The laser engraving printing original plate of the present embodiment is manufactured by the following laser engraving printing original plate manufacturing method.
In this embodiment, since the cured resin layer is a layer obtained by thermosetting, unlike the design concept of the photosensitive resin composition in which the function of forming a fine pattern is an important element, light is used. There is no need to form a fine pattern, and it is sufficient that the necessary mechanical strength can be ensured by curing by full exposure, so that the degree of freedom in selecting a material is extremely high.

The method for producing a laser engraving printing original plate according to the present embodiment includes (i) a step of applying the thermosetting resin composition for laser engraving printing original plate according to the present embodiment on a support to form a resin layer; and ii) a step of heating the resin layer.

In the step (i), it is preferable not to use a solvent from the viewpoint of simplifying the coating process and forming a resin layer having no bubbles in the resin.

In this Embodiment, the existing coating method can be used for the method of apply | coating the thermosetting resin composition for laser engraving printing original plates on a support body.
As the coating method, for example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, adjusting the thickness by calendaring with a roll, etc. are used. The method of spraying can be illustrated.
It is also possible to perform molding while heating in a range that does not cause thermal decomposition of the thermosetting resin composition. Moreover, you may perform a rolling process, a grinding process, etc. as needed.
When applying on a support, it is usually applied on a sheet-like support made of a material such as a film such as PET or a metal such as nickel or aluminum. It is also preferable to apply to a support (sleeve).
The cylindrical support is preferably a cylindrical support having at least one material selected from fiber reinforced plastic, film reinforced plastic, metal, and rubber as a constituent component.
Examples of the cylindrical support include cylindrical supports such as polyester resins reinforced with fibers such as glass fibers, aramid fibers, and carbon fibers, plastic sleeves such as epoxy resins, and polyester tubes such as polyethylene terephthalate. .
The cylindrical support is preferably hollow from the viewpoint of weight reduction of the printing plate and ease of handling.

In the present embodiment, the role of the sheet-like support or the cylindrical support is to ensure the dimensional stability of the cured resin.
It is preferable to select a support having high dimensional stability, and the dimensional stability can be evaluated using a linear thermal expansion coefficient.
From the viewpoint of dimensional stability of the support, the linear thermal expansion coefficient of the material of the support is preferably 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less.
Examples of the support material include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, and polyethersulfone resin. , Liquid crystal resins made of wholly aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins.

As a support, it can also be used as a laminated body of these resins. Moreover, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, or a film in which pores are formed can be used as the sheet-like support.
When a porous sheet is used as the sheet-like support, the resin cured product layer and the sheet-like support are integrated by impregnating the holes with the thermosetting resin composition for laser engraving printing original plate. Therefore, high adhesiveness can be obtained. Examples of fibers that form cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, sapphire fibers, and other inorganic fibers, cotton, hemp, etc. Natural fibers, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid.
Cellulose produced by bacteria is a highly crystalline nanofiber, and is a material for producing a thin nonwoven fabric with high dimensional stability, which is a suitable support material.

In the step (ii), it is preferably heated to 80 ° C. or higher and 250 ° C. or lower, more preferably 80 ° C. or higher and 200 ° C. or lower, and further preferably 100 ° C. or higher and 150 ° C. or lower.
In the present embodiment, the heating temperature means the temperature of the resin layer surface.
When the heating temperature is within the above range, the dimensional stability of the support can be ensured.
When the resin layer is heated to form a cured resin layer, when the thermosetting resin composition for laser engraving printing original plate is applied on the cylindrical support, it is heated while rotating the cylindrical support. This is preferable because liquid dripping in the direction of gravity can be suppressed.

In the step (ii), the method for heating the resin layer is selected from a method of irradiating hot rays, a method of blowing hot air, a method of exposing to an atmosphere where hot air is convected, and a method of contacting with a heated roll. It is preferred to use at least one method. In particular, from the viewpoint of ease of workability, a method of irradiating with heat rays and a method of contacting with a heated roll are preferable.
Examples of the heat rays include near infrared rays and infrared rays.

In the present embodiment, the thickness of the cured resin layer made of the cured resin obtained by thermosetting the thermosetting resin composition for laser engraving printing original plate is arbitrary within a range of 50 μm or more and 50 mm or less depending on the purpose of use. However, it is preferably 100 μm or more and 10 mm or less.
In the present embodiment, a resin cured product layer obtained by laminating a plurality of resin compositions for laser engraving printing original plates having different compositions as a resin layer and thermosetting the resin composition may be used.

In the present embodiment, a cushion layer may be provided between the cured resin layer and the support.
A cushion layer is a layer which plays the role which absorbs the impact by the vibration in a printing process.
The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 ° to 70 °, or an ASKER-C hardness of 20 ° to 85 ° as measured with an ASKER-C hardness tester.
When the Shore A hardness is 10 degrees or more or the ASKER-C hardness is 20 degrees or more, the cushion layer is appropriately deformed, so that the printing quality can be ensured.
If the Shore A hardness is 70 degrees or less or the ASKER-C hardness is 85 degrees or less, it can serve as a cushion layer.
Preferably, the Shore A hardness is 20 degrees or more and 60 degrees or less, and the ASKER-C hardness is 45 degrees or more and 75 degrees or less.

In the present embodiment, it is preferable that the Shore A hardness and the ASKER-C hardness are properly used depending on the material used for the cushion layer.
The difference between the two types of hardness stems from the difference in the shape of the pushers of the hardness meter used for measurement. When the cured resin layer has a uniform structure, it is preferable to use Shore A hardness as an index, and when the cured resin layer has a non-uniform structure, such as a foaming base material such as foamed polyurethane and foamed polyethylene. It is preferable to use ASKER-C hardness as an index.
Shore A hardness and ASKER-C hardness are measurement methods based on JIS K7312 standard.

The cushion layer is not particularly limited, and is not particularly limited as long as it has rubber elasticity such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer.
By containing a large amount of hollow fine particles and bubbles in the material forming the cushion layer, higher cushioning properties can be expressed.
When a cushion layer containing hollow fine particles or bubbles is used, it can be cured thickly. Therefore, it is preferable to select a thermosetting elastomer as a material.

The cushion layer preferably has hollow fine particles having a number average particle diameter of 0.1 μm or more and 500 μm or less, or bubbles having a number average diameter of 0.1 μm or more and 500 μm or less. Those having inorganic fine particles attached to the surface of the hollow fine particles can be used.
From the viewpoint of suppressing variations in performance of the cushion layer, it is preferable to use hollow fine particles. Among the hollow fine particles, those in which a shell is formed from an organic compound are particularly preferable.

The hollow fine particles are preferably hollow fine particles expanded by heating thermally expandable fine particles containing a volatile organic liquid inside with a thermoplastic elastomer as a partition wall. The heating temperature for thermal expansion is 60 ° C. or higher and 250 ° C. or lower, and more preferably 100 ° C. or higher and 200 ° C. or lower. Examples of the thermoplastic elastomer usually used include polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate and the like. Examples of the volatile organic liquid include hydrocarbons such as butane, isobutane, butene, isobutene, pentane, isopentane, neopentane, hexane, and heptene. By using thermally expandable fine particles, closed cells having a relatively uniform particle diameter can be formed when thermally expanded. Moreover, the partition may be coated with inorganic fine particles. Examples of inorganic fine particles include silica, calcium carbonate, and titanium oxide.

The density of the cushion layer is preferably 0.1 g / cm ³ or more and 0.9 g / cm ³ or less, more preferably 0.3 g / cm ³ or more and 0.7 g / cm ³ or less, and still more preferably 0. .4g / cm ³ or more 0.6g / cm ³ or less.
When the density of the cushion layer is within the above range, the impact applied to the cured resin layer that is the laser engraving layer in the printing process can be sufficiently absorbed.
Examples of the thermoplastic elastomer used for the cushion layer include SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), and SEBS (polystyrene-polyethylene / polybutylene-polystyrene), which are styrenic thermoplastic elastomers. Examples include olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, silicon-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers.
Examples of the photocurable elastomer include those obtained by mixing the thermoplastic elastomer with a photopolymerizable monomer, a plasticizer and a photopolymerization initiator, and a liquid photosensitive resin obtained by mixing a photopolymerizable monomer and a photopolymerization initiator with a liquid resin. A composition etc. can be mentioned.

The cushion layer may be a cushion layer made of a material such as polyurethane foam or polyethylene foam, and may have independent or open cells in the layer, and commercially available cushion materials and cushion tapes may be used.
A cushion layer in which an adhesive or a pressure-sensitive adhesive is applied on one side or both sides may be provided between the support and the cured resin layer.

By forming a modified layer on the surface of the cured resin layer of the present embodiment, it is possible to reduce the tack on the surface of the printing substrate and improve the ink wettability.
Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.

When the printing original plate is used as a printing plate by forming a recess using the laser engraving method, in the laser engraving method, the laser device is operated by using a computer as a digital data for the image to be formed, and the printing original plate Create a relief image. Any laser may be used for the laser engraving as long as the cured resin layer includes a wavelength having absorption, but in order to perform engraving at a high speed, a laser with a high output is desirable. An infrared or infrared emitting solid laser such as a gas laser, YAG laser, or semiconductor laser is preferable. Further, the second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser that has been wavelength-converted to the third or fourth harmonic are: It can be ablated by cutting the bonds of organic molecules and is suitable for fine processing. The laser may be continuous irradiation or pulse irradiation.
Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out under carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by high pressure spraying. Alternatively, it may be removed using a method of irradiating high-pressure steam.

In the thermosetting resin composition for a laser engraving printing original plate of the present embodiment, a pigment having a primary particle number average particle diameter of 5 nm or more and 10 μm or less is 0.1 wt% or more and 30 wt% of the total amount of the thermosetting resin composition. It is also suitable to contain further in% or less.
The number average particle diameter of the primary particles is preferably 10 nm or more and 1 μm or less, and more preferably 10 nm or more and 100 nm or less.
If the number average particle diameter of the primary particles is within the above range, there is an effect of improving the visibility of the laser engraving pattern. In particular, it is preferable to use a blue pigment or a red pigment. In the case of black pigments such as carbon black, carbon nanotubes, graphite and activated carbon, laser light can be absorbed when laser engraving is performed using a laser light source having an oscillation wavelength in the near-infrared region of 700 nm to 3 μm. And has the effect of enabling laser engraving.

In this embodiment, after engraving to irradiate a laser beam to form a recess, and subsequently removing the powdery or viscous liquid residue remaining on the surface of the printing plate, the surface of the printing plate on which the pattern is formed has a wavelength of 200 nm to It is preferable to carry out post-exposure by irradiating light of 450 nm, which is an effective method for removing tack on the surface.
The post-exposure can be performed in any environment of air, inert gas atmosphere, and water. Before the post-exposure process, the printing plate surface is treated with a treatment liquid containing a hydrogen abstraction type photopolymerization initiator and exposed. Also good.
You may expose in the state which immersed the printing plate in the process liquid containing a hydrogen drawing type photoinitiator.

The printing plate of the present embodiment is a printing plate obtained by forming a recess using the laser engraving method.
In another form of the present embodiment, the printing plate obtained by forming the concave portion is brought into contact with a thermoplastic resin, a thermosetting resin, a photocurable resin, and the concave portion is formed. It may be a printing plate obtained by transferring the corresponding convex portions to a thermoplastic resin, a thermosetting resin, or a photocurable resin, and curing the thermoplastic resin, thermosetting resin, or photocurable resin. .

The printing plate is used in at least one kind of printing application selected from flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing. Further, as described above, the printing plate is used as a mold, and the printing plate surface is brought into contact with the thermoplastic resin, thermosetting resin, and photocurable resin, and the concave pattern on the printing plate surface is transferred. It can also be used.

Hereinafter, the present embodiment will be further described with reference to examples and comparative examples, but the present embodiment is not limited to only these examples. The evaluation method and measurement method used in this embodiment are as follows.

(1) Residue rate of residue during laser engraving Laser engraving is a carbon dioxide laser engraving machine (“ZED-mini-1000”, manufactured by ZED, UK: laser oscillation wavelength 10.6 μm, output 250 W carbon dioxide laser (US Mounted on a coherent company).
After the laser engraving, the residue on the relief printing plate was wiped off using a nonwoven fabric impregnated with ethanol or acetone ("BEMOT (registered trademark) M-3", manufactured by Asahi Kasei Chemicals Corporation, Japan). The weight of each of the printing original plate before laser engraving, the printing plate after laser engraving, and the relief printing plate after wiping was measured, and the residue rate at the time of engraving was determined by equation (1).
Formula (1):
(Weight of printing plate immediately after engraving-Weight of printing plate after wiping) ÷ (Weight of printing original plate before engraving-Weight of printing plate after wiping) x 100
The case where the residue remaining rate was less than 10% was indicated by ◯, the case where it was 10% or more and less than 25% was indicated by Δ, and the case where it was greater than 25% was indicated by ×.

(2) Viscosity The viscosity of the thermosetting resin composition or the resin composition (A) was measured at 20 ° C. using a B-type viscometer (“B8H type”, manufactured by Tokyo Keiki Co., Ltd., Japan).

(3) Measurement of number average molecular weight The number average molecular weights of the resin (a) and the organic compound (b) were determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC apparatus (“HLC-8020”, manufactured by Tosoh Corporation, Japan) and a polystyrene packed column (“TSKgel GMHXL”, manufactured by Tosoh Corporation, Japan), the measurement was performed with tetrahydrofuran (THF). The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a THF solution having a resin concentration of 1 wt% was prepared, and the injection amount was 10 μL. A differential refractometer was used as the detector.

(4) Shore A Hardness The hardness of the cured resin was measured at 23 ° C. using a rubber hardness meter (“Type A durometer GS-719G type”, manufactured by Teclock Corporation, Japan). As the hardness value, a value 15 seconds after the start of measurement was obtained.

(5) Measurement of 10-hour half-life temperature The 10-hour half-life temperature of the organic peroxide was measured by dissolving a sample in benzene to a concentration of 0.1 mol / L and sealing it in a nitrogen-substituted glass tube. The tube was immersed in a thermostatic chamber adjusted to a predetermined temperature, and the temperature at which the active oxygen of the organic peroxide was reduced to half in 10 hours was measured. The analysis of active oxygen was performed by the iodometric titration method using potassium iodide as a reducing agent.

(6) Tack measurement of the printing original plate surface The tack measurement of the printing original plate surface was performed using "PICMA tack tester" (made by Toyo Seiki Co., Ltd., Japan). At 20 ° C., a smooth portion of the printing original plate is brought into contact with a 13 mm wide aluminum ring having a radius of 50 mm and a width of 13 mm, a load of 0.5 kg is applied to the aluminum ring and left for 4 seconds, and then a constant speed of 30 mm per minute. The aluminum ring was pulled up and the resistance force when the aluminum ring was separated from the sample was read with a push-pull gauge.
The larger this value, the greater the tack (stickiness) and the higher the adhesive strength.
A case where the tack value was less than 100 N / m was indicated by ◯, a case where the tack value was 100 N / m or more and less than 200 N / m was indicated by Δ, and a case where the tack value was 200 N / m or more was indicated by ×.

(7) Measurement of engraving depth Of the pattern obtained by laser engraving on the printing plate surface, the depth from the surface of the linear groove portion having a width of 2 mm and a length of 50 mm was measured, and this value was defined as the engraving depth. . For the measurement, an optical microscope (digital microscope “VHX-900”, manufactured by Keyence Corporation, Japan) that can capture data in the depth direction was used.

(8) Measurement of centerline surface roughness (Ra) The measurement of the centerline surface roughness (Ra) of the printing original plate surface is carried out using a stylus type surface roughness meter ("SE500", manufactured by Kosaka Laboratory, Japan). ) Was used. The radius of curvature of the tip portion was measured using a stylus having a diameter of 2 μm under the conditions of a cut-off λc = 0.8 mm, a measurement length of 4 mm, and a feed rate of 0.5 m / sec to obtain a center line average roughness Ra.

(9) Evaluation of printing quality When printing on tack paper, the one that the paper dust in the air did not adhere to the surface of the cylindrical printing plate and a good printed matter was obtained was marked on the surface of the cylindrical printing plate. A small amount of paper dust in the air is attached, and the portion where the paper dust is attached has a printing defect. Δ, the paper dust in the air is significantly attached to the surface of the cylindrical printing plate. The case where printing failure occurred was marked with x.

(10) Evaluation of grinding / polishing process
　 In the grinding / polishing process, “◯” indicates that no grinding waste is generated, “Δ” indicates that grinding waste is generated but no grinding trace is generated, and “x” indicates that grinding scrap is generated and grinding trace is generated.

(Production Example 1)
To a 1 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser was added 447.24 g of polycarbonate diol (“PCDL (registered trademark) L4672”, manufactured by Asahi Kasei, Japan: number average molecular weight 1990, OH value 56.4). After adding 30.83 g of diisocyanate and reacting at 80 ° C. for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate (“MOI”, Showa Denko, Japan) was added, and about 3 By reacting for a period of time, a resin (A) having a number average molecular weight of about 10,000 having a terminal having a methacrylic group (an average of about 2 polymerizable unsaturated groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 2)
A 1 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 759.5 g of hydrogenated polybutadiene diol (“GI-3000”, manufactured by Nisso, Japan: number average molecular weight 3940) and 46.21 g of tolylene diisocyanate. Was added and reacted at 80 ° C. for about 4 hours, followed by addition of 27.24 g of 2-hydroxypropyl methacrylate and further reaction for about 3 hours. A resin (I) having a number average molecular weight of about 10,000 having an average of about 2 groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 3)
In a 1 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 420.2 g of polyester diol (“P-3010”, manufactured by Kuraray, Japan; number average molecular weight 3000) and polyether diol (“PL”, Japan, Sanyo Chemical Co., Ltd .; 420.2 g of number average molecular weight 2500) and 63.22 g of tolylene diisocyanate were added and reacted at 80 ° C. with heating for about 4 hours, and then 42.07 g of 2-hydroxypropyl methacrylate was added. The resulting mixture was further reacted for 3 hours to produce a resin (c) having a number average molecular weight of about 18000, the terminal of which was a methacrylic group (average number of polymerizable unsaturated groups in the molecule was about 2 per molecule). This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

Example 1
As resin (a), 70 parts by mass of resin (a) prepared in Production Example 1, and as organic compound (b), phenoxyethyl methacrylate ("Light Ester (registered trademark) PO", manufactured by Kyoeisha Chemical Co., Ltd. in Japan: molecular weight 206 ) 20 parts by mass and 10 parts by mass of polypropylene glycol monomethacrylate (“PPM”, manufactured by NOF, Japan: molecular weight 400), and t-butylperoxy-2-ethylhexyl carbonate (“ 1 part by mass of “Perbutyl (registered trademark) E” (manufactured by Nippon Oil & Fats, Japan) was mixed at 70 ° C. to obtain a liquid resin composition (A).
As a stabilizer, 0.5 parts by mass of 2,6-di-t-butylacetophenone (“Ionol (registered trademark) CP”, manufactured by Japan Chemtech, Japan) was further mixed at 70 ° C. to form a thermosetting resin composition. A product was prepared. The viscosity of the thermosetting resin composition was 800 Pa · s. The 10-hour half-life temperature of “Perbutyl (registered trademark) E” was 100 ° C.

(Example 2)
Copper phthalocyanine blue ("Helogen (registered trademark)", which is a blue pigment, using phenoxyethyl methacrylate ("Light Ester (registered trademark) PO", manufactured by Kyoeisha Chemical Co., Japan) as a dispersion medium as one component of the organic compound (b). A 10% dispersion was prepared using a homomixer apparatus (manufactured by PRIMIX) and T4670 "(manufactured by BASF, Germany). The average particle size of the pigment particles was 300 nm as a result of measurement using a laser scattering particle size distribution meter (“FMR-1000”, manufactured by Otsuka Electronics, Japan). 70 parts by mass of the resin (A) prepared in Production Example 1, 20 parts by mass of the 10% dispersion, and 10 parts by mass of polypropylene glycol monomethacrylate (“PPM”, Nippon Oil, Japan: molecular weight 400), thermal polymerization As an initiator (c), 1 part by mass of t-butyl peroxy-2-ethylhexyl carbonate (“Perbutyl (registered trademark) E”, manufactured by Nippon Oil & Fats, Japan), as a stabilizer, 2,6-di-t- Resin composition (A) and thermosetting resin composition using 0.5 parts by weight of butylacetophenone (“Ionol (registered trademark) CP”, manufactured by Japan Chemtech) in the same manner as in Example 1. Got. The viscosity of the thermosetting resin composition was 900 Pa · s.

(Example 3)
The resin composition (A) mixed in Example 1 was further mixed with porous fine powder silica ("Cyrossphere (registered trademark) C-1504", manufactured by Fuji Silysia Chemical, Japan: number average particle size 4.5 μm. Specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g), 5 parts by mass, 2,6-di-t as a stabilizer -0.5 part by mass of butylacetophenone ("Ionol (registered trademark) CP", manufactured by Japan Chemtech) was mixed to prepare a thermosetting resin composition. The viscosity of the thermosetting resin composition was 1200 Pa · s.

Example 4
In the same manner as in Example 1, except that 2-2′-azobisisobutyronitrile (“ABN-R”, manufactured by Nihon Finechem, Japan) was used as the thermal polymerization initiator (c) (resin composition ( A) and a thermosetting resin composition were prepared. The viscosity of the thermosetting resin composition was 800 Pa · s. The 10 hour half-life temperature of “ABN-R” was 64 ° C.

(Comparative Example 1)
As resin (a), 70 parts by mass of resin (I) prepared in Production Example 2, and as organic compound (b), lauryl methacrylate ("Light Ester (registered trademark) L", manufactured by Kyoeisha Chemical Co., Ltd .: molecular weight 245) 25 parts by mass and 5 parts by mass of 1,3-butylene glycol dimethacrylate (“NK Ester (registered trademark) BG”, manufactured by Shin-Nakamura Chemical Co., Ltd., Japan: molecular weight 226), t-butyl as a thermal polymerization initiator (c) 1 part by weight of peroxybenzoate ("Perbutyl Z", manufactured by Nippon Oil & Fats, Japan), 2,6-di-t-butylacetophenone ("Ionol (registered trademark) CP"), Japan Chemtech, Japan as a stabilizer (Product made) Using 0.5 mass part, it carried out similarly to Example 1, and obtained the resin composition (A) and the thermosetting resin composition. The viscosity of the thermosetting resin composition was 800 Pa · s. The 10-hour half-life temperature of “Perbutyl (registered trademark) Z” was 104 ° C.

(Comparative Example 2)
As resin (a), 70 parts by mass of resin (c) prepared in Production Example 3, and as organic compound (b), diethylene glycol 2-ethylhexyl ether acrylate (“Aronix (registered trademark) M-120”, Toa Gosei, Japan Manufactured by: 30 parts by mass of molecular weight 272), 1,1-di (t-butylperoxy) percyclohexane ("Perhexa (registered trademark) C-75 (EB)" as a thermal polymerization initiator (c), Example using 1 part by mass of Nippon Oil & Fats Co., Ltd. and 0.5 part by mass of 2,6-di-t-butylacetophenone (“Ionol (registered trademark) CP”, manufactured by Japan Chemtech, Japan) as a stabilizer In the same manner as in Example 1, a resin composition (A) and a thermosetting resin composition were obtained. The viscosity of the thermosetting resin composition was 100 Pa · s.

(Comparative Example 3)
As a resin (a), 70 parts by mass of a styrene butadiene copolymer which is a thermoplastic elastomer resin (“Tufprene A (registered trademark)”, manufactured by Asahi Kasei Chemical, Japan: number average molecular weight 77,000, solid at 20 ° C.) As an organic compound (b), 30 parts by mass of phenoxyethyl methacrylate (“Light Ester (registered trademark) PO”, manufactured by Kyoeisha Chemical Co., Ltd .: molecular weight 206), as a thermal polymerization initiator (c), 1,1-di 1 part by mass of (t-butylperoxy) percyclohexane (“Perhexa® C-75 (EB)”, manufactured by Nippon Oil & Fats, Japan), 2,6-di-t-butylacetophenone (as stabilizer) 0.5 parts by mass of “Ionol (registered trademark) CP” (manufactured by Japan Chemtech) was mixed at 150 ° C. using an open kneader. Before the resin was uniformly mixed, the mixture partly gelled, and the resin could not be flowed to form and produce a printing original plate.

(Comparative Example 4)
Instead of the thermal polymerization initiator (c), as a photopolymerization initiator, 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Specialty Chemical, Switzerland), 0.6 parts by mass, benzophenone (“KAYACURE (registered trademark)” ) BP-100 "(manufactured by Nippon Kayaku, Japan) A photosensitive resin composition was prepared in the same manner as in Example 2 except that 1 part by mass was used. The photosensitive resin composition was solid.
The obtained photosensitive resin composition is molded into a sheet having a thickness of 3.0 mm on a PET film, and is exposed to 4000 mJ in the atmosphere using an exposure machine (“ALF type 213E”, manufactured by Asahi Kasei, Japan). Exposed. The light used for exposure was light from an ultraviolet fluorescent lamp (chemical lamp, manufactured by Toshiba, Japan: center wavelength: 370 nm) and a germicidal lamp (germisidal lamp, manufactured by Toshiba, Japan: center wavelength: 253 nm). The photosensitive resin composition was cured only 0.5 mm from the surface, resulting in poor internal curing.

(Comparative Example 5)
A solid photosensitive resin composition (“AFP SH”, manufactured by Asahi Kasei Chemicals, Japan: 1.7 mm) was used in an atmosphere of 4000 mJ using an exposure machine (“ALF-213E”, manufactured by Asahi Kasei, Japan). Exposed. An uneven pattern was formed on the surface of the obtained cured plate using a carbon dioxide laser engraving machine. The Shore A hardness of the cured plate was 65 degrees. Moreover, the surface stickiness was large and the tack value was 200 N / m. The solid photosensitive resin composition is a sheet-like photosensitive resin composition at 20 ° C. having a styrene-butadiene-styrene (SBS) thermoplastic elastomer as a main component and having no carbonate group in the molecule.

(Comparative Example 6)
As resin (a), 70 parts by mass of a styrene-butadiene copolymer (“Tufprene (registered trademark) A”, manufactured by Asahi Kasei Chemicals, Japan: number average molecular weight: 77,000), which is a thermoplastic elastomer, an organic compound (b ), 30 parts by mass of phenoxyethyl methacrylate (“Light Ester (registered trademark) PO”, manufactured by Kyoeisha Chemical Co., Ltd .: molecular weight 206), and 1,1-di (t-butylperoxide) as the thermal polymerization initiator (c). 1 part by mass of oxide) percyclohexane (“Perhexa C-75 (registered trademark)”, manufactured by Nippon Oil & Fats, Japan), 2,6-di-t-butylacetophenone (manufactured by Japan Chemtech Co., Ltd., “Ionol” (Registered trademark) CP ") 0.5 parts by mass was dissolved in 150 parts by mass of toluene and mixed to prepare a thermosetting resin composition. The viscosity of the thermosetting resin composition was 2000 Pa · s.
The prepared thermosetting resin composition was poured into a spacer having a thickness of 3 mm using a polyester film having a thickness of 100 μm (manufactured by Toray, Japan) as a support and allowed to stand at 80 ° C. for 5 hours. Then, it left still for 60 minutes in the oven (in air | atmosphere atmosphere) temperature-controlled at 160 degreeC. There were an infinite number of air bubbles of uneven size presumed to have occurred when toluene evaporated. Innumerable bubbles existed in the printing original plate. Therefore, when a pattern was formed by laser engraving, there were many points where the pattern was lost due to bubbles, particularly in the halftone dot pattern part, and there were halftone dots. The image could not be used as a printing plate. The tack value on the surface of the cured resin was 500 N / m, and the Shore A hardness was 35 degrees.
An uneven pattern was formed on the surface of the resin plate obtained in Comparative Examples 5 and 6 using a carbon dioxide laser engraving machine. A large amount of engraving debris is generated on the plate surface. Alkaline cleaning liquid ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and brush washer (manufactured by Techno Giken, Japan) complete engraving debris. Could not be removed. Thereafter, the engraving residue was wiped off with toluene to obtain a printing plate.
After affixing a 0.5mm thick cushion tape (US, 3M) on a cylinder of a flexographic printing machine (Iyo Machinery Co., Ltd., Japan), attach the prepared sheet-shaped printing plate to the tack paper Printing was performed. In both of the printing plates of Comparative Examples 5 and 6, paper dust in the air adhered to the surface of the printing plate, and the portion where the paper dust adhered was defective in printing.

(Comparative Example 7)
As resin (a), 70 parts by mass of resin (c) prepared in Production Example 3, and as organic compound (b), 2-ethylhexyldiethylene glycol monoacrylate (“Aronix® M-120”, Toa Gosei, Japan) Manufactured by: molecular weight 272) 30 parts by weight, 2,2-dimethoxy-2-phenylacetophenone (manufactured by Ciba Specialty Chemicals, Switzerland) as a photopolymerization initiator, 0.6 parts by weight, benzophenone (“KAYACURE® BP”) -100 ", Nippon Kayaku, Japan) 1 part by mass, 2,6-di-t-butylacetophenone (" Ionol (registered trademark) CP ", Japan, Chemtech, Japan) as a stabilizer. 5 mass parts was mixed at 70 degreeC, and the photosensitive resin composition was obtained. The viscosity of the photosensitive resin composition was 130 Pa · s.
The obtained photosensitive resin composition was molded into a 3.0 mm thick sheet on a 100 μm thick PET film (manufactured by Toray, Japan) and exposed to an exposure machine (“ALF type 213E”, Asahi Kasei, Japan). The product was exposed under the condition of 4000 mJ in the atmosphere. The light used for the exposure is that of an ultraviolet fluorescent lamp (“chemical lamp”, manufactured by Toshiba, Japan: central wavelength: 370 nm) and a germicidal lamp (“germisidal lamp”, manufactured by Toshiba, Japan: central wavelength: 253 nm). Met.
The tack value of the obtained resin cured product surface was 100 N / m, and the Shore A hardness was 80 degrees.
A pattern was formed on the surface of the sheet-shaped printing original plate obtained as described above using a laser engraving machine. The engraving residue generated a large amount of liquid, but was removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (manufactured by Techno Giken, Japan). . The engraving residue rate was 7%, and the engraving depth was 0.45 mm.
After affixing a 0.5mm thick cushion tape (US, 3M) on the cylinder of a flexographic printing machine (Iyo Machine Seisakusho, Japan), attach the prepared sheet-shaped printing plate to the tack paper Printing was performed. However, since the hardness of the printing plate is high, the ink transfer property of the solid portion is not sufficient, and the printing quality is not good.

The thermosetting resin compositions prepared in Examples 1 to 4 and Comparative Examples 1, 2, and 5 were liquid at 20 ° C. Further, the thermosetting resin composition was stable even when stored at 50 ° C. for 1 week, and did not react during storage. Further, the thermosetting resin compositions prepared in Examples 1 to 4 and Comparative Examples 1, 2, and 5 were sandwiched with 100 μm polyester film, and a press machine using a 3 mm-thick spacer was used at a temperature of 130 ° C. and 60 ° C. A pressure of 10 kg / cm ² was applied for 10 minutes to produce a resin plate having a thickness of 3.0 mm.
An uneven pattern was formed on the surface of the obtained resin plate using a carbon dioxide laser engraving machine.
Table 1 shows the composition of the thermosetting resin composition for each of Examples 1-4 and Comparative Examples 1-7, the curing method, the tack value of the obtained printing original plate, the engraving residue rate, and the bottom power of 70%. Shows engraving depth and hardness. The smaller the tack value, the lower the engraving residue rate, and the deeper the engraving depth, the better the laser engraving plate. The shape of the engraving halftone dot portion of the laser engraving printing plate prepared in Examples 1 to 4 was conical and good. In the laser engraving printing plate prepared in Example 3, the residue residue after engraving was powdery, and it was easier to remove the residue residue and was even better.
A plate containing a large number of bubbles was obtained as the resin plate prepared in Example 4. However, since a large number of bubbles existed in the printing original plate, when the pattern was formed by laser engraving, there were many portions where the pattern was lost due to bubbles, particularly in the halftone dot pattern portion. However, it was not possible to use as a printing plate for an image having a halftone dot portion.

(Example 5)
A polyethylene fiber reinforced plastic sleeve (made by AKL, Germany) having the same inner diameter and a thickness of 0.5 mm is fitted into an air cylinder having a diameter of 200 mm, and while rotating the air cylinder, the same as in Example 1 The thermosetting resin composition was applied to a thickness of 1.4 mm using a doctor blade. Then, while rotating an air cylinder, it heated for 30 minutes by the 150 degreeC thermostat in air | atmosphere, and obtained the thermosetting resin hardened | cured material of thickness about 1.4mm. The obtained cured resin was completely cured. After that, the surface of the cured resin is ground with a grinding wheel (made by Carborundum) using a grinding / polishing device (made by Techno Giken, Japan), polished with a # 1000 lapping film and finished, and a cylindrical printing original plate is obtained. Obtained. The centerline surface roughness Ra of the surface was 0.5 μm, and grinding marks were not observed, and a very good surface could be obtained. The tack value of the surface of the obtained cylindrical printing original plate was 55 N / m.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue remaining on the printing plate could be easily removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (manufactured by Techno Giken, Japan). . There was no stickiness on the surface of the printing plate. The residue rate after engraving was 7%, and the engraving depth was 0.44 mm.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. Good printed matter could be obtained.

(Example 6)
The thermosetting resin composition used in Example 1 was vigorously stirred in nitrogen gas to form fine bubbles in the resin composition. The obtained resin composition was applied in the same manner as in Example 5 onto a 0.45 mm thick polyethylene fiber reinforced plastic sleeve (manufactured by AKL, Germany) at a thickness of 0.5 mm, and 150 ° C. in an air atmosphere. And cured by heating for 30 minutes. The obtained cured resin was completely cured. In this way, a cushion layer made of a cured resin was formed. Separately, the cushion layer formed on the PET film was peeled off from the PET film and the density was measured, and it was 0.55 g / cm ³ .
Next, similarly to Example 5, a cured resin layer obtained by curing the curable resin composition used in Example 1 is formed on the formed cushion layer, and a cylindrical shape having a cushion layer is formed. A laser engraving printing original plate was prepared. The center line surface roughness Ra of the surface of the cylindrical printing original plate was 0.6 μm. The tack value of the surface of the obtained cylindrical printing original plate was 55 N / m.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue remaining on the printing plate can be easily removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (produced by Techno Giken, Japan). It was. There was no stickiness on the surface of the printing plate. The residue rate after engraving was 7%, and the engraving depth was 0.44 mm.
The cylindrical printing plate thus prepared was attached to the air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) with the above cylindrical printing plate having a cushion layer, and printing on tack paper was performed. Good printed matter could be obtained.

(Example 7)
As resin (a), 70 parts by mass of resin (a) prepared in Production Example 1, and as organic compound (b), phenoxyethyl methacrylate (“Light Ester (registered trademark) PO”, manufactured by Kyoeisha Chemical Co., Ltd .: molecular weight 206 ) 20 parts by mass and 10 parts by mass of trimethylolpropane triacrylate (“NK Ester (registered trademark) TMPT”, Shin-Nakamura Chemical Co., Ltd., Japan: molecular weight 338), t-butylperoxy- as the thermal polymerization initiator (c) 1 part by weight of 2-ethylhexyl carbonate ("Perbutyl (registered trademark) E", manufactured by Nippon Oil & Fats, Japan), porous fine powder silica ("Cyrossphere (registered trademark) C-1504", Japan, Fuji Silysia Chemical 3.5 parts by weight, 2,6-di-t-butylacetophenone (“Ionol (registered trademark) CP”, Japan, 0.5 parts by mass (manufactured by Japan Chemtech) were mixed at 70 ° C. to obtain a thermosetting resin composition. The viscosity of the thermosetting resin composition was 1200 Pa · s.
Using the obtained thermosetting resin composition, a cylindrical printing original plate was produced in the same process as in Example 5. The obtained cured resin was completely cured. Then, using a grinding / polishing apparatus (manufactured by Techno Giken, Japan), the surface of the cured resin was ground with a carborundum grinding wheel, polished with a # 1000 lapping film, and finished to obtain a cylindrical printing original plate. . The centerline surface roughness Ra of the surface was 0.4 μm, and grinding marks were not observed, and a very good surface could be obtained. The tack value of the surface of the obtained cylindrical printing original plate was 20 N / m. The Shore A hardness of the printing original plate surface was 68 degrees.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue is in powder form and can be easily removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (produced by Techno Giken, Japan). did it. There was no stickiness on the surface of the printing plate. The residue rate after engraving was 9% and the engraving depth was 0.44 mm.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. Good printed matter could be obtained.

(Example 8)
2-Methacryloyloxyisocyanate ("MOI", manufactured by Showa Denko, Japan) is reacted with the terminal hydroxyl group of polycarbonate diol ("T5650E", manufactured by Asahi Kasei Chemicals, Japan) having a carbonate bond in the molecule. Thus, a polycarbonate compound having a number average molecular weight of 800 having a methacryl group as a polymerizable unsaturated group at both ends (organic compound (b)) (hereinafter sometimes referred to as PCDMA) was synthesized.
As resin (a), 70 parts by mass of resin (a) prepared in Production Example 1, and as organic compound (b), 20 parts by mass of polycarbonate compound PCDMA synthesized as described above and trimethylolpropane triacrylate (“NK ester (registered) TMPT ", manufactured by Shin-Nakamura Chemical Co., Ltd., Japan: molecular weight 338), t-butyl peroxy-2-ethylhexyl carbonate (" Perbutyl (registered trademark) E ", Japan as thermal polymerization initiator (c) , Manufactured by Nippon Oil & Fats Co., Ltd.) 1 part by weight, porous fine powdered silica ("Cyrossphere (registered trademark) C-1504", manufactured by Fuji Silysia Chemical, Japan), 3.5 parts by weight, 2,6-di-stable as a stabilizer -Mixing 0.5 parts by weight of t-butylacetophenone (“Ionol (registered trademark) CP”, manufactured by Japan Chemtech Co., Ltd., Japan) at 70 ° C. To obtain a thermosetting resin composition. The viscosity at 20 ° C. was 1500 Pa · s.
Using the obtained thermosetting resin composition, a cylindrical printing original plate was produced in the same process as in Example 5. The obtained cured resin was completely cured. Then, using a grinding / polishing apparatus (manufactured by Techno Giken, Japan), the surface of the cured resin was ground with a carborundum grinding wheel, polished with a # 1000 lapping film, and finished to obtain a cylindrical printing original plate. . The centerline surface roughness Ra of the surface was 0.4 μm, and grinding marks were not observed, and a very good surface could be obtained. The tack value of the surface of the obtained cylindrical printing original plate was 20 N / m. The Shore A hardness of the surface of the printing original plate was 65 degrees.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue is in powder form and can be easily removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (produced by Techno Giken, Japan). did it. There was no stickiness on the surface of the printing plate. The residue rate after engraving was 8%, and the engraving depth was 0.5 mm.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. Good printed matter could be obtained.

Example 9
As resin (a), 70 parts by mass of resin (c) synthesized in Production Example 3, and as organic compound (b), number average molecular weight 800 having a methacryl group as a polymerizable unsaturated group at both ends synthesized in Example 8 As a thermal polymerization initiator (c), 55 parts by mass of the polycarbonate compound PCDMA and 10 parts by mass of trimethylolpropane triacrylate (“NK ester (registered trademark) TMPT”, manufactured by Shin-Nakamura Chemical Co., Ltd .: molecular weight 338) are used. 1 part by mass of 2-ethylhexyl carbonate ("Perbutyl (registered trademark) E", manufactured by Nippon Oil & Fats, Japan), porous fine powder silica ("Cyrossphere (registered trademark) C-1504", Japan, Fuji Silysia Chemical) 3.5 parts by mass, 2,6-di-t-butylacetophenone (“Ionol (registered trademark) CP”) as a stabilizer Japan, the Japan Co. Chemtech Ltd.) 0.5 part by mass at 70 ° C. to obtain a thermosetting resin composition. The viscosity at 20 ° C. was 900 Pa · s.
Using the obtained thermosetting resin composition, a cylindrical printing original plate was produced in the same process as in Example 5. The obtained cured resin was completely cured. Thereafter, the surface of the cured resin was ground with a grinding wheel made of Carborundum using a grinding / polishing apparatus (manufactured by Techno Giken), polished with a # 1000 lapping film, and finished to obtain a cylindrical printing original plate. The center line surface roughness Ra of the surface was 0.6 μm, and grinding marks were not observed, and a very good surface could be obtained. The tack value of the surface of the obtained cylindrical printing original plate was 70 N / m. The Shore A hardness of the printing original plate surface was 53 degrees.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue is in powder form and can be easily removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (produced by Techno Giken, Japan). did it. There was no stickiness on the surface of the printing plate. The residue rate after engraving was 11% and the engraving depth was 0.45 mm.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. Good printed matter could be obtained.

(Comparative Example 8)
A cylindrical printing original plate was produced in the same process as in Example 5 except that the thermosetting resin composition prepared in Comparative Example 1 was used. The surface of the cured resin obtained by thermosetting in the air atmosphere was very sticky, and the tack value of the smooth portion was 350 N / m.
Also, in the grinding process, grinding scraps adhered to the surface, and it was necessary to stop the apparatus to remove it occasionally. The grinding wheel partially bites the grinding debris, and deep grinding marks were observed on the surface of the cured resin. This grinding mark could not be removed even in the polishing step. Furthermore, the lapping film did not move smoothly even in the polishing process, and it was difficult to polish. The centerline surface roughness Ra of the surface of the cylindrical printing original plate was 1.5 μm. The grinding and polishing required three times or more time as compared with Example 5.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue generated a large amount of liquid, but was removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (manufactured by Techno Giken, Japan). . Stickiness on the surface of the printing plate remained.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. Paper dust in the air remarkably adhered to the surface of the cylindrical printing plate, and the portion where the paper dust adhered became defective printing.

(Comparative Example 9)
As resin (a), 70 parts by mass of resin (c) prepared in Production Example 3, and as organic compound (b), phenoxyethyl methacrylate ("Light Ester (registered trademark) PO", manufactured by Kyoeisha Chemical Co., Ltd. in Japan: molecular weight 206 ) 20 parts by mass and 10 parts by mass of trimethylolpropane triacrylate (“NK ester (registered trademark) TMPT”, Shin-Nakamura Chemical Co., Ltd., Japan: molecular weight 338), t-butylperoxybenzoate as thermal polymerization initiator (c) (“Perbutyl (registered trademark) Z”, manufactured by Nippon Oil & Fats, Japan), 1 part by mass, 2,6-di-t-butylacetophenone (“Ionol (registered trademark) CP”, Japan, Japan Chemtech) as a stabilizer Manufactured) and 0.5 mass part was mixed at 70 degreeC, and the thermosetting resin composition was obtained. The viscosity of the thermosetting resin composition was 130 Pa · s.
A cylindrical printing original plate was produced in the same process as in Example 5. The surface of the cured resin obtained by heat curing in the air atmosphere was very sticky, and the tack value of the smooth portion was 150 N / m.
Also, in the grinding process, grinding scraps adhered to the surface, and it was necessary to stop the apparatus to remove it occasionally. The grinding and polishing took about 1.5 times as long as Example 7. The centerline surface roughness Ra of the obtained cylindrical printing original plate surface was 1.1 μm.
A pattern was formed on the surface of the obtained cylindrical printing original plate using a laser engraving machine. The engraving residue generated a large amount of liquid, but was removed using an alkaline cleaning solution ("Sunwash (registered trademark) TL-75", manufactured by Lion, Japan) and a brush cleaning machine (manufactured by Techno Giken, Japan). . Stickiness on the surface of the printing plate remained.
The produced cylindrical printing plate was attached to an air cylinder of a flexographic printing machine (manufactured by Iyo Machinery Co., Ltd., Japan) via a cushion sleeve (manufactured by AKL, Germany), and printing on tack paper was performed. A little paper dust in the air adhered to the surface of the cylindrical printing plate, and the portion where the paper dust adhered became defective printing.

Table 2 shows Example 5-9 and Comparative Example 8-9 evaluated for the cylindrical printing plate and the cylindrical printing plate. In any of Examples 5-9, a printing original plate having good thermosetting in the atmosphere and a printing plate capable of printing on tack paper were obtained. Further, it can be seen from the tack value that when the resin (a) is changed to the resin (a), the thermosetting property in the atmosphere is even better.

This application is based on a Japanese patent application (Japanese Patent Application No. 2007-336119) filed on December 27, 2007, the contents of which are incorporated herein by reference.

The thermosetting resin composition of the present invention is suitably used in printing fields such as flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing.

Claims

A thermosetting resin composition for a laser engraving printing original plate,
A resin composition (a) having a number average molecular weight of 1,000 or more and 300,000 or less, an organic compound (b) having a number average molecular weight of less than 1,000 and having a polymerizable unsaturated group in the molecule, and a thermal polymerization initiator (c) ( A) containing
The resin (a) and / or the organic compound (b) includes at least one compound having a carbonate bond in the molecule,
A thermosetting resin composition for a laser engraving printing original plate, wherein the resin composition (A) is liquid at 20 ° C.
The thermal polymerization initiator (c) is an organic peroxide, and the content of the thermal polymerization initiator (c) is 0.1 wt% or more and 10 wt% with respect to the total amount of the thermosetting resin composition for the laser engraving printing original plate. The thermosetting resin composition for laser engraving printing original plate according to claim 1, wherein the thermosetting resin composition is at most%.
The pigment having a number average particle diameter of primary particles of 5 nm or more and 10 µm or less is further contained in an amount of 0.1 wt% or more and 30 wt% or less of the total amount of the thermosetting resin composition for a laser engraving printing original plate. 2. A thermosetting resin composition for a laser engraving printing original plate according to 2.
The laser engraving according to any one of claims 1 to 3, further comprising porous fine particles having a number average particle size of 5 nm to 10 µm, or nonporous fine particles having a number average particle size of 5 nm to 100 nm. Thermosetting resin composition for printing original plate.
The thermosetting resin composition for a laser engraving printing original plate according to any one of claims 1 to 4, wherein the thermal polymerization initiator (c) is liquid at 20 ° C.
A laser engraving printing original plate comprising a support and a cured resin layer laminated on the support,
A laser engraving printing original plate, wherein the cured resin layer is obtained by thermosetting the thermosetting resin composition for laser engraving printing original plate according to any one of claims 1 to 5.
The laser engraving printing original plate according to claim 6, wherein the cured resin layer has a thickness of 50 µm or more and 50 mm or less.
The laser engraving printing original plate according to claim 6 or 7, which has a sheet shape or a cylindrical shape.
The laser according to any one of claims 6 to 8, wherein the support is at least one selected from the group consisting of a fiber-reinforced plastic sleeve, a metal sleeve, a metal cylinder, and a rubber cylinder. A method for producing an engraving printing original plate.
The laser engraving printing original plate according to any one of claims 6 to 9, further comprising a cushion layer between the cured resin layer and the support.
The laser engraving printing original plate according to claim 10, wherein the cushion layer has hollow fine particles having a number average particle diameter of 100 nm to 500 µm or bubbles having a number average diameter of 100 nm to 500 µm.
A printing plate obtained by laser engraving the laser engraving printing original plate according to any one of claims 6 to 11.
The printing plate according to claim 12, which is a cylindrical printing plate.
14. A printing plate using the cylindrical printing plate according to claim 13 as a mold and having a concave pattern on the surface of the cylindrical printing plate as a convex portion.
The cylindrical printing plate according to claim 13, which is used in at least one kind of printing application selected from the group consisting of flexographic printing, letter press printing, dry offset printing, gravure printing, and rotary screen printing.
A method for producing a laser engraving printing original plate comprising a support and a cured resin layer laminated on the support,
(I) a step of applying the thermosetting resin composition for laser engraving printing original plate according to any one of claims 1 to 5 on the support to form a resin layer;
(Ii) A method for producing a laser engraving printing original plate, comprising the step of heating the resin layer.
The method for producing an original plate for laser engraving printing according to claim 16, wherein no solvent is used in the step (i).
The method for producing a laser engraving printing original plate according to claim 16 or 17, wherein, in the step (ii), the resin layer is heated at 80 ° C or higher and 250 ° C or lower.
In the step (ii), at least one method selected from the group consisting of a method of irradiating hot rays, a method of blowing hot air, a method of exposing to a hot air convection atmosphere, and a method of contacting with a heated roll The method for producing a laser engraving printing original plate according to any one of claims 16 to 18, wherein the resin layer is heated.
The method for producing a laser engraving printing original plate according to any one of claims 16 to 19, wherein, in the step (ii), the resin layer is heated in a state where the resin layer is exposed to the atmosphere.