JP2007148322A - Photosensitive resin composition for flexographic printing - Google Patents

Abstract

Provided is a photosensitive resin composition that simultaneously satisfies excellent fine line reproducibility and high ester solvent resistance.
At least a thermoplastic elastomer (a), a photopolymerizable unsaturated monomer (b), a hydrocarbon plasticizer (c), and a liquid conjugated diene rubber having a viscosity of 2000 (Pa · s) or less at 30 ° C. A photosensitive resin composition for flexographic printing comprising (d) and a photopolymerization initiator (e), wherein the hydrocarbon-based plasticizer (c) has a weight average molecular weight of 2000 or less and an unsaturated bond amount of 0.5 mol / A photosensitive resin composition for flexographic printing, having a refractive index of 100 g or less and a refractive index at 20 ° C. of 1.497 or more.
[Selection figure] None

Description

  The present invention relates to a photosensitive resin composition used for flexographic printing plates.

As described in Patent Documents 1 and 2, a photosensitive resin composition for flexographic printing generally contains a thermoplastic elastomer, a photopolymerizable unsaturated monomer, a plasticizer, and a photopolymerization initiator. It is.
As a structural body for flexographic printing plates, a polyester film or the like is used as a support, and on the photosensitive resin composition, a negative film is contacted on the photosensitive resin composition as necessary. For smoothing purposes, it is common to provide a slip layer or protective layer, or an ultraviolet shielding layer containing an infrared sensitive material that can be excised with an infrared laser.
In order to make a flexographic printing plate from such a photosensitive composition for a flexographic printing plate, first, the entire surface is exposed to ultraviolet rays (back exposure), a thin uniform cured layer is provided, and then through a negative film, or Image exposure (relief exposure) is performed directly on the surface of the photosensitive resin layer from above the UV shielding layer, and unexposed areas are washed away with a developing solvent, or absorbed and removed by an absorption layer after heat melting and post-process exposure. It is common to manufacture by doing.

In general printing using a photosensitive resin plate for flexographic printing, an ink containing an ester solvent or the like is supplied to the surface of a convex portion of an uneven resin plate by an ink supply roll or the like. It is performed by bringing the ink on the surface of the convex portion into contact with the printing medium and transferring the ink on the surface of the convex portion to the printing medium.
In such flexographic printing, if the shape (resolution) faithful to the negative film is not obtained or the solvent is not resistant to ester solvent, the printing plate will be destroyed or swelled during printing for a long time. Some parts may be printed.
Various plasticizers have been proposed for such photosensitive resin compositions.

Patent Document 3 uses a high-priced liquid polyisoprene having a large amount of unsaturated bonds in a molecule having a molecular weight of 25000 or more as a plasticizer for improving solvent resistance. In contrast, in Example 1, naphthenic oil having a low refractive index is used as a hydrocarbon plasticizer. In Examples 1 to 9, a styrene oligomer having a large amount of unsaturated bonds is used as the hydrocarbon plasticizer.
In Examples 1 to 3 of Patent Document 4, liquid paraffin having a low refractive index is used as the hydrocarbon plasticizer.

  In Patent Document 5, an elastomer resin, a weight average molecular weight of 2000 or less, an unsaturated bond amount of 0.5 mol / 100 g or less, and a refractive index at 20 ° C. of 1.497 are used to improve ink resistance including an ester solvent. A photosensitive resin composition comprising the above hydrogenated terpene resin, photopolymerizable unsaturated monomer, photopolymerization initiator, and, if necessary, a dye, a pigment, a polymerization inhibitor, an antioxidant and a photodegradation inhibitor Has been proposed. For example, the examples show a photosensitive resin composition containing benzyl dimethyl ketal as a styrene isoprene styrene block copolymer, a hydrogenated terpene resin, two photopolymerizable monomers, and a photopolymerization initiator. Yes.

As described above, in the prior art, a thermoplastic elastomer, a photopolymerizable unsaturated monomer, a hydrocarbon plasticizer having a weight average molecular weight of 2000 or less, a low amount of unsaturated bonds in the molecule, and a high refractive index. A photosensitive resin for flexographic printing containing a conjugated diene rubber and a photopolymerization initiator is not known.
JP 2000-155418 A Japanese Patent Laid-Open No. 02-108632 Japanese Patent Laid-Open No. 04-342258 Japanese Patent Laid-Open No. 10-288838 JP 2006-3570 A

  It is an object of the present invention to provide a photosensitive resin composition that (1) has high image reproducibility of a printing plate and (2) simultaneously satisfies ester solvent resistance.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the problems can be solved by using the following novel photosensitive resin composition, and has reached the present invention.
That is, the present invention is as follows.
1. At least a thermoplastic elastomer (a), a photopolymerizable unsaturated monomer (b), a hydrocarbon plasticizer (c), a liquid conjugated diene rubber (d) having a viscosity of 2000 (Pa · s) or less at 30 ° C., and A photosensitive resin composition for flexographic printing comprising a photopolymerization initiator (e), wherein the hydrocarbon-based plasticizer (c) has a weight average molecular weight of 2000 or less, an unsaturated bond amount of 0.5 mol / 100 g or less, and A photosensitive resin composition for flexographic printing, having a refractive index of 1.497 or more at 20 ° C.
2. 1. The vinyl content of the conjugated diene rubber (d) is 50 mol% or more. The photosensitive resin composition for flexographic printing described in 1.
3. 1. The vinyl content of the conjugated diene rubber (d) is 70 mol% or more. Or 2. The photosensitive resin composition for flexographic printing described in 1.
4). The content of the hydrocarbon plasticizer (c) in the photosensitive resin composition is 6 wt% to 30 wt%. ~ 3. The photosensitive resin composition for flexographic printing according to any one of the above.

5. The thermoplastic elastomer (a) is an aromatic block copolymer, and the content of the aromatic compound in the block copolymer is 28 wt% or less. ~ 4. The photosensitive resin composition for flexographic printing according to any one of the above.
6). 1. As a photopolymerizable unsaturated monomer (b), at least polyfunctional (meth) acrylate is contained in the photosensitive resin composition in an amount of 3 wt% or more. ~ 5. The photosensitive resin composition for flexographic printing according to any one of the above.
7). 1. The hydrocarbon plasticizer (c) is a resin obtained by hydrogenating a hydrocarbon resin having a cyclic structure. ~ 6. The photosensitive resin composition for flexographic printing according to any one of the above.
8). 1. The glass transition temperature of the hydrocarbon plasticizer (c) is −20 ° C. or higher and the refractive index at 20 ° C. is 1.510 or higher. ~ 7. The photosensitive resin composition for flexographic printing according to any one of the above.
9. 1. Support and formed on its surface ~ 8. A photosensitive composition for flexographic printing plates having a laminated structure comprising a layer of the photosensitive resin composition for flexographic printing according to any one of the above.

  The photosensitive resin composition of this invention has high image reproducibility of a printing plate, and satisfy | fills ester solvent tolerance simultaneously.

Hereinafter, the present invention will be specifically described.
The thermoplastic elastomer (a) in the present invention is a polymer that can be plasticized and molded at high temperatures and exhibits properties as a rubber elastic body at room temperature. Among them, shortening of plate making time and image reproducibility of printing plates In this respect, an aromatic thermoplastic block copolymer is preferred.
The thermoplastic block copolymer having an aromatic has at least a polymer block mainly composed of vinyl aromatic hydrocarbon and a polymer block mainly composed of conjugated diene.
In the present application, the “main body” refers to 70 wt% or more.
Examples of the vinyl aromatic hydrocarbon include styrene, P-methylstyrene, tertiary butylstyrene, α-methylstyrene, 1,1-diphenylethylene, and among them, styrene is preferable from the viewpoint of availability.

The content of the vinyl aromatic hydrocarbon in the thermoplastic block copolymer having an aromatic is preferably 13 wt% or more in terms of cold flow resistance of the uncured resin component, and 28 wt% in terms of solvent resistance. % Or less is preferable. The range of 14 wt% to 25 wt% is more preferable, and the range of 15 wt% to 25 wt% is more preferable.
Examples of the conjugated diene include butadiene and isoprene and / or a hydrogenated product thereof. These monomers may be used alone or in combination of two or more. Hydrogenation may be performed after the production of the aromatic block copolymer having aromatics.
Of these, butadiene and / or a hydrogenated product thereof is preferable from the viewpoints of lowering the tackiness of the surface, wear resistance of the printing plate, and anti-caking.

The vinyl content in the conjugated diene block is preferably in the range of 5 wt% to 40 wt% from the viewpoint of anti-caking property.
If necessary, a block mainly composed of ethylene or propylene may be contained.
The structure of the aromatic block copolymer having an aromatic group may be linear or 3 to 6-branched radial form in terms of ease of production.
The thermoplastic block copolymer having aromatics may contain a diblock body having a vinyl aromatic hydrocarbon block and a conjugated diene block in an amount of 10 wt% or more from the viewpoint of flexibility and anti-caking property of the printing plate. preferable.

The weight average molecular weight of the thermoplastic elastomer (a) is not particularly limited, but it should be excellent in the balance between molding processability and solid retention of the obtained photosensitive resin, and converted to polystyrene using gel permeation chromatography (GPC). 80,000 to 400,000 are preferable in terms of standard polystyrene.
The content of the thermoplastic elastomer (a) in the photosensitive resin composition is 40 wt% or more from the viewpoint of cold flow resistance and chipping resistance of the uncured resin structure, and 90 wt% or less from the viewpoint of flexibility. preferable. The range of 50 wt% to 90 wt% is more preferable, and the range of 60 wt% to 85 wt% is more preferable.
If necessary, another elastomer may be used in the photosensitive resin composition as long as it is 20 wt% or less.

The photopolymerizable unsaturated monomer (b) in the present invention is an ester such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, a derivative of acrylamide or methacrylamide, an allyl ester, styrene or a derivative thereof, N-substituted And maleimide compounds.
Specific examples include diacrylates and dimethacrylates of alkanediols such as hexanediol and nonanediol, or diacrylates and dimethacrylates of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, butylene glycol, and trimethylol. Propane tri (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N'-hexamethylenebisacrylamide And methacrylamide, styrene, vinyl toluene, divinyl benzene, diacryl phthalate, triallyl cyanu , Diethyl fumarate, dibutyl fumarate, dioctyl fumarate, distearyl fumarate, butyl octyl fumarate, diphenyl fumarate, dibenzyl ester fumarate, dibutyl maleate, dioctyl maleate Bis (3-phenylpropyl) fumarate, dilauryl fumarate, dibehenyl fumarate, N-laurylmaleimide and the like. These may be used alone or in combination of two or more.

If the content of the photopolymerizable unsaturated monomer (b) is too low, the formation of fine dots and characters will be reduced. If it is too high, the cold resistance when the photosensitive resin plate before exposure is laminated will be reduced. Since the flowability is lowered and the flexibility of the printing plate is lowered, the range of 1 wt% to 20 wt% in the photosensitive resin composition is preferable.
From the viewpoint of resistance to ester solvents, it is preferable to contain a photopolymerizable unsaturated monomer having a polyfunctional (meth) acrylate having two or more functions in a range of 3 wt% to 15 wt%. The range of 5 wt% to 15 wt% is more preferable, and it is preferable to use a polyfunctional acrylate and a polyfunctional methacrylate in combination.

The hydrocarbon plasticizer (c) essential for the present invention means that the weight average molecular weight is 2000 or less, the unsaturated bond amount is 0.5 mol / 100 g or less, and the refractive index at 20 ° C. is 1.496 or more. It is a featured hydrocarbon resin.
The hydrocarbon resin is substantially a resin composed of carbon and hydrogen. Specific examples thereof include natural resin rosin or terpene, synthetic resin aliphatic (C5) resin, aromatic (C9) resin, copolymer (C5 + C9). ) Resin, alicyclic resin, coumarone-indene resin, styrene resin, and / or their hydrogenated resins.
Natural resin-based rosins include gum rosin, polymerized rosin, modified rosin glycerin and pentaerythritol sell, etc. Terpenes include terpene resins (α-pinene, β-pinene, dipentene), aromatic modified terpene resins and terpene phenols Examples thereof include resins.

Synthetic resin-based aliphatic (C5) resins include polymers such as isoprene and piperylene, aromatic (C9) resins include polymers such as styrene, vinyltoluene and indene, and alicyclic resins include Polymers such as dicyclopentadiene are exemplified.
These may be used alone or in combination of two or more.
In the present invention, “substantially a resin composed of carbon and hydrogen” refers to an amount of elements such as nitrogen, oxygen, sulfur or chlorine other than carbon and hydrogen in the hydrocarbon resin of less than 1 mol / 100 g. In terms of ester solvent resistance, it is preferably less than 0.5 mol / 100 g, more preferably less than 0.2 mol / 100 g.

Among these, a resin obtained by hydrogenating (hydrogenating) a hydrocarbon resin having a cyclic structure is most preferable because of resistance to ester solvents.
The hydrogenation method is not particularly limited, and for example, a noble metal such as palladium, ruthenium, rhodium or the like supported on a carrier such as activated carbon, activated alumina, or diatomaceous earth is used as a catalyst. The method of performing is mentioned.
At this time, it is possible to use a batch system in which the reaction is performed while suspending and stirring the powdered catalyst, or a continuous system using a reaction tower packed with the molded catalyst, and there are no particular restrictions on the reaction format. Absent.

In the hydrogenation, the reaction solvent may not be used, but alcohols, ethers, esters, and saturated hydrocarbons are usually used.
The reaction temperature during hydrogenation is not particularly limited, but is usually 20 to 250 ° C, preferably 50 to 200 ° C. When the reaction temperature is less than 20 ° C., the hydrogenation rate becomes slow. On the other hand, when the reaction temperature exceeds 250 ° C., decomposition of the hydrogenated product may increase.
The weight average molecular weight of the hydrocarbon-based plasticizer (c) is 2000 or less, is easily dissolved in the resin, has high transparency, and provides a sharp fine line reproducibility. The range of 400-1500 is more preferable, and the range of 700-1500 is further more preferable.

The weight average molecular weight is a value determined from polystyrene conversion using gel permeation chromatography (GPC). Specifically, it was analyzed and calculated with an RI detector of HLC-8020 (GPC manufactured by Tosoh, trade name, column TSK-GEL-GMHXL).
The unsaturated bond amount of the hydrocarbon plasticizer (c) is 0.5 mol / 100 g or less, and ester solvent resistance is obtained. The lower the amount of unsaturated bonds, the higher the ester solvent resistance, preferably 0.33 mol / 100 g or less, more preferably 0.1 mol / 100 g or less.
The unsaturated bond amount is the total unsaturated bond amount in the hydrocarbon plasticizer and does not depend on the position in the main chain or side chain. For example, the number of unsaturated bonds in the benzene ring is 3.

The amount of unsaturated bonds can be determined from proton NMR (magnetic resonance spectrum). When an olefinic double bond is present, an H-spectrum appears in the vicinity of 4.5 to 6.0 ppm, and when a benzene ring is present, an H-spectrum appears near 7.0 ppm. be able to.
The refractive index of the hydrocarbon-based plasticizer (c) at 20 ° C. is 1.497 or more, and the fine line reproducibility and ester solvent resistance of the printing plate can be obtained. 1.510 or more is more preferable, and 1.520 or more is more preferable.
The refractive index can be measured by the JIS (K0062) method. If a smooth surface of the sample cannot be obtained, it can be obtained by dissolving in xylene, measuring in the same manner in a solution state of 30 wt%, 50 wt% and 70 wt%, and extrapolating to a concentration of 100 wt%.

The glass transition temperature of the hydrocarbon-based plasticizer (c) is preferably −20 ° C. or higher in terms of fine line reproducibility of the printing plate, resistance to ester solvents, or suppression of uneven density of minute halftone dots during printing. 0 degreeC or more is more preferable, and 20 degreeC or more is further more preferable.
The glass transition temperature can be measured by differential scanning calorimetry (DSC).
The content of the hydrocarbon-based plasticizer (c) in the photosensitive resin composition is preferably 6 wt% or more from the viewpoint of solvent resistance, and preferably 30 wt% or less from the viewpoint of microimage formation. The range of 8 wt% to 25 wt% is more preferable, and the range of 8 wt% to 20 wt% is more preferable.

The liquid conjugated diene rubber (d) having a viscosity of 2000 (Pa · s) or less at 30 ° C., which is essential for the present invention, contains 80% by weight or more of diene in the molecule and does not contain a reactive group such as an acrylate group or a methacrylate group. Is.
The viscosity can be measured according to JIS-K-7117.
The diene is preferably isoprene and / or butadiene from the viewpoint of availability, and butadiene is more preferable from the viewpoint of anti-caking property.
Specific examples include polybutadiene and polyisoprene.
The vinyl content in the conjugated diene rubber (d) is preferably higher in terms of the ability to form a fine image and the anti-scratch property, more preferably 50 mol% or more, 70 mol% or more, and even more preferably 75 mol% or more. . The vinyl content in the conjugated diene rubber can be determined from proton NMR (nuclear magnetic resonance spectrum).

  The weight average molecular weight in the conjugated diene rubber (d) is preferably low in terms of handleability and the compatibility of the photosensitive resin composition, and on the other hand, it is preferably high in terms of anti-caking property, and ranges from 1000 to 50000. Is preferable, the range of 2000 to 30000 is more preferable, and the range of 3000 to 20000 is more preferable. The content of the conjugated diene rubber (d) is preferably 3 wt% or more in the photosensitive resin composition from the viewpoint of image reproducibility, anti-scratch property, and flexibility. In this respect, 40 wt% or less is preferable, a range of 5 wt% to 30 wt% is more preferable, and a range of 7 wt% to 20 wt% is more preferable.

The photopolymerization initiator (e) referred to in the present invention is a compound that absorbs light energy and generates radicals, and various known compounds can be used, but various organic carbonyl compounds, particularly aromatic compounds. Carbonyl compounds are preferred.
Specific examples include thioxanthones such as benzophenone, 4,4-bis (diethylamino) benzophenone, t-butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,4-dichlorothioxanthone; Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 Acetophenones such as 2-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Acyl phosphine oxides such as methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenylacridine, and the like. These may be used alone or in combination of two or more.

If the content of the photopolymerization initiator (d) is too low, the formation of fine spots and characters will be reduced, and if it is too high, the transmittance of active light such as ultraviolet rays will be reduced, so in the photosensitive resin composition The range of 1 wt% to 5 wt% is preferable. The range of 1.5 wt% to 4 wt% is more preferable.
Further, various auxiliary additive components such as a plasticizer, a thermal polymerization inhibitor, an ultraviolet absorber, an antihalation agent, a light stabilizer and an antioxidant can be added as desired.
The Shore A hardness of the printing plate (2.84 mm thickness) of the present invention is preferably 45 ° or more from the viewpoint of printing reproducibility using an ester solvent-containing ink or ester solvent resistance. 50 ° or more is more preferable, and 55 ° or more is more preferable.

The flexographic printing plate composition of the present invention can be prepared by various methods.
For example, the raw material of the photosensitive resin composition is dissolved and mixed in a suitable solvent such as chloroform, tetrachloroethylene, methyl ethyl ketone, toluene, etc., and cast into a mold to evaporate the solvent. Can be made. Further, it can be molded to a desired thickness by a calender roll or a press after kneading with a kneader, roll mill or screw extruder without using a solvent, but the present invention is not limited to these preparation methods. .

  Since the photosensitive resin composition usually has adhesiveness, a solvent is applied to the surface of the resin layer in order to improve the contact property with the negative film superimposed on it during plate making or to enable reuse of the negative film. A soluble thin flexible protective layer (see, for example, Japanese Patent Publication No. 5-13305) may be provided. Instead of the flexible protective layer, an ultraviolet shielding layer containing an infrared sensitive substance may be provided, and the flexible layer itself may be used as a negative by direct drawing with an infrared laser. In any case, when the unexposed portion is washed out after the exposure is completed, the thin flexible protective layer is removed at the same time.

As a solvent-soluble thin flexible protective layer, for example, when a layer of polyamide, partially saponified polyvinyl acetate, cellulose ester or the like soluble in the washing solution is to be provided on the surface of the photosensitive resin layer, this is used. The photosensitive resin layer may be directly coated by dissolving in an appropriate solvent. Alternatively, the protective film may be transferred by coating (protective film) on a film of polyester, polypropylene, etc., and then laminating or press-pressing the protective film on the photosensitive resin layer.
The protective film and the support are usually adhered to the photosensitive resin composition by roll lamination after forming the sheet of the photosensitive resin composition, and a photosensitive resin layer with higher thickness accuracy can be obtained by heating and pressing after lamination.

As a general method for making a flexographic printing plate from a photosensitive composition for a flexographic printing plate, first, an ultraviolet exposure is performed on the entire surface through a support (back exposure), a thin uniform cured layer is provided, and then through a negative film, Alternatively, image exposure (relief exposure) is performed directly on the surface of the photosensitive resin layer from above the ultraviolet shielding layer, and the unexposed part is washed away with a developing solvent, or after heat-melting and absorbed and removed by the absorbing layer, post-processing exposure It is common to manufacture by doing.
As image exposure for changing the surface tension of the plate surface, ultraviolet light in a wavelength range of 200 nm to 300 nm may be exposed to ultraviolet light in a wavelength range of 310 nm to 400 nm.
Either the exposure from the negative film side (relief exposure) or the exposure from the support side (back exposure) may be performed first, or both may be performed simultaneously.

Examples of the exposure light source include a high pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, and a diode lamp.
Developer solvents used to develop unexposed areas include esters such as heptyl acetate and 3-methoxybutyl acetate, hydrocarbons such as petroleum fractions, toluene and decalin, and chlorinated organic solvents such as tetrachloroethylene. And a mixture of alcohols such as propanol, butanol and pentanol.
Washing out the unexposed area with the developing solvent is performed by jetting from a nozzle or by brushing with a brush.
As post-processing exposure, a method of irradiating the surface with light having a wavelength of 300 nm or less is common. If necessary, light larger than 300 nm may be used in combination.

  Hereinafter, the present invention will be described more specifically with reference examples, examples, and comparative examples, but the present invention is not limited to these examples.

[Reference example]
(1) Synthesis of thermoplastic elastomer A 10 L stainless steel reactor equipped with a jacket and a stirrer was sufficiently purged with nitrogen, and then 7000 cc of cyclohexane, 1 g of tetrahydrofuran, N, N, N ′, 0.8 g of N′-tetramethylethylenediamine, 170 g of styrene was charged, and warm water was passed through the jacket to set the contents at about 70 ° C. Thereafter, an n-butyllithium cyclohexane solution (1.15 g in pure content) was added to initiate styrene polymerization. After styrene is completely polymerized, 830 g of butadiene (1,3-butadiene) is added and polymerization is continued. After 4 minutes of complete polymerization of butadiene, 0.83 g of tetramethoxysilane is added and coupled. Reacted. A part of the obtained block copolymer solution was sampled, and then the solvent was removed by heating. The polymer had a styrene content of 17% by weight and a 1,2-vinyl bond content of the polyptadiene part of 35% by weight.
The styrene content was measured using ultraviolet spectroscopic analysis (UV). The vinyl bond amount was measured using infrared analysis (IR) and calculated by the Hampton method.

  Next, using the remaining block copolymer solution, hydrogenation was performed at a temperature of 70 ° C. using biscyclopentagenyl titanium chloride and n-butyl lithium as a hydrogenation catalyst. The hydrogenation rate was controlled by measuring the amount of hydrogen gas supplied with a flow meter and stopping the gas supply when the target hydrogenation rate was achieved. Thereafter, 10 g of water was added, and after stirring, 3.0 g of n-octadecyl-3- (3 ′, 5′di-tert-butyl-4′-hydroxyphenyl) propionate, 2,4-bis (n-octyl) 1.5 g of (thiomethyl) -O-cresol was added, and the resulting solution was subjected to steam stripping to remove the solvent and obtain a hydrous crumb. Subsequently, it was dehydrated and dried with a hot roll to obtain a sample of a thermoplastic elastomer having a hydrogenation rate of 15% in butadiene. The hydrogenation rate was confirmed using a nuclear magnetic resonance apparatus (NMR).

(2) Preparation of photosensitive resin composition and photosensitive structure As the photosensitive resin composition, the compositions shown in Tables 1 and 3 were mixed in a kneader at 140 ° C. for 60 minutes to obtain a photosensitive resin composition.
The obtained photosensitive resin composition is sandwiched between a support of a 125 μm thick polyester film coated with an adhesive containing a thermoplastic elastomer and a 100 μm polyester cover sheet having a 4 μm thick polyamide layer. The photosensitive structure for flexographic printing plates was molded using a 3 mm spacer with a press machine at 130 ° C. and a pressure of 200 kg / cm 2 for 4 minutes.

(3) Preparation of flexographic printing plate Remove the cover sheet of the photosensitive composition for flexographic printing plate of (2), and adhere a negative film on the polyamide protective film layer on the photosensitive resin layer. Using an ultraviolet fluorescent lamp having a central wavelength of 370 nm on a 1500 exposure machine (trade name, manufactured by Asahi Kasei Chemicals), first, an entire exposure of 300 mJ / cm 2 was performed from the support side, and then an image of 6000 mJ / cm 2 was passed through a negative film. (Relief) Exposure was performed.
The exposure intensity at this time was measured by measuring UV rays from the lower lamp on the side of the back exposure on a glass plate using a UV-35 filter with a UV illuminance meter MO-2 manufactured by Oak Manufacturing Co., Ltd. .3 mW / cm.sup.2, and the intensity of ultraviolet rays measured from the upper lamp on the relief exposure side was 12.5 mW / cm.sup.2.

  Next, using 3-methoxybutyl acetate as a developer, the plate was attached to a rotating cylinder of an AFP-1500 developing machine (trade name, manufactured by Asahi Kasei Chemicals) with double-sided tape, and developed at a liquid temperature of 25 ° C. for 5 minutes. Dry at 60 ° C. for 2 hours. Thereafter, as a post-processing exposure, the entire plate surface was exposed to 2000 mJ / cm 2 using a germicidal lamp having a central wavelength at 254 nm, and then exposed to 1000 mJ / cm 2 using an ultraviolet fluorescent lamp to obtain a flexographic printing plate. Here, the post-exposure amount with the germicidal lamp is calculated from the illuminance measured using the UV-25 filter of the MO-2 type machine.

(4) Evaluation Method 4-1) Image Reproducibility (4-1-1) Fine Line Reproducibility The shape of the 500 μm wide concave and convex fine lines of the relief image obtained in (3) was evaluated using a microscope. did. It is preferable that the groove of the concave fine wire is deep and the convex fine wire is sharp and not thick, and it is marked with ◯, and when the groove of the concave thin wire is shallow and the convex fine wire is not sharp and thick, it is x.
(4-1-2) Formability of Micro Image A 1% highlight portion of 59 lines (1 / cm) of the relief image obtained in (3) was evaluated using a microscope. If it was formed, it was good, and if it was not formed, it was a problem.

(4-2) Resistance to ester solvent (4-2-1) Change in thickness (4) Thickness change a after immersion of the printing plate obtained in (4) in a 20 wt% ethyl acetate-isopropyl alcohol solution at 25 ° C for 6 hours mm) = (thickness after immersion−initial thickness) and the sum (a + b) of thickness change b (mm) = (initial thickness−thickness after drying) when taken out after immersion and dried at 50 ° C. for 7 days, The smaller the change in the thickness, the higher the ester solvent resistance. The best one was ◎, the next best one was ○, and the one with the largest thickness change was ×.
(4-2-2) Scratch resistance The mechanical strength of the character portion on the plate when the printing plate was swollen by the solvent ink was evaluated by the following model experiment. NP-type printing durability test after immersing the printing plate with characters of 8 to 12 points as shown in FIG. 1 obtained in (4) in a 20 wt% ethyl acetate-isopropyl alcohol solution for 4 hours. Using a machine (manufactured by Shinmura Printing Co., Ltd., trade name, contact body: cloth, load 1 kg), after rubbing 100 times left and right, the degree of destruction of the characters was observed with a microscope. When only 8 point characters were destroyed, it was next better, ○, when 10 point characters were destroyed, next better, ○ ', and when 12 point characters were also destroyed, ×.

[Examples 1 to 3, Comparative Examples 1 to 4]
The evaluation test results of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 2.
Thermoplastic elastomer, photopolymerizable unsaturated monomer, hydrocarbon-based plasticizer having a weight average molecular weight of 2000 or less, an unsaturated bond amount of 0.5 mol / 100 g or less, and a refractive index of 1.497 or more, a liquid conjugate It can be seen that, by containing a diene rubber and a photopolymerization initiator, excellent reproducibility and high ester solvent resistance can be satisfied at the same time.

[Examples 1 and 4, Comparative Examples 5 and 6]
It can be seen that inclusion of a liquid conjugated diene rubber in the photosensitive resin composition satisfies the formability of microimages and the anti-fogging property during solvent swelling.

  The composition of the present invention can be suitably used in the field of a photosensitive resin composition for flexographic printing.

It is a conceptual diagram of an anti-choke test.

Claims (9)

At least a thermoplastic elastomer (a), a photopolymerizable unsaturated monomer (b), a hydrocarbon plasticizer (c), a liquid conjugated diene rubber (d) having a viscosity of 2000 (Pa · s) or less at 30 ° C., and A photosensitive resin composition for flexographic printing comprising a photopolymerization initiator (e), wherein the hydrocarbon-based plasticizer (c) has a weight average molecular weight of 2000 or less, an unsaturated bond amount of 0.5 mol / 100 g or less, and A photosensitive resin composition for flexographic printing, having a refractive index of 1.497 or more at 20 ° C.   The photosensitive resin composition for flexographic printing according to claim 1, wherein the conjugated diene rubber (d) has a vinyl content of 50 mol% or more.   The photosensitive resin composition for flexographic printing according to claim 1 or 2, wherein the vinyl content of the conjugated diene rubber (d) is 70 mol% or more. The photosensitive resin composition for flexographic printing according to any one of claims 1 to 3, wherein the content of the hydrocarbon plasticizer (c) in the photosensitive resin composition is 6 wt% to 30 wt%. object. The thermoplastic elastomer (a) is an aromatic block copolymer, and the content of the aromatic compound in the block copolymer is 28 wt% or less. The photosensitive resin composition for flexographic printing in any one. 6. The photopolymerizable unsaturated monomer (b) contains at least 3% by weight or more of a polyfunctional (meth) acrylate in the photosensitive resin composition. Photosensitive resin composition for flexographic printing. The photosensitive resin for flexographic printing according to any one of claims 1 to 6, wherein the hydrocarbon plasticizer (c) is a resin obtained by hydrogenating a hydrocarbon resin having a cyclic structure. Composition. The glass transition temperature of the hydrocarbon-based plasticizer (c) is -20 ° C or higher, and the refractive index at 20 ° C is 1.510 or higher, for flexographic printing according to any one of claims 1 to 7. Photosensitive resin composition.
~   The photosensitive structure for flexographic printing plates which has a laminated structure which consists of a support body and the layer of the photosensitive resin composition for flexographic printing in any one of Claims 1-8 formed on the surface.

Images