JPH11352687A - Photosensitive resin composition, its production, photosensitive resin original printing plate and photosensitive resin printing plate using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin original printing plate and a photosensitive resin printing plate satisfying conflicting requirement of water developing property and water resistance (especially ink resistance), excellent in workability and preservation stability and having excellent relief reproducibility and elasticity. SOLUTION: A photosensitive resin composition has phase separation structure composed of a continuous phase and a dispersion phase of fine particles dispersed in the continuous phase and the continuous phase contains an ethylenic unsaturated compound having a conjugated diene chain and an ethylenic unsaturated compound having a non-conjugated diene chain, which have number average molecular weight Mn of >=500, the weight average molecular weight to the number average molecular weight ratio Mw/Mn of >=2 and >=200 mPa/s viscosity at 20 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition which can be used in a photosensitive layer of a photosensitive resin printing original plate which can be developed with an aqueous developer, a method for producing the same, and a photosensitive resin printing original plate using the same. In particular, the present invention relates to a photosensitive resin composition useful for flexographic printing, a method for producing the same, a photosensitive resin printing plate using the same, and a photosensitive resin printing plate.

[0002]

2. Description of the Related Art As a conventional photosensitive resin original plate for flexographic printing, one developed with an organic solvent is known.
There were problems with human and environmental safety such as toxicity and flammability. Therefore, as an alternative to these, a printing original plate that can be developed with an aqueous developer has been proposed, and for example, comprises a photosensitive resin composition described below.

A copolymer obtained by homopolymerizing or copolymerizing a conjugated diene hydrocarbon, an α, β-ethylenically unsaturated carboxylic acid or a salt thereof, or a monoolefinic unsaturated compound, and a photopolymerizable unsaturated monomer Resin composition containing a monomer and a photosensitizer (JP-A-52-134655, JP-A-53-10648, JP-A-61-22)
No. 339), a conjugated diene-based hydrocarbon polymer or a copolymer of a conjugated diene-based hydrocarbon and a monoolefinic unsaturated compound, a hydrophilic polymer compound, a non-gaseous ethylenically unsaturated compound, and photopolymerization initiation Elastomer composition containing an agent as an essential component (JP-A-60-2
No. 11451), a photosensitive resin composition containing as essential components a hydrophobic oligomer having an α, β-ethylenically unsaturated group, an elastomer water-swellable substance and a photopolymerization initiator (Japanese Patent Application Laid-Open No. 60-173055). Gazette).

In order to improve the mechanical strength and rebound resilience of the printing plate, a photosensitive resin composition containing hard organic resin fine particles (see JP-A-63-8648), Resin compositions containing fine particles of a crosslinkable resin (JP-A-2-175702, JP-A-3-228060, JP-A-Heisei 4) for the purpose of imparting properties, imparting aqueous ink resistance, and improving printability. -293
907, JP-A-4-293909, JP-A-4-294353, JP-A-4-340968, JP-A-5-32743, JP-A-5-1504
No. 51, JP-A-5-204139),
A photosensitive resin composition having a two-phase structure for the purpose of improving the ink receptivity of a printing plate, containing a diazo compound and a dichromate in a continuous phase, and containing particles of 10 μm or less in a dispersed phase (Japanese Patent Publication No. No. 36731).

[0005]

However, in the printing original plate using the above-mentioned photosensitive resin composition, development with an aqueous developer, for example, an aqueous alkaline solution or an aqueous alkaline solution-organic solvent system is possible. , PH 5.0-
9.0 is difficult to develop with so-called domestic water, and the relief of the printing plate is insufficient in water resistance and resistance to ink containing water and / or alcohol (hereinafter also referred to as ink resistance). There's a problem. Further, in order to express the water resistance of the relief portion, when the content of the photopolymerizable ethylenically unsaturated compound is increased, the workability is reduced due to a decrease in the viscosity of the photosensitive resin composition before photopolymerization, and A cold flow phenomenon in which the resin starts to flow during storage occurs, and after photopolymerization, problems such as a loss of rubber elasticity due to an excessively high crosslink density occur.

In a printing plate using the above-mentioned or the photosensitive resin composition, it is necessary that a hydrophilic component is contained in a continuous phase in order to enable aqueous development. The content of the hydrophilic component needs to be larger than the content of the dispersed phase-forming component in terms of thermodynamic safety. Therefore, the water resistance of the relief part (especially the ink resistance)
Is inferior. In the above case, in order to express the water resistance of the relief portion, when the content of the photopolymerizable unsaturated compound is increased, the viscosity of the photosensitive resin composition before photopolymerization decreases, and the workability decreases, and A cold flow phenomenon in which the resin starts to flow during storage occurs, and after photopolymerization, problems such as a loss of rubber elasticity due to an excessively high crosslink density occur. On the other hand, when the content of the conjugated diene-based hydrocarbon polymer or the like is increased in order to maintain rubber elasticity, the viscosity of the photosensitive resin composition decreases similarly to the above, the workability decreases, and the resin during storage is reduced. The cold flow phenomenon that starts to flow occurs.

[0007] In the printing plate using the photosensitive resin composition described above, the image reproducibility of the relief portion of the printing plate,
The balance between resolution, hardness, rubber elasticity, mechanical strength, and water developability and water resistance (especially ink resistance) is governed by the particle size and content of the hard organic resin fine particles, and each property can be satisfied simultaneously. Have difficulty.

In the printing original plate using the above-mentioned photosensitive resin composition, water developability can be imparted by the crosslinked resin fine particles, but the hydrophilic component is bonded to the crosslinked resin fine particles. Due to the fusion and agglomeration of resin fine particles, stable performance cannot be exhibited or the distribution state of particles changes, causing the viscosity of the photosensitive resin composition to fluctuate before photopolymerization. There is a problem that a flow phenomenon occurs.

In the printing original plate using the above-mentioned photosensitive resin composition, a thin plate such as a planographic printing plate is practical, but it is difficult to apply it to a thick plate such as a flexographic plate. Also in this case, similarly to the above, due to the fusion and aggregation of the resin fine particles in the photosensitive resin composition, stable performance cannot be exhibited or the distribution state of the particles changes, so that the photosensitive particles are exposed before photopolymerization. There is a problem that the viscosity of the conductive resin composition fluctuates, and the workability is reduced and the cold flow phenomenon occurs.

The photosensitive resin composition is required to have good compatibility, low light scattering coefficient and proper refractive index. However, the hydrophilic component for enabling the above-mentioned aqueous development is required. Has a high polarity, so that it is compatible with water developability and ink resistance and develops good photosensitivity, and a type of a hydrophobic component that can be sufficiently compatible when mixed with the hydrophilic component, and There is a problem that the mixing ratio between the hydrophilic component and the hydrophobic component is limited. Furthermore, the copolymerization ratio of the monomers constituting the polymer as the hydrophilic component (for example, the copolymerization ratio of the monomer having a different hydrophilic group, the copolymerization ratio of the monomer having a hydrophilic group and the monomer having a hydrophobic group), the hydrophobic component However, there is a problem that the copolymerization ratio of the monomers constituting the polymer (for example, the copolymerization ratio of monomers having different hydrophobic groups), usable photopolymerization components, other components, and the mixing ratio thereof are limited. is there.

The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to prevent dispersion phase aggregation, excellent workability and storage stability, aqueous developing property and water resistance. It is an object of the present invention to provide a photosensitive resin printing plate and a photosensitive resin printing plate that satisfy the conflicting requirements of (especially ink resistance), have good relief reproducibility, and have excellent elasticity.

[0012]

Means for Solving the Problems In the phase structure of the photosensitive resin, the present inventors have proposed that the continuous phase contains an ethylenically unsaturated compound having a predetermined structure, a molecular weight, a molecular weight distribution and a viscosity. Have been found to solve the various problems described above, and have completed the present invention.

That is, the present invention has the following features. (1) A photosensitive resin composition having a phase separation structure consisting of a continuous phase and a particulate dispersed phase dispersed in the continuous phase, wherein the continuous phase has a number average molecular weight Mn of 500 or more and a weight relative to Mn. The ratio Mw / Mn of the average molecular weight Mw is 2 or more,
And a viscosity at 20 ° C. of 2000 mPa / s or more,
A photosensitive resin composition comprising an ethylenically unsaturated compound having a conjugated diene chain and an ethylenically unsaturated compound having a non-conjugated diene chain. (2) The photosensitive resin composition of (1) above, wherein the dispersed phase is a core-shell particle comprising a core phase containing a hydrophobic polymer and a shell phase containing the hydrophilic polymer and covering the core phase. . (3) The photosensitive resin composition according to (2), wherein the continuous phase is different from the hydrophobic polymer contained in the core phase, and further contains a hydrophobic polymer compatible with the ethylenically unsaturated compound. . (4) Number average molecular weight Mn is 500 or more, ratio of weight average molecular weight Mw to Mn Mw / Mn is 2 or more, and 20 ° C.
The viscosity at 2000 mPa / s or more is different from the ethylenically unsaturated compound having a conjugated diene chain and the ethylenically unsaturated compound having a non-conjugated diene chain, a hydrophilic polymer, a hydrophobic polymer, and the hydrophobic polymer. And mixing a hydrophobic polymer that is compatible with the ethylenically unsaturated compound and a solvent that dissolves or swells the hydrophilic polymer to form a continuous phase and a dispersed phase of core-shell particles by phase separation. A method for producing a photosensitive resin composition. (5) A support, and an original plate for photosensitive resin printing, wherein a photosensitive layer containing the photosensitive resin composition according to any one of claims (1) to (3) is laminated. . (6) A photosensitive resin printing plate, which is obtained by exposing and then developing the photosensitive resin printing original plate according to (5).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The photosensitive resin composition of the present invention has a phase separation structure composed of a continuous phase and a particulate dispersed phase dispersed in the continuous phase. As such a phase structure, for example, the following 3
Two structures are illustrated. A structure in which the hydrophobic polymer is a particulate dispersed phase and the hydrophilic polymer is a continuous phase surrounding it. A core-shell particle having a hydrophobic polymer as a core and a hydrophilic polymer as a shell is a dispersed phase, and a continuous phase mainly composed of a hydrophobic polymer different from the hydrophobic polymer surrounds the dispersed phase. A structure in which the hydrophilic polymer is a particulate dispersed phase and the hydrophobic polymer is a continuous phase surrounding it.

Hereinafter, the present invention will be described in detail based on a photosensitive resin composition having the following phase structure. The phase structure of
Since the content of the hydrophobic polymer can be increased and the content of the hydrophilic polymer can be reduced, the photosensitive layer using the photosensitive resin composition has ink resistance, and at the time of development, the hydrophilic polymer in the dispersed phase is used. Is swelled by water absorption and dispersed in the developing solution, but at the same time, the core made of a hydrophobic polymer is also dispersed in the developing solution, so that water developability can be exhibited while maintaining ink resistance.

The photosensitive resin composition having the phase structure of
A continuous phase c containing a specific ethylenically unsaturated compound which can become a hydrophobic polymer by photopolymerization; a core phase a containing a hydrophobic polymer; and a shell phase b covering the core phase and containing a hydrophilic polymer Is a photosensitive resin composition having a phase-separated structure in which the core-shell particles are dispersed in the continuous phase c.

In the present invention, the term hydrophilic refers to a property of dissolving or swelling in water or a developer containing water as a main component, and the term hydrophobic refers to a property containing water or water as a main component. It does not dissolve or swell in a developing solution.

In the photosensitive resin composition of the present invention, the shell phase b is formed around the core phase a by adsorption and / or association, and the core-shell particles are not bonded to the continuous phase c. The compounds used for the phase a, the shell phase b and the continuous phase c are selected such that these phases are not bonded to each other but are phase separated.

A. Core Phase In the present invention, a hydrophobic polymer (hereinafter, also referred to as a core phase forming hydrophobic polymer) is used as a polymer forming the core phase in order to make the photosensitive resin composition exhibit ink resistance and rubber elasticity. . Examples of such a hydrophobic polymer include hydrophobic polymers used as general-purpose elastomers, and specifically include non-conjugated diene-based elastomers and conjugated diene-based elastomers.

1) Non-conjugated diene-based elastomer Examples of the non-conjugated diene-based elastomer include a polyolefin-based elastomer having a chlorine atom and a polyolefin-based elastomer having no chlorine atom, and any of them is preferably used. Examples of the polyolefin elastomer having a chlorine atom include an elastomer obtained by chlorinating a polyolefin elastomer; an elastomer obtained by polymerizing a monomer having a chlorine atom; a monomer having a chlorine atom and having a chlorine atom. Elastomers obtained by copolymerization with unreacted monomers;
Alternatively, an elastomer obtained by reacting chlorine or an active substance having a chlorine atom with a polymer having no chlorine atom can be used. Specific examples of such a polyolefin-based elastomer having a chlorine atom include, for example, chlorinated polyethylene (Eraslen manufactured by Showa Denko KK, Daisorak manufactured by Daiso, HOLTA manufactured by Hoechst)
LIZ, DOW-CPE manufactured by Dow Chemical Co., Ltd., chlorinated ethylene-propylene rubber (Eraslen manufactured by Showa Denko KK), butyl chloride rubber, chlorinated polypropylene, vinyl chloride copolymer, polyvinylidene chloride, epichlorohydrin rubber , A copolymer of epichlorohydrin and ethylene oxide, a copolymer of epichlorohydrin and propylene oxide, a copolymer of epichlorohydrin and allyl glycidyl ether (Epichromer manufactured by Daiso Corporation,
Goodrich Co., Ltd. HYDRIN, Nippon Zeon Co., Ltd.
Zeospan manufactured by Hercules Co., Ltd.
R) and the like are exemplified, and among them, chlorinated polyethylene and chlorinated ethylene propylene rubber are preferable. These polymers are used alone or in combination of two or more.

The viscosity of the above-mentioned polyolefin elastomer having a chlorine atom is, for example, the Mooney viscosity of ML _{1 + 4} (121 ° C.) in consideration of the phase separation from the ethylenically unsaturated compound described below, for example. As one
It is preferably from 0 to 150.

The chlorine content of the above-mentioned polyolefin elastomer having a chlorine atom is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. The photosensitive resin composition may be damaged or deteriorate in heat stability, and the photosensitive resin composition may be hardened or colored.

Polyolefin-based elastomer having no chlorine atom
As the stomer, ethylene-propylene rubber, isobutane
Tylene rubber, ethylene-propylene-butadiene ternary
Polymer, acrylic rubber, ethylene-acrylic rubber, ethylene
Len-vinyl acetate copolymer, butyl rubber, butyl iodide
Rubber, hydrogen-reduced styrene-isoprene rubber, etc.
It is. The viscosity of these polymers is
Considering the phase separation from unsaturated compounds, for example,
The Mooney viscosity of Tylene-propylene rubber is ML _{1 + 4}(1
(00 ° C.) is preferably 20 to 150.

2) Conjugated Diene-Based Elastomer As the conjugated diene-based elastomer, a polymer obtained by polymerizing a conjugated diene-based hydrocarbon or a copolymer obtained by polymerizing a conjugated diene-based hydrocarbon and a monoolefin-based unsaturated compound is used. Polymers.

Examples of the conjugated diene hydrocarbon include, for example, 1,3-butadiene, isoprene,
Chloroprene and the like. These compounds alone,
Alternatively, two or more kinds are used in combination.

Specific examples of the above monoolefinically unsaturated compounds include, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene.
Methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide,
Methacrylamide, methacrylamide vinyl acetate,
Acrylic esters, methacrylic esters and the like can be mentioned.

The polymer obtained by polymerizing the conjugated diene-based hydrocarbon or the copolymer obtained by polymerizing a conjugated diene-based hydrocarbon and a monoolefin-based unsaturated compound is, specifically, Butadiene polymer, isoprene polymer, chloroprene polymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-
Chloroprene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chloroprene copolymer, acrylate-butadiene copolymer, methacrylate-butadiene copolymer, acrylate-isoprene Copolymer, methacrylate-isoprene copolymer, acrylate-chloroprene copolymer, methacrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-isoprene-styrene copolymer And acrylonitrile-chloroprene-styrene copolymer.

With respect to the viscosity of the conjugated diene elastomer, considering the phase separation from the ethylenically unsaturated compound described later, for example, the Mooney viscosity of acrylonitrile-butadiene rubber is 25 to ML _{1 + 4} (100 ° C.).
95, Mooney viscosity of polybutadiene rubber is ML
_{1 + 4} (100 ° C.) is 25 to 65, and the Mooney viscosity of polyisoprene rubber is 30 to ML _{1 + 4} (100 ° C.).
Preferably it is 100.

B. Shell phase The hydrophilic polymer used for the shell phase is a polymer that is soluble or swells in water or a developer containing water as a main component (hereinafter, also referred to as a shell phase-forming hydrophilic polymer).
It is. Such a hydrophilic polymer is selected depending on the type of the core phase-forming hydrophobic polymer or the ethylenically unsaturated compound, and has a higher affinity with the core phase-forming hydrophobic polymer, but the ethylenically unsaturated polymer described later. The compound has a structure having a lower affinity (for example, a compound having a common structure in the molecule with the hydrophobic polymer forming the core phase, a compound having a similar solubility parameter (SP value), a compound having a similar viscosity,
Empirical rules that have affinity) are selected. Examples of such a hydrophilic polymer include-
COOM ¹ group, -SO ₃ M ² group, -CONH ₂ group, -N
Examples thereof include polymers having a hydrophilic group such as an H ₂ group, —OH group, and —PO ₃ M ³ , and include a crosslinked polymer and a chain polymer that is not crosslinked.

Specifically, polyvinyl alcohol (PV
A), general-purpose resins such as carboxymethyl cellulose,
(T) Diene obtained by copolymerizing acrylic acid and diene compound
Rubber, liquid polybutadiene modified with maleic anhydride
, Liquid polyacrylonitrile-butadiene and the like.
However, the above hydrophilic group is added in an amount of 50 to 50,000 equivalent / 10
⁶It is preferable to use a hydrophilic polymer having g. This
50 equivalents / 10 of these groups⁶Less than g, parent to water
Poor compatibility, develop photosensitive resin printing plate with neutral water
May be difficult, and conversely, 50,000 equivalents / 1
0⁶If the amount exceeds g, the ink resistance of the photosensitive resin printing plate is poor.
There are cases.

The above M ¹ , M ² and M ³ are respectively
Hydrogen ion, monovalent metal ion (for example, Li ⁺ , Na
⁺ , K ^+, etc.) and divalent metal ions (eg, Ca ²⁺ , M
g ²⁺ ) or any of trivalent metal ions (eg, Al ³⁺ ) or substituted or unsubstituted ammonium ions.

[0032] Representative polymers with ¹ group -COOM, polyurethanes with ¹ group -COOM, -C
Polyureaurethane having OOM ¹ group, —COOM ¹
Epoxy compounds having a polyester, a ¹ group -COOM having a group, polyamic acid having ¹ group -COOM, -
Acrylonitrile having COOM ¹ group - butadiene copolymer, a styrene having ¹ group -COOM - butadiene copolymer, polybutadiene having a ¹ group -COOM, polyisoprene having ¹ group -COOM, -COO
A polychloroprene having an M ¹ group, a polyolefinene having a —COOM ¹ group, sodium polyacrylate,
Polyacrylamide, polyvinyl alcohol (PV
A), carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), and derivatives thereof, but are not limited thereto.

The above -COOM ¹ group is in an acid or salt form. The polymer in which the —COOM ¹ group is in the form of a salt is obtained by neutralizing the polymer having the —COOH group. Compounds used for neutralization include hydroxides of alkali metals such as lithium hydroxide, potassium hydroxide and sodium hydroxide; alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; potassium-t Alkoxides of alkali metals such as butoxide and sodium methoxide; hydroxides of polyvalent metals such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; polyvalent metal alkoxides such as aluminum isopropoxide; triethylamine, tri-n- Tertiary amines such as propylamine; secondary amines such as diethylamine and di-n-propylamine; cyclic amines such as morpholine; amino group-containing (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylate; Ammonium such as ammonium salts ; Magnesium acetate, calcium acetate, acetic acid metal salts such as aluminum acetate and the like. These may be used alone or in combination of two or more.

The above-mentioned hydrophilic polymer forming a shell phase may further have a polyoxyalkylene moiety as a hydrophilic group, and may have an ethylenically unsaturated group at a molecular terminal or a molecular inner chain so as to act as a crosslinking agent. May be included.

The hydrophilic polymer forming the shell phase is preferably 3 to 100 parts by weight, more preferably 10 to 70 parts by weight, based on 100 parts by weight of the hydrophobic polymer forming the core phase.
It is blended in a ratio of parts by weight. If the amount is less than 3 parts by weight, the water developability of the photosensitive resin printing plate prepared from the photosensitive resin composition may be insufficient.
If the amount is more than 00 parts by weight, the water resistance of the photosensitive resin printing plate may be insufficient, which is not preferable.

The shell phase may contain other components as long as they are compatible with the above-mentioned shell phase-forming hydrophilic polymer. Examples of such a component include an ethylenically unsaturated compound, a plasticizer, and an elastomer that are compatible with the hydrophilic polymer.

C. Continuous Phase In the present invention, the continuous phase contains a specific ethylenically unsaturated compound. 1) Ethylenically unsaturated compound The ethylenically unsaturated compound used in the present invention contains at least one ethylenically unsaturated bond, and has the property of undergoing chain growth addition polymerization with free radicals to form a high-molecular polymer. . That is, a compound capable of photopolymerization reaction,
The polymer is polymerized by ultraviolet irradiation or the like to become a hydrophobic polymer.

The ethylenically unsaturated compound used in the present invention has a number average molecular weight (Mn) of 500 or more, preferably 500 to 300,000, more preferably 500 to 100,000.
000 and a parameter representing the molecular weight distribution, a ratio Mw / Mn of the weight average molecular weight Mw to Mn.
Is 2 or more, preferably 2 to 15, and the viscosity at 20 ° C is 2000 mPa / s or more, preferably 250 mPa / s.
0 mPa / s or more, more preferably 3000 mPa / s
It has the above high molecular weight and high viscosity. The upper limit of the viscosity is about 1,000,000 mPa / s. In the present invention, the above-mentioned high molecular weight and high viscosity ethylenically unsaturated compound having a conjugated diene chain and the above high molecular weight and high viscosity ethylenically unsaturated compound having a non-conjugated diene chain are used in combination. Is done. In the present invention, the conjugated diene chain includes not only the conjugated diene chain itself but also a chemically modified one.

Since the ethylenically unsaturated compound used in the present invention has a high molecular weight and a high viscosity, the photosensitive resin composition of the present invention maintains a good solid state before photopolymerization,
Work becomes easy, and no cold flow phenomenon occurs during storage. In addition, when each component of the photosensitive resin composition is mixed, the high molecular weight and high viscosity ethylenically unsaturated compound is phase-separated without being compatible with the solid core phase forming hydrophobic polymer, so that the core-shell particles Can be prevented from coagulating and fusing in the continuous phase. Therefore, the relief reproducibility of the photosensitive resin printing plate using such a composition is improved.

When the Mn of the ethylenically unsaturated compound is less than 500, the molecular weight in the vicinity of the ethylenically unsaturated group, which is a cross-linking point, is small, so that the structure near the cross-linking point has a rigid structure, and the flexibility of the polymer is impaired. . When the ethylenically unsaturated group is polyfunctional, the compound has an Mw of 5
If it is less than 00, the distance between the cross-linking points becomes small for reasons other than those described above, so that the flexibility of the polymer is impaired. When Mw / Mn is less than 2, the molecular weight distribution near the ethylenically unsaturated group, which is a cross-linking point, becomes small, and the flexibility of the polymer is impaired. If the viscosity at 20 ° C. is less than 2000 mPa / s, the prepared photosensitive resin composition cannot be solidified well at room temperature, so that workability is poor and a cold flow phenomenon occurs during storage.
In addition, the core phase forming hydrophobic polymer cannot be phase separated.

In the present invention, since the ethylenically unsaturated compound having a conjugated diene chain and the ethylenically unsaturated compound having a non-conjugated diene chain are used in combination, the type and the mixing ratio of the ethylenically unsaturated compound are adjusted. It is possible to control the presence state of the core phase, the shell phase and the continuous phase in the photosensitive resin composition according to characteristics such as a desired water development speed, photosensitive characteristics, printing characteristics, and morphological stability during storage. Become.

Examples of the ethylenically unsaturated compound having a conjugated diene chain include unsaturated esters of polyols having a conjugated diene chain. For example, polybutadiene polyol (di) (meth) (urethane) acrylate, polynitrile butadiene polyol (di) (meth) (urethane) acrylate, polyisoprene polyol (di)
(Meth) (urethane) acrylate, polyconjugated diene polyol (di) (meth) such as polystyrene butadiene polyol (di) (meth) (urethane) acrylate
(Urethane) acrylates and the like; maleic esters of the above-mentioned high molecular weight polyols and the like, including those in which a part of a conjugated diene chain is reduced, are not limited thereto. These compounds can be used alone or in combination of two or more. Of course, as the ethylenically unsaturated compound having a conjugated diene chain, those having Mn, Mw / Mn, and the viscosity at 20 ° C. within the above range are used.

Examples of the ethylenically unsaturated compound having a non-conjugated diene chain include those obtained by reducing the entire conjugated diene chain of the unsaturated ester having a conjugated diene chain. Examples of such a compound include those obtained by reducing the above-mentioned polyol having a conjugated diene chain into an unsaturated ester, those obtained during or after the production of the above-described unsaturated ester having a conjugated diene chain, and the like. .

Examples of the ethylenically unsaturated compound having a non-conjugated diene chain include, for example, polyethylene glycol (di) (meth) (urethane) acrylate, polypropylene glycol (di) (meth) (urethane) acrylate, polytetramethylene Glycol (di) (meta)
Polyester polyols such as (urethane) acrylates (di) (meth) (urethane) acrylates; polyester polyols obtained by the condensation reaction of polyols such as polyethylene glycol and polycarboxylic acids such as terephthalic acid and adipic acid with unsaturated esters Polyester polyol (di) (meth) (urethane) acrylate incorporating polyethylene; polyethylene polyol (di) (meth) (urethane) acrylate, polypropylene polyol (di)
Polyolefin polyols (di) (meth) (urethane) acrylates such as (meth) (urethane) acrylate and polyethylene propylene polyol (di) (meth) (urethane) acrylate; maleic esters of the above-mentioned high molecular weight polyols; , But is not limited to this. These compounds can be used alone or in combination of two or more. Of course, the above ethylenically unsaturated compounds having a non-conjugated diene chain include Mn, Mw / Mn,
Those having a viscosity at 0 ° C. within the above range are used.

The method for introducing an unsaturated ester into the polyol includes a direct esterification reaction by a dehydration reaction between the polyol and the unsaturated carboxylic acid, and a transesterification reaction by a dealcoholation reaction between the polyol and the unsaturated carboxylic acid ester. Usual esterification methods can be used. Of these reactions, the direct esterification reaction of the polyol and the unsaturated carboxylic acid by the dehydration reaction involves a dehydration reaction of the polymerized polyol formed by the dehydration reaction of the polyols with the unsaturated carboxylic acid in advance. To obtain an ethylenically unsaturated compound.

The content ratio of the ethylenically unsaturated compound having a conjugated diene chain and the ethylenically unsaturated compound having a non-conjugated diene chain in the photosensitive resin composition of the present invention is such that the non-conjugated compound is The ethylenically unsaturated compound having a diene chain is preferably 0.01 to 80 parts by weight, more preferably 0.1 to 70 parts by weight, particularly preferably 0.5 to 70 parts by weight.
６０60 parts by weight. When the content of the ethylenically unsaturated compound having a non-conjugated diene chain is less than 0.01 part by weight, the oxidation resistance and ozone resistance of the photosensitive resin composition tend to be insufficient, If the amount exceeds 80 parts by weight, the rubber elasticity of the photosensitive resin composition tends to be insufficient, and phase separation occurs inside the continuous phase and light is scattered. There is a tendency that a good image cannot be formed by the printing plate.

The total amount of the ethylenically unsaturated compound used in the present invention is preferably from 10 to 200 parts by weight, more preferably from 15 to 150 parts by weight, based on 100 parts by weight of the core phase-forming hydrophobic polymer. Parts are blended. When the compounding amount is less than 10 parts by weight, the core-shell particles are aggregated and fused in the obtained photosensitive resin composition,
Further, it may not be possible to impart water resistance to the photosensitive resin printing plate, and conversely, if the compounding amount exceeds 200 parts by weight, the water developability of the photosensitive resin printing original plate may be insufficient, Not preferred.

An ethylenically unsaturated compound other than the above-mentioned ethylenically unsaturated compounds may be blended, and examples thereof include unsaturated esters of aliphatic alcohols such as cetyl alcohol and stearyl alcohol. Other examples include unsaturated esters of polyols. For example, ethylene glycol (di) (meth) acrylate, diethylene glycol (di) (meth) acrylate, glycerol (di) (meth) acrylate, 1,3-propanediol (di) (meth) acrylate, 1,4-butanediol (Di) (meth) acrylate, 1,2,4-butanetriol (di) (meth) acrylate, 1,2,4-butanetriol (tri) (meth) acrylate, 1,4
-Cyclohexanediol (di) (meth) acrylate, 1,6-cyclohexanediol (di) (meth) acrylate, trimethylolpropane (di) (meth) acrylate, diallyl phthalate, trimethylolpropane (tri) (meth) acrylate, Diallyl phthalate, diethyl fumarate, dibutyl maleate, 1,9-
Nonanediol (di) (meth) acrylate, N-substituted maleamide compound (for example, N-methylmaleamide, N-
Ethylmaleamide, N-laurylmaleamide, etc.).

2) Hydrophobic Polymer The continuous phase may contain a hydrophobic polymer in addition to the above-mentioned ethylenically unsaturated compound in terms of improving the physical properties and elasticity of the composition after photopolymerization. This hydrophobic polymer is a hydrophobic elastomer, which is compatible with the above-mentioned ethylenically unsaturated compound and different from the core phase forming hydrophobic polymer. Examples of such a hydrophobic elastomer include conjugated diene elastomers (for example, polybutadiene, acrylonitrile-butadiene rubber, polyisoprene, styrene-butadiene rubber, polyisoprene-styrene block copolymer, polybutadiene-styrene block copolymer, etc. ), Chlorine-free polyolefin-based elastomers (such as ethylene propylene rubber and butyl rubber), acrylic rubber, and ethylene vinyl acetate.

The continuous phase hydrophobic polymer is preferably 400 parts by weight based on 100 parts by weight of the core phase forming hydrophobic polymer.
It is blended in the composition at a ratio of 5 parts by weight or less, more preferably 5 parts by weight to 120 parts by weight. If the amount is more than 400 parts by weight, the ratio of the hydrophobic polymer forming the core phase becomes small, and it becomes difficult to develop the water-developability of the photosensitive resin printing plate precursor.

The photosensitive resin composition of the present invention contains, in addition to the above-mentioned hydrophobic polymer, hydrophilic polymer and ethylenically unsaturated compound, other components such as a photopolymerization initiator, a thermal polymerization inhibitor and a plasticizer. It may be blended.

Examples of the photopolymerization initiator used in the present invention include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzylalkyl ketals, anthraquinones, thioxanthones and the like. Contains benzophenone,
Chlorobenzophenone, benzoin, acetophenone,
Benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal,
Benzyl diethyl ketal, benzyl diisopropyl ketal, anthraquinone, 2-chloroanthraquinone,
2-ethylanthraquinone, thioxanthone, 2-chlorothioxanthone, methylnaphthoquinone, and the like,
Among them, benzyldimethyl ketal, methylnaphthoquinone and 2-ethylanthraquinone are preferred.

Such a photopolymerization initiator can be used in the composition 100
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on parts by weight. If the amount is less than 0.01 part by weight, the photopolymerization initiating ability tends to be insufficient. If the amount exceeds 10 parts by weight, the inside of the photosensitive layer does not harden due to its own shading, and the image tends to be easily chipped by development.

The thermal polymerization inhibitor is blended in order to prevent only the polymerization reaction due to heat without suppressing the photopolymerization reaction. Hydroquinone, hydroquinone monomethyl ether, catechol, pt-butyl catechol, 2,6-
Examples thereof include di-t-butyl-p-cresol, and among them, hadroquinone monomethyl ether and 2,6-di-t-butyl-p-cresol are preferable.

Such a thermal polymerization inhibitor is used in the composition 100
The amount is preferably 0.01 to 10 parts by weight, more preferably 0.001 to 5 parts by weight, based on parts by weight.

Examples of the plasticizer used in the present invention include liquid polybutadiene rubber, liquid polyacrylonitrile butadiene rubber, liquid polystyrene butadiene rubber,
Liquid rubbers such as liquid isoprene rubber, dioctyl phthalate, phthalic acid esters of aliphatic hydrocarbons including diheptyl phthalate, trimellitic acid esters including trioctyl trimellitate, 2-ethylhexyl adipate and the like Plasticizers such as adipic acid ester, and plasticizers such as adipic acid-based polyester or polyether ester having a molecular weight of about 400 to 3000 can be used, and these can be used alone or in combination of two or more.

The photosensitive resin composition of the present invention comprises a core phase-forming hydrophobic polymer, a shell phase-forming hydrophilic polymer, a specific ethylenically unsaturated compound having a conjugated diene chain,
By mixing a specific ethylenically unsaturated compound having a non-conjugated diene chain with a solvent that dissolves or swells the hydrophilic polymer, the affinity between the hydrophobic polymer forming the core phase and the hydrophilic polymer forming the shell phase becomes higher. A dispersed phase that is a core-shell particle is formed by adsorption and / or association based on the nature, and the ethylenically unsaturated compound forms a continuous phase. Such a photosensitive resin composition is prepared by utilizing the phase separation behavior of each component, but an apparatus and a method for promoting the phase separation are not limited.

Examples of the method for preparing the photosensitive resin composition of the present invention include a method in which the above-mentioned components are mixed or mixed in an arbitrary order, and a method in which the components are swelled and dispersed in an arbitrary solvent to obtain a uniform mixture. After that, a method of removing the solvent may be mentioned. The photosensitive resin composition thus obtained is usually molded into a desired shape.

In the preparation of the photosensitive resin composition, since the ethylenically unsaturated compound forming the continuous phase has a high molecular weight and a high viscosity, the ethylenically unsaturated compound does not dissolve in the core phase forming hydrophobic polymer and separates. , A core phase is formed. The shell phase-forming hydrophilic polymer dissolved or swollen by the solvent has a higher affinity with the core phase-forming hydrophobic polymer, but has a lower affinity with the ethylenically unsaturated compound in the continuous phase. It coats around the core phase in which phase is separated.

When a hydrophobic polymer different from the core phase forming hydrophobic polymer and compatible with the ethylenically unsaturated compound is further added, the hydrophobic polymer is compatible with the ethylenically unsaturated compound and becomes continuous. Form a phase.

Since the photosensitive resin composition of the present invention contains the above-mentioned high molecular weight and high viscosity ethylenically unsaturated compound as a continuous phase, it maintains a good solid state before photopolymerization. It becomes easy and no cold flow phenomenon occurs during storage. The photosensitive resin composition of the present invention is represented by (a / 2800) × 100% (amount of change in thickness of photosensitive layer: amm) measured by applying a load of 10 g on a photosensitive layer having a thickness of 2800 mm. Shape stability has a performance of preferably 5% or less, more preferably 2% or less.

Further, the photosensitive resin composition of the present invention comprises a combination of the above-mentioned ethylenic compound having a high molecular weight conjugated diene chain and an ethylenic compound having a high molecular weight non-conjugated diene chain. Form a continuous phase of the composition. For this reason, the photosensitive resin composition exhibits rubber elasticity, which is a characteristic of conjugated diene chains, and also has non-conjugated diene chains, so that oxidation deterioration and ozone deterioration, which are disadvantages of conjugated diene chains, are significantly improved. In addition, a polymer having a conjugated diene chain and a polymer having a non-conjugated diene chain can be used in combination as the hydrophobic polymer constituting the continuous phase, so that good oxidation deterioration resistance and ozone resistance can be maintained while maintaining good rubber elasticity. Deterioration can be exhibited.
Furthermore, when the photosensitive resin composition of the present invention is used as a flexographic printing plate, the anti-adhesion step by germicidal lamp treatment can be omitted because it has resistance to oxidation deterioration and ozone deterioration, and paper dust and dust are reduced. A good printed matter without sticking can be obtained.

The high-molecular-weight, high-viscosity ethylenically unsaturated compound used in the present invention is phase-separated without being compatible with the core-phase-forming hydrophobic polymer, so that the core-shell particles aggregate and fuse in the continuous phase. Can be prevented. The photosensitive resin composition of the present invention has the performance that the maximum particle size of the core-shell particles is preferably 30 μm or less, more preferably 20 μm or less. Therefore, the relief reproducibility of the photosensitive resin printing plate using such a composition is improved.

Furthermore, since the disperse phase is a core-shell particle containing a hydrophobic polymer, it is not necessary to increase the amount of ethylenically unsaturated compound for imparting water resistance, so that both water developability and water resistance can be achieved. Becomes As described later, the photosensitive resin printing plate prepared from the photosensitive resin composition of the present invention was subjected to photopolymerization and dried weight ag at 20 ° C.
The water swelling ratio represented by (ba) / a × 100% when weighed as bg after immersion in ion exchanged water for 24 hours is preferably 10% or less, more preferably 5% or less. Has performance.

Furthermore, since the dispersed phase is core-shell type particles, it is not necessary to increase the amount of ethylenically unsaturated compound for the development of water resistance, so that the photosensitive resin prepared from the photosensitive resin composition of the present invention can be used. The degree of crosslinking (hardness) of the resin printing plate does not increase. The photosensitive resin printing plate is JIS-K630
The hardness measured by the spring hardness test (A type) method according to 1 is preferably 30 to 80 degrees, more preferably 3 to 80 degrees.
It has a performance of 0 to 75 degrees and a rebound resilience of preferably 20% or more, more preferably 25% or more. Therefore, a photosensitive resin printing plate having good elasticity can be obtained.

In the photosensitive layer having the phase structure of (1), the hydrophilic polymer forming the shell phase and the ethylenically unsaturated compound in the continuous phase are preferably not chemically crosslinked in the uncured state. The hydrophilic polymer may be crosslinked or uncrosslinked in an uncured state. The shell phase-forming hydrophilic polymer and the continuous phase ethylenically unsaturated compound may or may not be chemically bonded to each other after curing.

The production apparatus used for mixing the components may have any structure as long as it produces the above-described phase separation behavior. Preferred examples of the production apparatus include a twin-screw extruder, a single-screw extruder, a pressure kneader, a Banbury type mixer, and a mixer having a general stirring function (for example, a ribbon-type stirring blade, an anchor-type stirring blade, a propeller, etc.). But not limited thereto. Examples of the production method for preparing the resin plate comprising the photosensitive resin matrix of the present invention by mixing the respective components include, but are not limited to, a method such as a casting method.

The original plate for printing a photosensitive resin of the present invention preferably comprises an adhesive layer, a photosensitive layer comprising the above-mentioned photosensitive resin composition, an anti-adhesion layer and a cover film on a support. As the production method, between the support having the adhesive layer formed thereon and the cover film having the anti-adhesion layer formed thereon,
A photosensitive resin printing plate is prepared by sandwiching the photosensitive resin composition on a sandwich (with both the adhesive layer and the anti-adhesion layer inside) and heat-pressing. The anti-adhesion layer contains polyvinyl alcohol, polyacrylamide, cellulose, polyamide and the like. As the support, a polyester film, a polyethylene film, a polypropylene film, or the like is used, and preferably, a polyester film can be used.

When such a photosensitive resin printing plate is irradiated with ultraviolet rays, at least the ethylenically unsaturated compound is polymerized and cured. The UV light applied during curing is
Those having a wavelength of 150 to 500 nm, particularly 300 to 450 nm, are preferable. Examples of such ultraviolet light sources include low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, ultraviolet fluorescent lamps, chemical lamps, xenon lamps, and the like.
A zirconium lamp or the like is desirable.

The photosensitive resin printing plate of the present invention is obtained by exposing the above-described photosensitive resin printing plate to an image exposure by irradiating ultraviolet rays with a negative film having a transparent image adhered thereto under the above-mentioned light source, and then exposing the uncured uncured resin. Approximately 20 ° C to 5
It is obtained by forming a relief image by removing with a developing solution at 0 ° C. The uncured photosensitive resin dissolved and removed remains in the developing tank as an emulsion or a suspension.

The developer used is a water-based developer to which a surfactant is added, and the above-mentioned hydrophilic polymer for forming a shell phase is one which is dissolved or dispersed in the developer to which the surfactant is added. It is important to use. That is, a usable developer is determined in view of work safety, environmental safety, availability, and the like, and a hydrophilic polymer used in the photosensitive layer is selected in accordance with the determined developer.

As the above-mentioned surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be widely used.
The addition amount of the surfactant is preferably 0.01 to 10% by weight in the developer. Further, a plurality of the above surfactants may be used in combination so as to perform optimal development.

The developer is preferably an aqueous developer in consideration of the safety of workers and the environment. If necessary, a water-based developer such as ethanol, isopropanol, cellosolve, glycerin, polyethylene glycol, dimethylformamide, dimethylacetamide, or acetone may be used. And an organic solvent miscible with water.

Further, the developer may be neutral, such as sodium carbonate, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium sulfate, sodium borate, sodium acetate, magnesium acetate, sodium citrate, and sodium succinate. Acidic or alkaline inorganic or organic salts; polymeric additives such as carboxymethylcellulose and methylcellulose; acids such as sulfuric acid, hydrochloric acid and phosphoric acid for adjusting pH, sodium hydroxide, potassium hydroxide and calcium hydroxide Alkali; other, viscosity modifiers, dispersion stabilizers, flocculants,
Various additives such as zeolite may be added as necessary.

For development, the photosensitive resin printing plate is immersed in a developer, and if necessary, the photosensitive resin layer is rubbed with a brush.
This is performed by removing uncured portions. The temperature during development is 20-50
C is preferred.

The photosensitive resin printing plate thus obtained has rubber elasticity and is useful as a flexographic printing plate. In addition, it has excellent ink resistance, ink transferability, and printing durability.

The photosensitive resin composition of the present invention can be used not only for flexographic printing plates but also for photoresists.
It can also be used for sandplasts, and can also be used as elastomers that can be cured by ultraviolet rays, adhesives, films, paints, and the like.

[0078]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition,
In the examples, parts mean parts by weight. The relief depth, hardness, rebound resilience, water swelling ratio, shape stability, presence / absence of core-shell formation, and presence / absence of particle aggregation are shown below.

1. Measurement conditions of Mn and Mw / Mn of ethylenically unsaturated compound Equipment used: GPC LC-4A manufactured by Shimadzu Corporation Sample used: 1 wt% THF solution Flow rate: 1 ml / min Column: Shodex KF-805L Measurement temperature: 20 ° C. UV wavelength: 220nm

2. Measurement method of viscosity of ethylenically unsaturated compound JIS by rotor type Brookfield viscometer
It measured at 20 degreeC according to K-6726.

3. Relief depth With respect to the photosensitive resin printing plate, a difference in height between an image area and a non-image area after development was measured by OG-911 manufactured by ONO SOKKI.

4. Hardness The photosensitive resin printing plate was measured at 20 ° C. by a spring-type hardness test (A method) according to JIS-K6301.

5. Rebound resilience: For a photosensitive resin printing plate, a steel ball having a diameter of 10 mm (weight of 4.16 g) was dropped from a height of 20 cm, and the rebound height (a) was read.
(A / 20) × 100% was set as a display value.

6. Water swelling ratio: The photosensitive layer resin composition was formed into a sheet having a thickness of 0.1 cm, a length of 2.0 cm, and a width of 5.0 cm, and exposure was performed at a dose of 4000 mJ / cm ² . The sheet was dried at 60 ° C. in a vacuum drier for 24 hours. This weight was weighed (a (g)). 20 ℃
Immersed in ion-exchanged water for 24 hours and weighed (b)
(G)). The indicated value was (ba) / a × 100% as the water swelling ratio.

7. Shape stability: Support the detection terminal of a thickness gauge (DG-911 manufactured by Ono Sokki Co., Ltd.) with a cylindrical detection terminal (detection terminal diameter: 10 mm, load: 10 g weight) on which a photosensitive layer made of a photosensitive resin composition is formed. Body (total thickness 2800m
m) for 60 seconds on the photosensitive layer side, and the amount of change (amm)
Was read, and (a / 2800) × 100% was taken as a display value.

8. Existence of Core-Shell Particles and Particle Aggregation The photosensitive resin composition was immersed in a 1.0% aqueous solution of a cationic dye (primocyanin: crystal violet) at 25 ° C. for 30 minutes to selectively dye the hydrophilic polymer. The state was observed using an optical microscope to determine whether core-shell particles were formed in the matrix. Furthermore, it was also observed whether or not the plurality of core-shell particles were aggregated with each other. It was evaluated that when a plurality of core-shell particles were close to or fused, particle aggregation occurred.

9. Evaluation of Ozone Degradation Resistance The hardness of a 5 × 20 × 1 mm photosensitive resin printing plate after being left at 25 ° C. for 24 hours in an O ₃ atmosphere (1 ppm, 1 m ³ / min) is a spring hardness according to JIS-K6301. It was measured at 20 ° C. by the test (Method A). In addition, the external shape was observed, and a comparison with the shape immediately after preparation of the photosensitive resin printing plate was shown by the degree of shrinkage.

Example 1 <Preparation of hydrophilic polymer I> 276 parts of hexamethylene diisocyanate, 145 parts of dimethylolpropionic acid,
Polyoxytetramethylene glycol (PTMG-85
0: 175 parts of Hodogaya Chemical Co., Ltd.), 60 parts of hydroxyethyl methacrylate, acrylonitrile-butadiene oligomer having an amino group at a terminal (HYCAR-A)
RBN1300 × 16: Ube Industries, Ltd.) 343 parts,
After dissolving 20 parts of di-n-butyltin dilaurate in 1000 parts of tetrahydrofuran in a 2 liter flask equipped with a condenser, the reaction was carried out at 60 ° C. for 4 hours. The completion of the reaction was confirmed by quantifying the amount of residual NCO. The -COOH group in the formed polymer was neutralized using lithium hydroxide monohydrate and magnesium acetate tetrahydrate in half equivalents to obtain a hydrophilic polymer I.

<Preparation of Ethylenically Unsaturated Compound I> A liquid polybutadiene having a hydroxyl group at the terminal (Poly-bd R-45HT, manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight 2800) was mixed with acrylic acid to dehydrate. And a number average molecular weight of 8000, Mw / Mn of 4.3, 20
An ethylenically unsaturated compound I having a viscosity at 9 ° C. of 9500 mPa / s was obtained. The obtained ethylenically unsaturated compound I is a polybutadiene component 9 having an acrylate group.
Non-conjugated diene component having 5% by weight and acrylate group 5
% By weight.

<Preparation of Photosensitive Resin Composition> Ten parts of the above hydrophilic polymer I, chlorinated polyethylene (Eraslen: 301MA, manufactured by Showa Denko KK); Glass transition temperature:
46 parts, polybutadiene (Nippon Synthetic Rubber Co., Ltd .: BRO2LL, glass transition temperature: -1)
02 ° C to -75 ° C) 14 parts, ethylenically unsaturated compound I
27 parts, benzyldimethyl ketal 1 part, hydroquinone monomethyl ether 0.1 part, 2,6-di-t-butylcresol 0.2 part, methylnaphthoquinone 0.05
Part, 2-ethylanthraquinone 0.5 part, toluene 10
0 parts and 10 parts of water were kneaded at 75 ° C. in a pressure kneader, and the solvent was removed to obtain a photosensitive resin composition.

Example 2 <Preparation of Ethylenically Unsaturated Compound II> A liquid polybutadiene having a hydroxyl group at its terminal (manufactured by Idemitsu Petrochemical Co., Ltd .: P
(poly-bd R45HT, number average molecular weight 2800) and methyl acrylate are mixed and subjected to a dehydration reaction to obtain an ethylenic substance having a number average molecular weight of 5700, Mw / Mn of 3.1, and a viscosity at 20 ° C. of 4100 mPa / s. The unsaturated compound II was obtained.

<Preparation of ethylenically unsaturated compound III>
A liquid polyolefin having a hydroxyl group at the terminal (manufactured by Mitsubishi Chemical Corporation: polytail HA, number average molecular weight 2,000) and acrylic acid are mixed, and a dehydration reaction is performed. The number average molecular weight is 9,000 and Mw / Mn is 4.2. An ethylenically unsaturated compound II having a viscosity at 2O <0> C of 21000 mPa / s was obtained.

<Preparation of Photosensitive Resin Composition> The procedure of Example 1 was repeated except that 25 parts of the ethylenically unsaturated compound II and 2 parts of the ethylenically unsaturated compound III were used in place of 27 parts of the ethylenically unsaturated compound I. A photosensitive resin composition was obtained in the same manner as in Example 1.

Example 3 <Preparation of ethylenically unsaturated compound IV> Ethylenically unsaturated compound IV was obtained by reacting polytetramethylene glycol (number average molecular weight 650), isophorone diisocyanate and hydroxyethyl acrylate.
The obtained ethylenically unsaturated compound IV had a number average molecular weight of 2000, Mw / Mn of 3.1, and a viscosity at 20 ° C of 3000 mPa / s.

<Preparation of Photosensitive Resin Composition> The procedure of Example 1 was repeated, except that 25 parts of the ethylenically unsaturated compound II and 2 parts of the ethylenically unsaturated compound IV were used in place of 27 parts of the ethylenically unsaturated compound I. A photosensitive resin composition was obtained in the same manner as in Example 1.

Example 4 In Example 1, acrylated polyisoprene (UCL-1, manufactured by Kuraray Co., Ltd., number average molecular weight 25,000, Mw) was used in place of 27 parts of the ethylenically unsaturated compound I.
/Mn=3.5, viscosity at 20 ° C. 8000 mPa /
s) A photosensitive resin composition was obtained in the same manner as in Example 1, except that 24 parts and 3 parts of the ethylenically unsaturated compound III were used.

Example 5 In Example 1, instead of 46 parts of chlorinated polyethylene, 46 parts of acrylonitrile-butadiene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd .: JSR N230SH) and 27 parts of ethylenically unsaturated compound I were used. A photosensitive resin composition was obtained in the same manner as in Example 1, except that 22 parts of the ethylenically unsaturated compound I and 5 parts of 1,9-nonanediol dimethacrylate were used.

Example 6 In Example 1, instead of 46 parts of chlorinated polyethylene, polyisoprene rubber (IR-1 manufactured by Kuraray Co., Ltd.) was used.
0) A photosensitive resin composition was obtained in the same manner as in Example 1, except that 46 parts were used.

Example 7 Example 1 was repeated except that 46 parts of styrene-isoprene-styrene block polymer (TR1107P, manufactured by Shell Japan K.K.) was used instead of 46 parts of chlorinated polyethylene. A photosensitive resin composition was obtained in the same manner.

Example 8 In Example 1, ethylene-propylene rubber (Nippon Synthetic Rubber Co., Ltd.) was used instead of 46 parts of chlorinated polyethylene.
Manufactured by JSR-EP-51) except that 46 parts were used.
A photosensitive resin composition was obtained in the same manner as in Example 1.

Example 9 In Example 1, acrylic rubber (NIPOL manufactured by Zeon Corporation) was used instead of 46 parts of chlorinated polyethylene.
AR54) A photosensitive resin composition was obtained in the same manner as in Example 1, except that 46 parts were used.

Comparative Examples 1 to 9 In Examples 1 to 9, 1,6-hexamethylene diacrylate 5 was used as the ethylenically unsaturated compound.
(Poly-bd R-45HT, manufactured by Idemitsu Petrochemical Co., Ltd .; number-average molecular weight: 2800) obtained by mixing 22 parts by weight with a polybutadiene having a hydroxyl group at the terminal (number-average molecular weight: 2800, Mw / Mn = 2) Example 3 except that a viscosity of 3000 mPa / s at 20 ° C.) was used.
In the same manner as in Examples 9 to 9, photosensitive resin compositions were obtained.

The photosensitive resin compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 9 were evaluated for shape stability, presence / absence of core-shell particles and particle aggregation, water swellability and ozone deterioration resistance. Table 1 shows the results.

<Preparation of a photosensitive resin printing plate> A polyester film having a urethane-based adhesive layer having a thickness of 125 μm on one side and a polyester film having a polyvinyl alcohol layer having a thickness of 100 μm on one side were prepared. Examples 1 to 14 and Comparative Example 1 with the adhesive layer and the polyvinyl alcohol layer inside.
To 14 were sandwiched between sandwiches, and 100 kg / kg at 100 ° C. with a heat press machine.
A pressure of ² cm ² was applied to obtain a sheet having a thickness of 2.9 mm.
Next, only the polyester film having the polyvinyl alcohol layer was peeled off, and the polyvinyl alcohol layer was left on the photosensitive resin layer to obtain a photosensitive resin printing original plate.

<Preparation of Photosensitive Resin Printing Plate> A negative film having an image was adhered onto the polyvinyl alcohol layer of the obtained photosensitive resin printing plate, and a high-intensity lamp (a hot bulb lamp manufactured by Anderson and Briland Co., Ltd.) was used. ), Exposure was performed at a dose of 4000 mJ / cm ² . After removing the negative film, development with a brush was performed at 40 ° C. for 15 minutes with neutral water containing 2% by weight of sodium alkylnaphthalenesulfonate to obtain a photosensitive resin printing plate. The resulting photosensitive resin printing plate was evaluated for relief depth, hardness and rebound resilience. Table 1 shows the results.

[0106]

[Table 1]

As shown in Table 1, all of the photosensitive resin compositions obtained in Examples 1 to 9 had no aggregation of core-shell particles.
The shape stability, water swelling property and ozone deterioration resistance are also good. All of the photosensitive resin printing plates have a relief depth of 1.4 to 2.0 mm and faithfully reproduce the image of the negative film used. The ink had good elasticity, had good ink transferability, and showed a clear image.

However, in the photosensitive resin compositions obtained in Comparative Examples 1 to 9, aggregation of core-shell particles was observed, and shape stability and ozone deterioration resistance were also poor. The photosensitive resin printing plate has a relief depth of 0.7 mm or less, does not faithfully reproduce the image of the negative film used, and has poor elasticity. Cracks occurred.

[0109]

As is apparent from the above description, according to the present invention, a photosensitive resin composition which is free from agglomeration of a dispersed phase, excellent in workability and storage stability can be provided. The present invention can provide a photosensitive resin printing plate and a photosensitive resin printing plate which satisfy the conflicting requirements of resilience (particularly ink resistance), have good relief reproducibility, and have excellent elasticity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 511 G03F 7/027 511 (72) Inventor Atsushi Kachi 2-1-1 Katada, Otsu City, Shiga Prefecture Toyobo Co., Ltd. Within the Research Institute

Claims (6)

[Claims] 1. A photosensitive resin composition having a phase-separated structure comprising a continuous phase and a fine-particle dispersed phase dispersed in the continuous phase, wherein the continuous phase has a number average molecular weight Mn of 500 or more and Mn. Containing an ethylenically unsaturated compound having a conjugated diene chain and an ethylenically unsaturated compound having a non-conjugated diene chain, having a weight average molecular weight Mw ratio of 2 or more and a viscosity at 20 ° C. of 2000 mPa / s or more. A photosensitive resin composition characterized in that: 2. The disperse phase is a core-shell particle comprising a core phase containing a hydrophobic polymer and a shell phase covering the core phase and containing a hydrophilic polymer. 3. The photosensitive resin composition according to item 1. 3. The continuous phase according to claim 2, wherein the continuous phase is different from the hydrophobic polymer contained in the core phase and further contains a hydrophobic polymer compatible with the ethylenically unsaturated compound. Photosensitive resin composition. 4. The number average molecular weight Mn is 500 or more, the ratio Mw / Mn of the weight average molecular weight Mw to Mn is 2 or more,
And a viscosity at 20 ° C. of 2000 mPa / s or more,
An ethylenically unsaturated compound having a conjugated diene chain and an ethylenically unsaturated compound having a non-conjugated diene chain; a hydrophilic polymer; a hydrophobic polymer; Production of a photosensitive resin composition characterized by mixing a compatible hydrophobic polymer and a solvent for dissolving or swelling the hydrophilic polymer, and forming a continuous phase and a dispersed phase of core-shell particles by phase separation. Method. 5. An original plate for printing a photosensitive resin, comprising a support and a photosensitive layer containing the photosensitive resin composition according to claim 1. 6. A photosensitive resin printing plate, which is obtained by exposing and then developing the photosensitive resin printing plate precursor according to claim 5.