JPH11349628A - Ethylenically unsaturated compound, photosensitive resin composition using the same, its preparation, photosensitive resin printing original sheet and photosensitive resin printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylenically unsaturated compound suitable for a photosensitive resin composition which has a high rubber elasticity, expresses a good flexibility, shows a good adhesion to various components and especially, is free from flocculation of the dispersion phase and has high workability and storage stability, a photosensitive resin composition containing this compound, a photosensitive resin printing original sheet or photosensitive resin printing plate which satisfies contradicting properties of an aqueous developability and a water resistance (especially ink resistance), shows a good relief reproducibility and has a good elasticity. SOLUTION: An ethylenically unsaturated compound has at least one ethylenically unsaturated bond within its molecule and has a number average molecular weight Mn of 500 or larger, a ratio Mw/Mn of the weight average molecular weight Mw to Mn of 2 or larger and a viscosity at 20 deg.C of 2,000 mPa/s or larger. Furthermore, a photosensitive resin composition has a phase-separating structure comprising a continuous phase containing this ethylenically unsaturated compound and a fine particulate dispersed phase dispersed in the continuos phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ethylenically unsaturated compound which can be polymerized by light, heat, etc., a photosensitive resin composition using the same, a method for producing the same, a photosensitive resin printing plate, and The present invention relates to a photosensitive resin printing plate. More specifically, metal, paper, coating such as film, coating, lining or primer, an ethylenically unsaturated compound widely applicable to the adhesion of various components, particularly a photosensitive resin composition that can be developed with an aqueous developer. The present invention relates to an ethylenically unsaturated compound suitable as a constituent, a photosensitive resin composition using the same, a method for producing the same, a photosensitive resin printing plate, 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).

[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.

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.

[0010] The photopolymerizable ethylenically unsaturated compound which has been conventionally used in the photosensitive resin composition includes:
There are many other than the above. For example, α, β
-Relatively low molecular weight compounds such as esters of ethylenically unsaturated carboxylic acids and polyols, N-substituted maleimide compounds, and oligo (meth) acrylates (JP-A-3-19042). These compounds themselves have no elasticity, and when used as a component of the photosensitive resin composition, problems such as a decrease in handling workability, generation of a cold flow phenomenon, and a decrease in rubber elasticity occur.

On the other hand, urethane-modified (meth) acrylates (JP-B-58-1128, JP-B-55-80) are used as ethylenically unsaturated compounds having a relatively high molecular weight.
No. 90, JP-B-56-1326, JP-B-54
And the like, and various attempts have been made to use them for applications such as adhesion and coating of various constituent materials such as metals. All of these are acrylates having a polyester as a main chain, and have problems such as low rubber elasticity and insufficient adhesion to constituent materials.

The present invention has been made to solve the above-mentioned problems, and has as its object to have high rubber elasticity, exhibit excellent flexibility, and have good adhesiveness to various constituent materials. In particular, an ethylenically unsaturated compound suitable for a photosensitive resin composition having excellent workability and storage stability without aggregation of a dispersed phase, and a photosensitive resin composition containing the compound, aqueous developability and water resistance (Especially ink resistance), and the reproducibility of relief is good.
An object of the present invention is to provide a photosensitive resin printing plate and a photosensitive resin printing plate having excellent elasticity.

[0013]

Means for Solving the Problems The present inventors have solved the above various problems by including an ethylenically unsaturated compound having a predetermined molecular weight, molecular weight distribution and viscosity in a continuous phase. As a result, the present invention has been completed.

That is, the present invention has the following features. (1) having at least one ethylenically unsaturated bond in the molecule, having a number average molecular weight Mn of 500 or more, a ratio Mw / Mn of weight average molecular weight Mw to Mn of 2 or more, and 20
An ethylenically unsaturated compound having a viscosity at 2000C of 2000 mPa / s or more. (2) reacting (A) an unsaturated carboxylic acid or an alkyl ester thereof with (B) at least one selected from the group consisting of polyether polyols, polyester polyols, polyconjugated diene-based polyols and polyolefin polyols The ethylenically unsaturated compound according to the above (1). (3) A photosensitive resin composition characterized by having a phase separation structure consisting of a continuous phase containing the ethylenically unsaturated compound according to (1) and a particulate dispersed phase dispersed in the continuous phase. Stuff. (4) The photosensitive resin according to (3), wherein the dispersed 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. Composition. (5) The photosensitive resin composition according to (4), 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. (6) The ethylenically unsaturated compound described in (1) above, a hydrophilic polymer, a hydrophobic polymer, and a hydrophobic polymer different from the hydrophobic polymer and compatible with the ethylenically unsaturated compound. Mixing a solvent for dissolving or swelling the hydrophilic polymer to form a continuous phase and a dispersed phase of core-shell particles by phase separation. (7) An original plate for printing a photosensitive resin, comprising a support and a photosensitive layer containing the photosensitive resin composition according to any one of the above (3) to (5). (8) A photosensitive resin printing plate, which is obtained by exposing and then developing the photosensitive resin printing original plate according to (7).

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The ethylenically unsaturated compound of 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, it is a compound capable of undergoing a polymerization reaction by light, heat, or the like, and is polymerized by ultraviolet irradiation, heating, or the like. The compound has a number average molecular weight Mn of 500 or more, a ratio Mw / Mn of the weight average molecular weight Mw to Mn of 2 or more, and a viscosity at 20 ° C. of 2000 mPa / s or more.

Since the ethylenically unsaturated compound of the present invention has such a high molecular weight and a high viscosity, the photosensitive resin composition of the present invention containing the compound as a constituent can be obtained at room temperature before polymerization. Maintains a solid state, making work easier,
Also, no cold flow phenomenon occurs during storage. After the polymerization, rubber elasticity and relief reproducibility are improved.

Further, since the ethylenically unsaturated compound of the present invention has a property of exhibiting thermosetting property by adding a thermal polymerization initiator, the compound is used in addition to the use as a constituent of the photosensitive resin composition. It can be applied to a wide range of applications such as adhesion of various materials, painting and coating.

The ethylenically unsaturated compound of the present invention is not particularly limited as long as it has the above-mentioned physical properties. (A) Unsaturated carboxylic acid or its alkyl ester and (B) a high molecular weight compound having a hydroxyl group at a molecular terminal. Those obtained by reacting polyols are exemplified.

As the unsaturated carboxylic acid or the alkyl ester thereof as the component (A), acrylic acid, methacrylic acid,
Examples include, but are not limited to, unsaturated carboxylic acids such as maleic acid, or alkyl esters thereof, such as methyl acrylate and hydroxyethyl (meth) acrylate. These can be used alone or in combination of two or more.

The high molecular weight polyols having a hydroxyl group at the molecular terminal of component (B) include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; polyols such as polyethylene glycol and terephthalic acid, adipic acid and the like. Polycondensed diene polyols such as polybutadiene polyol, polynitrile butadiene polyol, polyisoprene polyol and polystyrene butadiene polyol; polyolefin polyols such as polyethylene polyol, polypropylene polyol and polyethylene propylene polyol; However, the present invention is not limited thereto. These can be used alone or in combination of two or more.

The ethylenically unsaturated compound of the present invention comprises a component
(A) and (B) can be obtained by performing known esterification. Specific esterification methods include a direct esterification reaction by a dehydration reaction between a polyol and an unsaturated carboxylic acid and a transesterification reaction by a dealcoholation reaction between a polyol and an unsaturated carboxylic acid ester. In the direct esterification reaction by the dehydration reaction between a polyol and an unsaturated carboxylic acid, a polyol which has been polymerized by performing a dehydration reaction between polyols having hydroxyl groups at ends using an acid catalyst is obtained in advance to obtain a polyol which has been polymerized. A method for obtaining an ethylenically unsaturated compound by a dehydration reaction with a saturated carboxylic acid is also included.

Examples of the solvent used in the above reaction include common hydrocarbon solvents such as cyclohexane and n-heptane.

The ethylenically unsaturated compound of the present invention has a number average molecular weight (Mn) of 500 or more, preferably 500 to 3
00000, more preferably 500 to 100,000, and the ratio Mw / Mn of the weight average molecular weight (Mw) to Mn, which is a parameter representing the molecular weight distribution, is 2 or more, preferably 2 to 15, and the viscosity at 20 ° C. Is 2000 mPa / s or more, preferably 2500 mP
a / s or higher, more preferably 3000 mPa / s or higher, and high viscosity. The upper limit of the viscosity is about 1,000,000 mPa / s.

When the Mn of the ethylenically unsaturated compound is less than 500, the molecular weight near the ethylenically unsaturated group, which is the 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 obtained 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 obtained 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.

The ethylenically unsaturated compound of the present invention may contain various stabilizers, if necessary, for the purpose of improving the physical properties and handling workability and adjusting the compatibility, as in the case of general radical polymerization type curable resins. Agents, plasticizers, reinforcing agents, fillers and the like can be used in combination.

The method of polymerizing the ethylenically unsaturated compound of the present invention by light is particularly preferable. In this case, the compound and a known photopolymerization initiator are mixed and dissolved in an arbitrary solvent, and then concentrated and molded or dried by coating. Then, only necessary parts are irradiated with light to carry out polymerization, and insoluble parts are removed with a developing solution such as water, so that they can be used for an intended image, sealant, or adhesive application. Examples of the photopolymerization initiator that can be used in the present invention include benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzylalkyl ketals, anthraquinones, thioxanthones, and the like. , 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-ethyl Examples include anthraquinone, thioxanthone, 2-chlorothioxanthone, and methylnaphthoquinone. Ketal, methyl naphthoquinone, and 2-ethyl anthraquinone are preferable.

In addition, the ethylenically unsaturated compound of the present invention is not polymerized by heat. In this case, the compound is dissolved in an arbitrary solvent, and after coating and drying, polymerization is performed by heat treatment, or melt molding. Thereafter, a method of performing polymerization by heat treatment, or the like can be given. If necessary, an arbitrary amount can be blended according to the physical properties of a polymer from which a known thermal polymerization initiator can be obtained. For example, organic peroxides used in general radical polymerization type curable resins such as benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauroyl peroxide, dicumyl peroxide and cumene hydroperoxide. Oxides can be used. If necessary, a promoter such as dimethylaniline or cobalt naphthenate can be used in combination. A temperature range suitable for thermal polymerization and melt molding is 70 to 200 ° C.

The thermal polymerization initiator is preferably used in an amount of 0.001 to 100 parts by weight of the ethylenically unsaturated compound.
5 parts by weight, more preferably 0.05 to 3 parts by weight is blended.

Since the ethylenically unsaturated compound of the present invention has a relatively long hydrocarbon chain in the molecule, it has excellent compatibility with general-purpose resins. Specifically, a general-purpose elastomer having a glass transition temperature of 5 ° C. or lower can be used.

The ethylenically unsaturated compound of the present invention has a high viscosity and is polymerizable and compatible with general-purpose resins, so that it can be applied to image forming materials such as flexographic printing plates, photoresists, and sandblasts. ,heat,
It can be used as a polymer polymerized by light or electron beam, for example, an adhesive, a paint, a sealant, a binder and the like.

Such an ethylenically unsaturated compound can be suitably used as a constituent of a photosensitive resin composition. Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises a continuous phase,
It has a phase-separated structure consisting of a fine-particle dispersed phase dispersed in the continuous phase. As such a phase structure, for example, the following three structures are exemplified. 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 as described above has ink resistance, and at the time of development, the hydrophilic property of the dispersed phase is high. The polymer shell absorbs and swells and disperses in the developing solution. At the same time, the hydrophobic polymer core also disperses 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 that can become a hydrophobic polymer by photopolymerization, a core phase a containing a hydrophobic polymer, and a shell phase covering the core phase and containing a hydrophilic polymer b) is a photosensitive resin composition having a phase-separated structure in which core-shell particles composed of b) are dispersed in a continuous phase c.

In the present invention, hydrophilicity means a property of dissolving or swelling in water or a developer containing water as a main component, and hydrophobicity means 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 As the non-conjugated diene-based elastomer, a polyolefin-based elastomer having a chlorine atom and a polyolefin-based elastomer having no chlorine atom can be mentioned, and all of them are 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, ML _{1 + 4} (121 ° C.) in consideration of the phase separation from an ethylenically unsaturated compound described below, in consideration of the phase separation. As one
It is preferably from 0 to 150.

The chlorine content of the above-mentioned polyolefin elastomer having chlorine atoms 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 Elastomers Conjugated diene-based elastomers include polymers obtained by polymerizing conjugated diene-based hydrocarbons and copolymers obtained by polymerizing conjugated diene-based hydrocarbons with monoolefinic unsaturated compounds. Polymers.

As the conjugated diene-based hydrocarbon, specifically, 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-mentioned monoolefinically unsaturated compound 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 monoolefinic unsaturated compound is specifically described as follows. 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.

Considering the phase separation of the conjugated diene elastomer from the ethylenically unsaturated compound described below, 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 and an —OH group, and include a crosslinked polymer and a non-crosslinked chain polymer.

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-mentioned 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 M¹, M^TwoAre hydrogen ions
Monovalent metal ions (eg, Li ⁺, Na⁺, K⁺
Etc.) divalent metal ions (eg, Ca²⁺, Mg
²⁺Etc.) trivalent metal ions (eg, Al³⁺Etc.) or
Either a substituted or unsubstituted ammonium ion
U.

[0050] 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 -COOM ¹ group is in the form of an acid or a salt. 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 shell phase-forming hydrophilic polymer 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 obtained photosensitive resin composition may be insufficient, and if it exceeds 100 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 it is 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 the above-mentioned ethylenically unsaturated compound. Since the ethylenically unsaturated compound used in the present invention has a high molecular weight and a high viscosity as described above, the photosensitive resin composition of the present invention maintains a good solid state before photopolymerization. The work becomes easy, and the cold flow phenomenon does not occur during storage. Furthermore, at the time of mixing each component of the photosensitive resin composition, 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 core-shell particles are formed. Agglomeration and fusion in the continuous phase can be prevented. Therefore,
The relief reproducibility of a photosensitive resin printing plate using such a composition is improved.

The above ethylenically unsaturated compound is preferably used in an amount of 10 to 200 parts by weight, more preferably 15 to 1 part by weight, based on 100 parts by weight of the core phase-forming hydrophobic polymer.
It is blended in a proportion of 50 parts by weight. When the amount is less than 10 parts by weight, the core-shell particles may be aggregated and fused in the obtained photosensitive resin composition, or may not be able to impart water resistance to the photosensitive resin printing plate. If the amount is more than 200 parts by weight, the water-developability of the photosensitive resin printing plate may be insufficient, which is not preferable.

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 preferably contains a hydrophobic polymer in addition to the above ethylenically unsaturated compound from the viewpoint 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 may contain, in addition to the above-mentioned hydrophobic polymer, hydrophilic polymer, and ethylenically unsaturated compound, other components such as the above-mentioned photopolymerization initiator and the like, or a thermal polymerization inhibitor. And a plasticizer and the like.

The photopolymerization initiator is preferably blended in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the composition. 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 by heat without suppressing the photopolymerization reaction, and includes 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 can be 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 is obtained by mixing a hydrophobic polymer forming a core phase, a hydrophilic polymer forming a shell phase, an ethylenically unsaturated compound, and a solvent that dissolves or swells the hydrophilic polymer. Thus, the core phase-forming hydrophobic polymer and the shell phase-forming hydrophilic polymer form a dispersed phase, which is a core-shell particle, by adsorption and / or association based on their affinity, and the ethylenically unsaturated compound forms a continuous phase. Form. 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 of mixing or collectively mixing the above components in an arbitrary order, and a method of uniformly swelling and dispersing each component in an arbitrary solvent. 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 is phase-separated. , 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.

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

The photosensitive resin composition of the present invention maintains a good solid state before photopolymerization by containing a high-molecular-weight and high-viscosity ethylenically unsaturated compound as a continuous phase. 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 is preferably 5%
Or less, more preferably 2% or less.

Further, since the high molecular weight and high viscosity ethylenically unsaturated compound is not compatible with the core phase forming hydrophobic polymer and undergoes phase separation, it is possible to prevent the core-shell particles from coagulating and fusing in the continuous phase. . The photosensitive resin composition of the present invention,
The core-shell particles preferably have a maximum particle size of 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 the ethylenically unsaturated compound in order to develop 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 above phase structure, 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-mentioned 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-described 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,
An original photosensitive resin printing plate is prepared by sandwiching the photosensitive resin composition on a sandwich (with the adhesive layer and the anti-adhesion layer both 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 the 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-mentioned photosensitive resin printing plate to a negative film having a transparent image under the above-mentioned light source and irradiating the film with ultraviolet rays to expose the image. 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 has been added, and the above-mentioned hydrophilic polymer should be one which dissolves or disperses in the developer to which this surfactant has been added. is important. 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, and if necessary, a water-based developer such as ethanol, isopropanol, cellosolve, glycerin, polyethylene glycol, dimethylformamide, dimethylacetamide, or acetone. And an organic solvent miscible with water.

Further, the developing solution may be neutral, such as sodium carbonate, sodium tripolyphosphate, potassium pyrophosphate, sodium silicate, sodium sulfate, sodium borate, sodium acetate, magnesium acetate, sodium citrate, sodium succinate, and the like. 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 very 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 are cured by ultraviolet rays, such as adhesives, films, and paints.

[0085]

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. In addition, the acid value, viscosity, Mn and Mw / Mn and adhesiveness of the ethylenically unsaturated compound, water swellability of the photosensitive resin composition, shape stability and the presence or absence of formation of core-shell particles and particle aggregation, photosensitive resin printing The relief depth, hardness and rebound resilience of the plate were measured by the following methods.

1. Method for measuring acid value of ethylenically unsaturated compound JIS standards K-0070, K-3504, K-880
4 JOCS Measurement method of viscosity of ethylenically unsaturated compound JIS by rotor type Brookfield viscometer
It measured at 20 degreeC according to K-6726. 3. Measurement 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: 220 nm

4. Measurement of Adhesiveness of Ethylenically Unsaturated Compound A tensile speed of 20 was applied to various plate-like materials according to JIS-K6854.
The strength at the time of peeling at 0 mm / min was measured. 5. Measurement of Relief Depth of Photosensitive Resin Printing Plate For the photosensitive resin printing plate, a difference in height between an image portion and a non-image portion after development was measured by OG-911 manufactured by ONO SOKKI. 6. 6. Measurement of Hardness of Photosensitive Resin Printing Plate The photosensitive resin printing plate was measured at 20 ° C. by a spring-type hardness test (A method) according to JIS-K6301. Measurement of the rebound resilience of the photosensitive resin printing plate The diameter of the photosensitive resin printing plate was 10 mm (the weight was 4.16).
g) The steel ball was dropped from a height of 20 cm, and the rebound height (a) was read, and (a / 20) × 100% was taken as a display value.

8. Measurement of shape stability of photosensitive resin composition Cylindrical detection terminal (detection terminal diameter: 10 mm, load 10 g
Weight) and a detection terminal of a thickness gauge (DG-911 manufactured by Ono Sokki Co., Ltd.) is placed on the photosensitive layer side of the support (total thickness 2800 mm) on which the photosensitive layer made of the photosensitive resin composition is formed for 60 seconds,
The amount of change (amm) is read, and (a / 2800) ×
100% was taken as the indicated value. 9. Measurement of Water Swelling Ratio of Photosensitive Resin Composition 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 the irradiation amount was 4000 mJ / c.
An exposure of m ² was performed. The sheet was dried at 60 ° C. in a vacuum drier for 24 hours. This weight was weighed (a
(G)). This was immersed in ion exchanged water at 20 ° C. for 24 hours and weighed (b (g)). The water swelling ratio is (ba)
/ A × 100% was set as a display value.

10. Presence or absence of core-shell particles and particle aggregation of the photosensitive resin composition The photosensitive resin composition is 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. did. 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.

Example 1 900 parts of liquid polybutadiene having a hydroxyl group terminal (Poly-bd R-45HT, manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight 2800), 74 parts of acrylic acid, 0.3 part of hydroquinone monomethyl ether and A solution prepared by dissolving 0.09 part of maleic anhydride in 900 parts of n-heptane was placed in a flask equipped with a stirrer, heated to 80 ° C. and refluxed. When the acid value became 14 or less, the reaction was terminated. After cooling, the reaction was diluted with 346 parts of n-heptane, filtered with a pressure filter, and concentrated and the concentration was adjusted while keeping the acid value at 10 or less. Thus, an ethylenically unsaturated compound I was obtained. This ethylenically unsaturated compound I has a number average molecular weight of 7100, Mw / M
n is 3.8, viscosity at 20 ° C. is 7500 mPa / s
Met.

Example 2 In the same manner as in Example 1, a liquid polybutadiene having a hydroxyl group at a terminal (manufactured by Idemitsu Petrochemical Co., Ltd .: Poly-
bd R45HT, number average molecular weight 2800) and acrylic acid, and a dehydration reaction was performed to obtain a number average molecular weight 800
0, Mw / Mn is 4.3, viscosity at 20 ° C. is 950
An ethylenically unsaturated compound II having 0 mPa / s was obtained.

Example 3 In the same manner as in Example 1, a liquid polybutadiene having a hydroxyl group at a terminal (manufactured by Idemitsu Petrochemical Co., Ltd .: Poly-
(bd R-45HT, number average molecular weight 2800) and methyl acrylate, and transesterification was carried out to obtain a number average molecular weight (Mn) of 5700, Mw / Mn 3.1, and 20 ° C.
, An ethylenically unsaturated compound III having a viscosity of 4100 mPa / s was obtained.

Example 4 In the same manner as in Example 1, a hydroxyl-terminated polyisoprene (Poly-I manufactured by Idemitsu Petrochemical Co., Ltd.) was used.
P) and acrylic acid were mixed to perform a dehydration reaction to obtain an ethylenically unsaturated compound IV having a number average molecular weight (Mn) of 8000, Mw / Mn of 4.0, and a viscosity at 20 ° C of 8000 mPa / s.

Example 5 In the same manner as in Example 1, an ethylenically unsaturated compound V was obtained by reacting polytetramethylene glycol (number average molecular weight 650), isophorone diisocyanate and hydroxyethyl acrylate. The obtained ethylenically unsaturated compound V had a number average molecular weight of 2,000 and Mw /
Mn = 3.1, viscosity at 20 ° C. is 3000 mPa /
s.

Example 6 Hydrogenated polybutadiene-terminated polyol (polytail HA manufactured by Mitsubishi Chemical Corporation) 253.7
g, hexamethylene diisocyanate 40.8 g, di-
2.9 g of n-butyltin dilaurate was mixed, and N ₂ was added.
After reaction at 80 ° C. for 4 hours, 27 g of hydroxyethyl acrylate and 0.005 g of phenothiazine were added, and the reaction was further carried out at 80 ° C. for 4 hours to obtain an ethylenically unsaturated compound VI. The obtained ethylenically unsaturated compound VI had a number average molecular weight of 9,500 and Mw / Mn = 3.9,2.
The viscosity at 0 ° C. was 10,000 mPa / s or more.

For the ethylenically unsaturated compounds obtained in Examples 1 to 6, Mn, Mw / Mn and viscosity were measured. Table 1 shows the results.

[0097]

[Table 1]

Also, 300 parts of the ethylenically unsaturated compound obtained in Examples 1 to 4 and styrene 100 were kneaded, and 1.0% of methyl ethyl ketone peroxide (55% solution of dimethyl phthalate) and 1.0% of cobalt naphthenate (Co
0.3% (6% content, mineral spirit solution) was added and cured at room temperature. The adhesiveness of the obtained resin to various plate-like objects was measured. Table 2 shows the results.

[0099]

[Table 2]

Example 7 <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 photosensitive resin composition> 27 parts of the ethylenically unsaturated compound I obtained in Example 1, 10 parts of the above hydrophilic polymer I, chlorinated polyethylene (Showa Denko KK)
Made: Eraslen: 301MA; Glass transition temperature: -30
46 ° C., polybutadiene (Nippon Synthetic Rubber Co., Ltd .: BRO2LL, glass transition temperature: −102 ° C.)
14 parts, benzyldimethyl ketal 1 part,
Hydroquinone monomethyl ether 0.1 part, 2,6-
0.2 parts of di-t-butylcresol, 0.05 parts of methylnaphthoquinone, 0.5 parts of 2-ethylanthraquinone, 3 parts of glycerol tristearate, (melting point 71 ° C.), 100 parts of toluene, and 10 parts of water, The mixture was kneaded with a pressure kneader at 75 ° C., and the solvent was removed to obtain a photosensitive resin composition.

Example 8 A photosensitive resin composition was prepared in the same manner as in Example 7 except that 27 parts of the ethylenically unsaturated compound II was used instead of 27 parts of the ethylenically unsaturated compound I. Obtained.

Example 9 In Example 7, nitrile butadiene rubber (manufactured by Nippon Synthetic Rubber Co., Ltd.) was used instead of 46 parts of chlorinated polyethylene.
A photosensitive resin composition was obtained in the same manner as in Example 7, except that 46 parts of JSR222SH) were used.

Example 10 In Example 7, the same chlorinated polyethylene as in Example 1 was used instead of 46 parts of chlorinated polyethylene, 14 parts of polybutadiene and 27 parts of ethylenically unsaturated compound I.
Part, polyisoprene rubber (Kuraray: IR-10)
4 parts, 21 parts of ethylenically unsaturated compound I, 6 parts of stearyl methacrylate, 10 parts of dioctyl phthalate
Except that part was used, a photosensitive resin composition was obtained in the same manner as in Example 7.

Example 11 In Example 8, 21 parts of ethylenically unsaturated compound II was used instead of 27 parts of ethylenically unsaturated compound II.
A photosensitive resin composition was obtained in the same manner as in Example 8, except that 6 parts of 1,9-nonanediol methacrylate was used.

Example 12 <Preparation of hydrophilic polymer II> 299 parts of hexamethylene diisocyanate, 144 dimethylolpropionic acid
Part, polyoxytetramethylene glycol (PTMG-
850: 68 parts by Hodogaya Chemical Co., Ltd., 60 parts of hydroxyethyl methacrylate, acrylonitrile-butadiene oligomer having an amino group at a terminal (HYCAR-)
ARBN1300 × 16: Ube Industries, Ltd.) 429
And 20 parts of di-Nbutyltin dilaurate were dissolved in 1000 parts of tetrahydrofuran in a 2 liter flask equipped with a condenser, and the mixture was reacted at 60 ° C. for 4 hours. The completion of the reaction was confirmed by quantifying the amount of residual NCO. The -COOH group present in the reaction solution was neutralized with a half equivalent of lithium hydroxide monohydrate and magnesium acetate tetrahydrate in an aqueous solution to obtain a hydrophilic polymer II.

<Preparation of Photosensitive Resin Composition> In Example 11, 10 parts of hydrophilic polymer I and 21 parts of ethylenically unsaturated compound II were replaced by 10 parts of hydrophilic polymer II.
And a photosensitive resin composition was obtained in the same manner as in Example 11, except that 21 parts of the ethylenically unsaturated compound III was used.

Example 13 A photosensitive resin composition was prepared in the same manner as in Example 7, except that 27 parts of the ethylenically unsaturated compound IV was used instead of 27 parts of the ethylenically unsaturated compound I. I got

Example 14 In Example 7, an 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. 80,000 mPa
/ S) was obtained in the same manner as in Example 7, except that 27 parts of / s) were used.

Example 15 In Example 7, instead of 27 parts of the ethylenically unsaturated compound I, oligobutadiene urethane acrylate (manufactured by Idemitsu Petrochemical Co., Ltd .: ACR-LC, hydroxyl-terminated polybutadiene (R45HT, number average molecular weight 2800)) Urethane acrylate, number average molecular weight 12000, Mw / M
n = 3.5, viscosity at 20 ° C. 45000 mPa /
A photosensitive resin composition was obtained in the same manner as in Example 7, except that 27 parts of s) was used.

Example 16 The procedure of Example 7 was repeated, except that 27 parts of the ethylenically unsaturated compound I was replaced by 20 parts of the ethylenically unsaturated compound I and 7 parts of the ethylenically unsaturated compound V.
A photosensitive resin composition was obtained in the same manner as in the above.

Example 17 In Example 11, the ethylenically unsaturated compound VI was used instead of 6 parts of 1,9-nonanediol methacrylate.
A photosensitive resin composition was obtained in the same manner as in Example 11 except that 6 parts of was used.

Example 18 In Example 7, 46 parts of a styrene-butadiene-styrene block copolymer (glass transition temperature: -90 ° C., Clayton 1101 manufactured by Shell Petrochemical Co.) was used in place of 46 parts of the chlorinated polyethylene. Except for this, the photosensitive resin composition was obtained in the same manner as in Example 7.

Example 19 In Example 7, 40 parts of ethylene propylene rubber (glass transition temperature: −60 ° C. to −50 ° C., JSR-EP51: manufactured by Nippon Synthetic Rubber Co., Ltd.), isobutylene rubber (glass transition temperature: − 75 ° C to -63 ° C, JSR-Butyl
365: 15 parts by Nippon Synthetic Rubber Co., Ltd., butadiene oligomer having a terminal carboxyl group (HYCAR-CTB)
2000 × 162: manufactured by Ube Industries, Ltd.) 14 parts, ethylenically unsaturated compound I 25 parts, and the same photopolymerization initiator and thermal polymerization inhibitor as in Example 7 were used. A photosensitive resin composition was obtained in the same manner.

Example 20 In Example 7, instead of 46 parts of chlorinated polyethylene, acrylic rubber (NIPOL, manufactured by Nippon Zeon Co., Ltd.) was used.
A photosensitive resin composition was obtained in the same manner as in Example 7, except that 46 parts of AR54) were used.

Comparative Examples 1 to 14 In Examples 7 to 20, instead of the ethylenically unsaturated compound, Mn exceeded 500, Mw / Mn exceeded 2.0, and the viscosity at 20 ° C. was 2000 mP.
A photosensitive resin composition was obtained in the same manner as in Examples 7 to 20, except that 1,6-hexamethylene diacrylate exceeding a / s was used.

The photosensitive resin compositions obtained in Examples 7 to 20 and Comparative Examples 1 to 14 were evaluated for shape stability, presence or absence of core-shell particles and particle aggregation, and water swellability. Table 3 shows the results.

<Preparation of Photosensitive Resin Printing Master Plate> A polyester film having a urethane-based adhesive layer having a thickness of 125 μm on one surface and a polyester film having a polyvinyl alcohol layer having a thickness of 100 μm on one surface were prepared. 7 to 20 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 is closely 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.) is 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 3 shows the results.

[0120]

[Table 3]

From Table 3, it can be seen that the photosensitive resin compositions obtained in Examples 7 to 20 have no core-shell particle aggregation, good shape stability and good water swellability. Has a relief depth of 1.1 to 2.0 mm, faithfully reproduces the image of the negative film used, has good elasticity, and shows a clear image with good ink transferability. Was.

However, in the photosensitive resin compositions obtained in Comparative Examples 1 to 14, aggregation of core-shell particles was observed and shape stability was poor. The photosensitive resin printing plate had a relief depth of 0.3 to 0.7 mm, did not faithfully reproduce the image of the used negative film, and had poor elasticity.

[0123]

As apparent from the above description, since the ethylenically unsaturated compound of the present invention has polymerizability, high viscosity and compatibility with general-purpose resins, it can be used for coating agents, paints, adhesives, and the like. This is a very useful material as a constituent material of a photosensitive resin printing plate, particularly a flexographic printing plate. In addition, when the compound is used as a constituent material, a photosensitive resin composition having excellent workability and storage stability without aggregation of a dispersed phase can be provided, and aqueous developability and water resistance (particularly ink resistance) can be provided. The present invention can provide a photosensitive resin printing original plate and a photosensitive resin printing plate which satisfy the contradictory requirements, have good relief reproducibility, and have excellent elasticity.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08F 2/48 C08F 2/48 10/00 10/00 36/06 36/06 290/04 290/04 290/06 290/06 C08G 63/91 C08G 63/91 65/48 65/48 G03F 7/00 501 G03F 7/00 501 7/004 512 7/004 512 7/027 502 7/027 502 7/032 7/032 // C09D 109 / 00 C09D 109/00 167/07 167/07 171/00 171/00 B C09J 109/00 C09J 109/00 167/07 167/07 171/00 171/00 B (72) Inventor Kumiko Imai Otsu, Shiga Prefecture 2-1-1 Katata Ichito Toyobo Co., Ltd. (72) Inventor Keizo Kawahara 2-1-1 Katata Katsuta Otsu-shi Shiga Pref.Toyobo Co., Ltd. (72) Inventor Satoshi Imahashi Otsu Shiga Pref. 2-1-1, Katata-shi, Toyobo Co., Ltd. Research Laboratory (72) Inventor Atsushi Kaji Otsu, Shiga Prefecture Katata chome No. 1 No. 1, manufactured by Toyobo Co., Ltd. achievements Research Institute in

Claims (8)

[Claims] 1. A compound having at least one ethylenically unsaturated bond in the molecule and having a number average molecular weight Mn of 500 or more,
An ethylenically unsaturated compound having a weight average molecular weight Mw ratio of Mw / Mn of at least 2 and a viscosity at 20 ° C. of at least 2,000 mPa / s. 2. The reaction of (A) an unsaturated carboxylic acid or an alkyl ester thereof with (B) at least one selected from the group consisting of polyether polyols, polyester polyols, polyconjugated diene-based polyols and polyolefin polyols. The ethylenically unsaturated compound according to claim 1, wherein: 3. A photosensitive resin having a phase separation structure comprising a continuous phase containing the ethylenically unsaturated compound according to claim 1, and a finely dispersed phase dispersed in the continuous phase. Composition. 4. The dispersed phase is a core-shell particle composed of 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. 5. The continuous phase according to claim 4, wherein the continuous phase further contains a hydrophobic polymer different from the hydrophobic polymer contained in the core phase and compatible with the ethylenically unsaturated compound. Photosensitive resin composition. 6. The ethylenically unsaturated compound according to claim 1, a hydrophilic polymer, a hydrophobic polymer, and a hydrophobic polymer different from the hydrophobic polymer and compatible with the ethylenically unsaturated compound. 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. 7. An original plate for printing a photosensitive resin, comprising a support and a photosensitive layer containing the photosensitive resin composition according to claim 3. 8. A photosensitive resin printing plate obtained by exposing and then developing the photosensitive resin printing plate precursor according to claim 7.