JP3480515B2 - Photosensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, particularly a photosensitive resin composition.

[0002]

2. Description of the Related Art Styrene-based thermoplastic elastomers such as styrene / isoprene / styrene and styrene / butadiene / styrene have been used as resins for photosensitive resin compositions used in the production of printing plate materials. But,
These resins are not water-developable, and water-developable resins are desired from the viewpoint of work safety and the like.

As a resin for a water-developable photosensitive resin composition, poval or water-soluble nylon is used. However, these have a problem that the impact resilience required for printing on a cardboard is low and water-based ink cannot be used. Further, there is an emulsion type resin described in JP-A-3-228060. However, when an emulsion type resin is used, an opaque printing plate is obtained, and the obtained image is not clear. Furthermore, JP-A-6
No. 41256 discloses a water-soluble block copolymer obtained in a non-aqueous reaction step. However, this water-soluble block copolymer uses an expensive polymerization catalyst and has to undergo a complicated manufacturing process including a hydrolysis process.

[0004]

The problem to be solved by the present invention is to provide a photosensitive resin composition having water developability, high impact resilience and easy to manufacture.

[0005]

The photosensitive resin composition of the present invention comprises a polymer (a) having a carboxyl group having an acid value of 30 mgKOH / g or more and a glass transition temperature of 30 ° C. or more and one molecule. A compound (c) having two isocyanate groups in the molecule and an orient having two hydroxyl groups in one molecule.
A few selected from the group consisting of gomers and polymer compounds
At least one compound (b 1 ) and two hydroxides in one molecule
It contains a resin obtained by reacting a low molecular weight compound having a group (b2) as an essential component, a photopolymerizable unsaturated monomer (e), and a photopolymerization initiator (f).

[0006]

It is preferable that the resin has a photopolymerizable double bond .

[0008]

The polymer (a), compound (b1), compound
The compounding ratio of the compound (b2) and the compound (c) is a weight ratio.
And polymer (a): [compound (b1) + compound (b2)]
+ Compound (c)] = 5 to 50:50 to 95 is preferable.
Good The essential repeating unit of the polymer (a) is preferably at least one selected from the group consisting of methacrylic acid ester-based monomers and aromatic vinyl-based monomers. The number average molecular weight of the polymer (a) is 1,000 to 1.
It is preferably 0,000.

The flexographic printing composition of the present invention contains the above-mentioned photosensitive resin composition as an essential component. ************ The photosensitive resin composition of the present invention is described in detail below.
The polymer (a) used in the present invention has an acid value of 30 mgK.
There is no particular limitation as long as it has a glass transition temperature of 30 ° C. or higher at OH / g or higher and has a carboxyl group. The method for producing the polymer (a) is not particularly limited, and the polymer (a) can be produced by any method. As the method for producing the polymer (a),
For example, there is a method of copolymerizing a monomer having a carboxyl group and an unsaturated monomer.

The monomer having a carboxyl group is not particularly limited as long as it is a monomer having at least one carboxyl group in the molecule. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, itaconic acid, itaconic acid monoester, and cinnamic acid. You may use together 2 or more types of these monomers.

The unsaturated monomer copolymerized with the monomer having a carboxyl group is, for example, a methacrylic acid ester-based monomer, an aromatic vinyl-based monomer, or a copolymerizable with these monomers. Other vinyl-based monomers may be mentioned.
By using the unsaturated monomer, the polymer (a)
Has a glass transition temperature of 30 ° C. or higher. The methacrylic acid ester-based monomer is not particularly limited as long as it is a conventionally known methacrylic acid ester-based monomer, and for example, methacrylic acid; methyl methacrylate, ethyl methacrylate,
Butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, and other methacrylate alkyl esters; benzyl methacrylate and other methacrylate aryl esters; glycidyl methacrylate, 2-aminoethyl methacrylate,
Methacrylic acid substituent-containing alkyl esters such as; Methacrylic acid derivatives such as methoxyethyl methacrylate, ethylene oxide adducts of methacrylic acid; perfluoromethyl methacrylate, perfluoroethyl methacrylate, perfluoropropyl methacrylate, methacrylic acid Perfluorobutyl, perfluorooctyl methacrylate, trifluoromethylmethyl methacrylate, 2-trifluoromethylethyl methacrylate, diperfluoromethymethacrylate, 2-perfluoroethylethyl methacrylate, 2-perfluoromethylmethacrylate- 2-
Perfluoroethylmethyl, triperfluoromethylmethyl methacrylate, 2-perfluoroethyl-2-perfluorobutylethyl methacrylate, 2-methacrylic acid
Fluorine-containing methacrylic acid ester monomers such as perfluorohexylethyl, 2-perfluorodecylethyl methacrylate, 2-perfluorohexadecylethyl methacrylate; γ- (methacryloyloxypropyl)
Silicon-containing methacrylic acid ester monomers such as trimethoxysilane; 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, methacrylic acid 3
-Hydroxypropyl, hydroxy group of polymethacryloyl ester of polyethylene glycol, monomethacrylic acid ester of polypropylene glycol, polycaprolactone modified product of 2-hydroxyethyl methacrylate (trade name: Praxel F series (manufactured by Daicel Chemical Industries, Ltd.)) Examples thereof include addition-polymerizable monomers, and two or more kinds of these monomers may be used in combination.

The aromatic vinyl-based monomer is not particularly limited as long as it is a conventionally known aromatic vinyl-based monomer. For example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene. , P-methylstyrene, chlorostyrene, styrene sulfonic acid and its sodium salt. You may use together 2 or more types of these monomers.

When the essential repeating unit of the polymer (a) is at least one selected from the group consisting of methacrylic acid ester-based monomers and aromatic vinyl-based monomers, the photosensitive resin composition is exposed to light. It is preferable because the impact resilience and the transparency of the composition are increased. Further, the glass transition temperature of the polymer (a) can be increased. As the repeating unit of the polymer (a), only the above-mentioned methacrylic acid ester-based monomer and aromatic vinyl-based monomer may be used, and another vinyl-based monomer which is copolymerizable with these monomers You may use together with a body. The vinyl-based monomer is not particularly limited, but for example, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2
-Acrylic monomers such as ethylhexyl; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, monoacrylic acid ester of polyethylene glycol, monoacrylic acid ester of polypropylene glycol, acrylic acid 2-hydroxyethyl modified polycaprolactone (trade name: Praxel F series (Daicel Chemical Industries, Ltd.)
Hydroxyl group-containing addition-polymerizable monomers such as (meth) allyl alcohol 4-hydroxymethylstyrene; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid. And dialkyl esters; aromatic vinyl monomers such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrenesulfonic acid and sodium salts thereof; fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene and vinylidene fluoride. -Based monomers; vinyl monomers containing trialkyloxysilyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octyl Reimido, dodecyl maleimide,
Maleimide derivatives such as stearyl maleimide, phenyl maleimide and cyclohexyl maleimide; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamido; vinyl acetate, propion Examples thereof include vinyl esters such as vinyl acid salt, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride and allyl chloride. You may use together 2 or more types of these monomers.

The acid value of the polymer (a) is 30 mgKOH / g
In order to achieve the above, an acidic monomer having an acidic functional group may be used in addition to the monomer having a carboxyl group. Examples of the acidic monomer include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl methacrylate, 2-sulfoethyl acrylate, vinyl. Examples thereof include sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid. You may use together 2 or more types of these monomers.

The method for producing the polymer (a) is not particularly limited, and a conventionally known polymerization method can be adopted. For example, radical polymerization, anionic polymerization, and cationic polymerization are mentioned. When a methacrylic acid ester-based monomer or an aromatic vinyl-based monomer is used, radical polymerization or anion polymerization is preferable. The radical polymerization initiator (g) used in the radical polymerization method is not particularly limited, and examples thereof include isobutyryl peroxide, cumyl peroxy neodecanoate, diisopropyloxy dicarbonate,
Di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, t-butylperoxyneodecano Ate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octate, succinic acid peroxide, acetyl Peroxide, t-butylperoxy (2-ethylhexanate), m-toluoyl peroxide, benzoyl peroxide, t-butylperoxyisobutyrate, 1,1
-Bis (t-butylperoxy) cyclohexane, t-
Butyl peroxy maleic acid, t-butyl peroxy laurate, cyclohexanone peroxide, t-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-di (benzoyl peroxyhexane, t-
Butyl peroxyacetate, 2,2-bis (t-butyl peroxy) butane, t-butyl peroxybenzoate, n-butyl-4,4-bis (t-butyl peroxy) valerate, di-t-butyl per Oxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α′-bis (t-butylperoxy-m-isopropyl) Benzene, t-butyl cumyl peroxide, diisobutyl benzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t
-Butylperoxy) hexyne-3,1,1,3,3,3
-Organic peroxides such as tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate;
2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,2
4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2 -(Carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-
2,4-dimethylvaleronitrile, 2,2 'azobis (2-amidinopropane) dihydrochloride, 2,2'
-Azobis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azobis (isobutyramide) dihydrate, 4,4'-
Azo compounds such as azobis (4-cyanopentanoic acid) and 2,2'-azobis (2-cyanopropanol); hydrogen peroxide-Fe (II) salt, persulfate-sodium hydrogen sulfite, cumene hydroperoxide-Fe (II) Salts, redox type initiators such as benzoyl peroxide-dimethylaniline; and photosensitizers such as diacetyl, dibenzyl and acetophenone. You may use together 2 or more types of these radical polymerization initiators.

As the polymerization mode, any polymerization mode may be used, and examples thereof include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and solid phase polymerization. Further, the raw material monomer and the radical polymerization initiator (g) may be charged all at once to carry out the polymerization, or the polymerization may be carried out while supplying the above-mentioned components to the polymerization container at any time. In addition, after preliminarily charging a part of the solvent in the polymerization container, the raw material monomer and the radical polymerization initiator (g) are supplied to the polymerization container (feed).
The polymerization may be carried out by the method.

The polymerization vessel used for producing the polymer (a) may be any polymerization vessel. As a polymerization container,
For example, flask type polymerization vessel, batch type polymerization vessel such as kneader, piston flow tube type polymerization vessel,
Depending on the viscosity of the polymer, a continuous type such as a twin-screw extruder or a semi-batch type polymerization vessel is used. The polymerization temperature at the time of producing the polymer (a) is not particularly limited, and may be within the temperature range in which ordinary polymerization is performed.

The pressure of the polymerization vessel for producing the polymer (a) may be any of reduced pressure, normal pressure and increased pressure. Other methods for producing the polymer (a) include, for example, a method in which a methacrylic acid ester or an acrylic acid ester is copolymerized under the same reaction conditions as described above, and then hydrolyzed, glycidyl acrylate or methacrylic acid. Examples thereof include a method in which glycidyl acid is copolymerized under the same reaction conditions as described above and then reacted with a dicarboxylic acid.

The acid value of the polymer (a) used in the present invention is 30 mgKOH / g or more. Acid value is 30mgKOH
If it is less than / g, the water-solubility and alkali-solubility of the resin to be described later will be reduced, and the photosensitive resin composition after exposure will not be water developable. The acid value of the polymer (a) is 90 mgK
OH / g or more, preferably 120 mgKOH
/ G or more is more preferable.

The glass transition temperature of the polymer (a) used in the present invention is 30 ° C. or higher. Glass transition temperature is 30
If the temperature is less than ℃, the hard segment property of the resin decreases,
The elastomeric property of the exposed photosensitive resin composition is reduced. The glass transition temperature of the polymer (a) is preferably 60 ° C or higher, more preferably 90 ° C or higher. The number average molecular weight of the polymer (a) is preferably 1,000 to 100,000.
When the number average molecular weight is less than 1,000, the water-soluble portion and the alkali-soluble portion of the resin are reduced and the water developability of the exposed photosensitive resin composition is lowered. In addition, the hard segment property of the resin is lowered, and the elastomeric property of the photosensitive resin composition exposed is reduced. Number average molecular weight is 10
When it exceeds 10,000, the hard segment property of the resin becomes too large, and the elastomer property of the photosensitive resin composition exposed to light decreases. The number average molecular weight of the polymer (a) is 2,
000 to 50,000 is preferable, 5,000 to 20,
000 is more preferable. There is no particular limitation on the control of the number average molecular weight and the molecular weight distribution of the polymer. For example, in radical polymerization, it can be controlled by the initiator concentration, the monomer concentration, the polymerization temperature and the addition of a chain transfer agent. In particular, when a compound having one mercapto group and one hydroxyl group such as mercaptoethanol is used as a chain transfer agent, a polymer having a hydroxyl group at one end is obtained, which is also included in the polymer (a). .

The method of introducing the photopolymerizable double bond into the polymer (a) is not particularly limited. For example, after copolymerizing a monomer having a carboxyl group, glycidyl acrylate or methacrylic acid is used. A method of reacting glycidyl;
A method in which methacrylic acid ester or acrylic acid ester is hydrolyzed after copolymerization and then reacted with glycidyl acrylate or glycidyl methacrylate; after copolymerization with glycidyl acrylate or glycidyl methacrylate, acrylic acid, methacrylic acid, maleic acid, Examples thereof include a method of reacting a compound having a carboxyl group such as maleic acid monoester, fumaric acid, fumaric acid monoester, itaconic acid, itaconic acid monoester, and cinnamic acid with a photopolymerizable double bond.

By introducing a photopolymerizable double bond into the polymer (a), the resin comes to have a photopolymerizable double bond and becomes a resin having a photopolymerizable double bond. The printed image becomes clear, and the expansion of the plate making by the ink can be reduced. The compound (c) having two isocyanate groups in one molecule used in the present invention is
There is no particular limitation as long as it does not have a functional group that reacts with an isocyanate group. Further, it is preferable that the compound (c) has a hydrophilic functional group, because the water developability when the photosensitive resin composition is exposed to light can be improved. The compound (c) may be a low molecular weight compound, an oligomer or a polymer. As the compound (c), for example, 1,
4-phenylene diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, 4,4-diisocyanate-3,3-dimethyldiphenyl, diphenyldimethylmethane-4,4'-diisocyanate, 1,3-
Or 1,4-cyclohexyl diisocyanate, 1,
4-tetramethylene diisocyanate, bis (isocyanatomethyl) cycloxane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, isopropylbenzene-2,4-diisocyanate, cyclohexanephenylene diisocyanate , Chlorophenylene diisocyanate, naphthalene-1,5-diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 1 in the compound (b) having two hydroxyl groups in one molecule described later. 2 in the molecule
The compound which has two isocyanate groups in 1 molecule obtained by making the compound which has one isocyanate group react can be mentioned. Blocked isocyanate may also be used. You may use together 2 or more types of these compounds (c).

[0024]

The group consisting of oligomers and polymer compounds having two hydroxyl groups in one molecule used in the present invention .
The selected at least one compound (b 1 ) is not particularly limited as long as it is an oligomer or polymer compound having no functional group that reacts with isocyanate other than the two hydroxyl groups. In addition, two hydroxyl groups in one molecule used in the present invention
The low molecular weight compound (b2) having a group is other than two hydroxyl groups.
Molecular weight reduction without functional group that reacts with isocyanate
It is not particularly limited as long as it is a compound. In addition, the compound (b 1 )
It is preferable that (b2) and (b2) have a hydrophilic functional group, because the water developability of the photosensitive resin composition that has been exposed can be improved . Examples of the compound (b2) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butane-1ol, 1,3-butanediol, 1,6-hexanediol, Trimethylene glycol, pentaerythritol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 2-methyl-2,4-pentanediol, 2-ethyl. -1,3-hexanediol, 2,2-methyl-2,
Aliphatic diols such as 4-pentanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, tripropylene glycol and cyclohexane-1,4-diol; 1,4-cyclohexane glycol,
Alicyclic diols such as hydrogenated bisphenol A; aromatic diols such as xylylene glycol, 1,4-dihydroxyethylbenzene and ethylene oxide adducts of bisphenol A; thiol-containing diols such as dithiodiethanol and thiodiethylene glycol Is mentioned. Further, as the compound (b1), oligomeric and polymeric compounds having OH groups at both ends, for example, polyethylene glycol, polypropylene glycol, polyether diols such as polybutylene glycol; manufactured by Mitsubishi Kasei of Polytail, KURARAY Polyolefin diols such as hydrogenated polyisoprene containing hydroxyl groups at both ends of E. and Epol manufactured by Idemitsu Petroleum; F. Polybutadiene diol such as OH-terminated HTBN manufactured by Goodrich; polyester diol such as Kurapol manufactured by Kuraray; polycarbonate diols; polyurethane diols; polyorganosiloxane diols; and acrylic having hydroxyl groups at both ends described in JP-A-5-262808. Examples include polyacrylic diols such as polymer. These compounds (b
Two or more of each of 1 ) and (b2) may be used in combination. The glass transition temperature of the resin formed by the reaction of the compounds (b 1 ) and (b2) with the compound (c) was 0 ° C.
The following is more preferable.

The resin used in the present invention, the polymer (a), compound (b 1), thus obtained reaction to compound (b2) and the compound (c) Required.

Below, the polymer (a), the compound (b 1 ) ,
The reaction in which the compound (b2) and the compound (c) are essential will be described in detail. The amount of compound (b 1) and (b2) are compounds NCO group with a compound of (c) and (b 1)
The equivalent ratio to the hydroxyl group of (b2) (NCO group / hydroxyl group) is in the range of 0.5 to 3.0, preferably 0.7 to 2.0, and more preferably 0.8 to 1.5. And is appropriately determined depending on the type of compound used.

Polymer (a), compound (b 1 ) , compound
The blending ratio of (b2) and compound (c) is a weight ratio,
Polymer (a): [compound (b 1 ) + compound (b2) + compound (c)] = 5 to 50:50 to 95 are preferable. The glass transition temperature of the resin obtained by reacting the compound (b 1 ) and the compound (b2) with the compound (c) is 0 ° C.
The following is preferable, -30 ° C is more preferable, and -50 ° C is most preferable. The resin obtained by reacting the compound (b 1 ) and the compound (b2) with the compound (c) is preferably water-soluble or hydrophilic.

Further, the compound (b 1 ) and the compound (b
In order to promote the reaction between 2) and the compound (c), di-n
-Butyltin dilaurate, stannas octoate, triethylenediamine, diethylenediamine, triethylamine, metal naphthenates, metal octylates such as lead octylate can be used as the urethane-forming catalyst. If necessary, the compound (b 1 ) and the compound (b2)
A solvent may be used in the reaction between and the compound (c). Examples of the solvent used in the reaction include ketones such as acetone, MEK, MIBK and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, trichlene and perkrene, THF and dioxane. And ethers such as, and esters such as cellosolve acetate, ethyl acetate and butyl acetate. You may use together 2 or more types of these solvents.

In this reaction, the conventionally known one-shot method, prepolymer method, etc. can be used, and the order of introducing each component is not particularly limited .

[0031]

[0032] Photosensitivity containing resin thus obtained
When exposed to light, the resin composition has water developability and impact resilience.
Is high.

The resin thus obtained is photopolymerizable 2
In the case of a resin having a heavy bond, a plate-making product obtained by exposing a photosensitive resin composition containing these resins to light has a clear printed image and less swelling of the plate-making product with ink. The photopolymerizable unsaturated monomer (e) used in the present invention is not particularly limited, and examples thereof include (meth) acrylic acid and salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) acrylic such as butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate Acid alkyl esters; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; (meth) acrylic acid substituent-containing alkyls such as glycidyl (meth) acrylate and 2-aminoethyl (meth) acrylate Esters; methoxyethyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, and the like ( A) acrylic acid derivatives; perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluoro (meth) acrylate Octyl, trifluoromethylmethyl (meth) acrylate, (meth) acrylic acid 2
-Trifluoromethylethyl, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, (meth) Triperfluoromethylmethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Fluorine-containing (meth) acrylic acid ester-based monomers such as 2-perfluorohexadecylethyl (meth) acrylate; Silicon-containing (meth) such as γ- (methacryloyloxypropyl) trimethoxysilane
Acrylic ester-based monomers; (meth) acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, methyl 2-hydroxymethylacrylate, ethyl 2-hydroxymethylacrylate, butyl 2-hydroxymethylacrylate, (meth ) Tetramethylene glycol acrylate, mono (meth) acrylic acid ester of polyethylene glycol, mono (meth) acrylic acid ester of polypropylene glycol, (meth) acrylic acid 2-
Polycaprolactone modified product of hydroxyethyl (trade name: Praxel F series (Daicel Chemical Industries, Ltd.)
,), Hydroxyl-containing addition-polymerizable monomers such as (meth) allyl alcohol 4-hydroxymethylstyrene, maleic anhydride, maleic acid, maleic acid salts, monoalkyl and dialkyl esters of maleic acid; fumaric acid, fumaric acid Acid salts, fumaric acid monoalkyl and dialkyl esters, itaconic acid, itaconic acid salts, itaconic acid monoalkyl esters and dialkyl esters; styrene, α-methylstyrene, methylstyrene, chlorostyrene, styrenesulfonic acid and the like. Aromatic vinyl monomers such as sodium salts; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexyl Maleimide derivatives such as silmaleimide; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, 1,6-hexamethylenebis ( (Meth) acrylamide, diethylenetriamine tris (meth) acrylamide, N- (hydroxymethyl) (meth) acrylamide, N- (hydroxyethyl) (meth) acrylamide, N, N'-bis (β-hydroxyethyl) (meth) acrylamide, etc. Amide group-containing vinyl monomers; phenoxy polyethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri (di) methacrylate Ethylene glycol, diallyl itaconic acid, glycerol di (meth) acrylate, glycerol tri (meth) acrylate,
Tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol, tri (meth) acrylic acid glycerol polypropylene glycol, di (meth) acrylic acid 1,3-propylene glycol, di (meth) acrylic acid 1, 4-Cyclohexanediol, 1,2,4-butanetriol tri (meth) acrylate, glycerol polypropylene glycol tri (meth) acrylate, 1,4-benzenediol di (meth) acrylic acid, tetra (meth) acrylic acid penta Erythritol, di (meth) acrylic tetramethylene glycol, di (meth) acrylic acid 1,5-pentanediol,
Di (meth) acrylic acid 1,6-hexanediol, divinyl adipate, divinyl phthalate, acrylated or methacrylated urethane may be mentioned. You may use together 2 or more types of these monomers. Among them, the photopolymerizable unsaturated monomer (e) is preferably a water-soluble monomer or a crosslinkable monomer.

Examples of the water-soluble monomer include (meth) acrylic acid and salts thereof, mono (meth) acrylic acid ester of polyethylene glycol, 2-hydroxymethyl methyl acrylate, 2-hydroxymethyl ethyl acrylate, and 2-hydroxymethyl acrylate. Examples include butyl hydroxymethyl acrylate, maleic acid and salts thereof. Further, the crosslinkable monomer is not particularly limited as long as it is a monomer having two or more double bonds in one molecule.

The photopolymerization initiator (f) used in the present invention is not particularly limited and includes, for example, α, α-dimethoxy-α-phenylacetophenone, α, α-diethoxyacetophenone, α-hydroxy-α, Benzoin ethers such as α-dimethylacetophenone, 1-benzoylcyclohexanol, benzoin isopropyl ether, benzoin isobutyl ether, anthraquinone,
Examples thereof include anthraquinones such as 2-methylanthraquinone and 2-ethylanthraquinone, and xanthones such as xanthone and thioxanthone. You may use together 2 or more types of these photopolymerization initiators.

The photosensitive resin composition of the present invention contains a resin, a photopolymerizable unsaturated monomer (e) and a photopolymerization initiator (f). When the resin does not contain a double bond, the resin, the photopolymerizable unsaturated monomer (e) and the photopolymerization initiator (f) are mixed in a proportion of 30 to 95 parts by weight of the resin. Saturated monomer (e) 5 to 70 parts by weight, photopolymerization initiator (f) 0.
It is preferably from 01 to 10 parts by weight. When the amount of the resin is less than 30 parts by weight, the shape of the resin plate made of the photosensitive resin composition may be deformed during storage before exposure, or the water developability of the exposed resin plate may be poor. Further, when the amount of the resin exceeds 95 parts by weight, the hardness of the resin plate after photocuring becomes insufficient. When the amount of the photopolymerizable unsaturated monomer (e) is less than 5 parts by weight, the hardness of the resin plate after exposure becomes insufficient. If the amount of the photopolymerizable unsaturated monomer (e) exceeds 70 parts by weight, the shape of the resin plate may be deformed before exposure. The photopolymerization initiator (f) is 0.01
If it is less than part by weight, curing by exposure is not sufficient,
If it exceeds 10 parts by weight, the image may become unclear.

The resin, the photopolymerizable unsaturated monomer (e) and the photopolymerization initiator (f) are mixed in such a proportion that the resin is photopolymerizable 2
In the case of containing a heavy bond, the resin is 30 to 100 parts by weight, the photopolymerizable unsaturated monomer (e) is 0 to 70 parts by weight, and the photopolymerization initiator (f) is 0.01 to 10 parts by weight. preferable. When the amount of the resin is less than 30 parts by weight, the shape of the resin plate made of the photosensitive resin composition may be deformed during storage before exposure, or the water developability of the exposed resin plate may be poor. When the amount of the photopolymerizable unsaturated monomer (e) exceeds 70 parts by weight, the shape of the resin plate may be deformed before exposure. The photopolymerization initiator (f) is 0.01
If it is less than part by weight, curing by exposure is not sufficient,
If it exceeds 10 parts by weight, the image may become unclear.

Another photosensitive resin composition of the present invention contains a resin having a photopolymerizable double bond and a photopolymerization initiator (f). The compounding ratio is 80 to 100 parts by weight of the resin having a photopolymerizable double bond, and 0.01 to 0.01 of the photopolymerization initiator (f).
It is preferably 10 parts by weight. If the amount of the resin having a photopolymerizable double bond is less than 80 parts by weight, the shape of the resin plate made of the photosensitive resin composition may be deformed during storage before exposure, or the water developability of the exposed resin plate may be poor. is there. If the photopolymerization initiator (f) is less than 0.01 parts by weight, curing by photosensitization will not be sufficient, and if it exceeds 10 parts by weight, the image may become unclear.

The photosensitive resin composition of the present invention comprises, in addition to the above-mentioned components, a thermal polymerization inhibitor, a coloring agent such as a dye or a pigment, a plasticizer and a surfactant which are used in conventional photosensitive resin compositions. And an additive of a viscosity modifier can be appropriately blended. The photosensitive resin composition is mixed with the resin, the photopolymerizable unsaturated monomer (e) and the photopolymerization initiator (f) by, for example, mixing with a pressure kneader or the like.

The method for mixing the photosensitive resin composition from the resin having a photopolymerizable double bond and the photopolymerization initiator (f) is as described above, for example, by mixing with a pressure kneader or the like. Done. The method for molding a printing plate using the photosensitive resin composition of the present invention is carried out, for example, on a support made of a metal plate such as aluminum, copper or stainless steel or a synthetic resin plate such as polyethylene terephthalate or polypropylene. , Cast molding method, extrusion molding method, compression molding method, and calendar processing method.

The printing plate material using the photosensitive resin composition of the present invention is widely used in printing for newspapers, newspaper printing, general commercial printing and photoresists, such as flexographic printing plate making and printed wiring boards. It is useful for the production of printing plate materials. In particular, a flexographic printing composition containing the photosensitive resin composition of the present invention as an essential component provides a printing plate material having high transparency and high image clarity, water developability, and high impact resilience. You can

[0042]

EXAMPLES Hereinafter, specific examples of the present invention and comparative examples will be described together, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.
The number average molecular weight and gel fraction in the following Examples and Comparative Examples were determined by the following methods unless otherwise specified.

Number average molecular weight It was determined from a calibration curve using standard polystyrene using gel permeation chromatography (GPC). Gel Fraction Represents the weight% of the insoluble matter remaining without being extracted when the resin was subjected to a Soxhlet extractor using THF as a solvent for 8 hours.

Production Example 1 [ Production of Polymer [A-1]] 75 parts of methyl ethyl ketone (hereinafter abbreviated as MEK) was charged into a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser tube, and the inside of the flask was charged. After performing the nitrogen substitution in (1), the temperature is raised to 80 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel became stable, AIBN1.
After 10% of the mixed solution prepared by dissolving 2 parts in 63 parts of methyl methacrylate and 12 parts of acrylic acid was initially charged into the reaction vessel, the temperature in the reaction vessel was stabilized at 80 ° C. and the rest of the mixed solution remained. 90% of was added dropwise over 2 hours. After 30 minutes from the completion of the dropping, 0.1 part of AIBN was added and stirring was continued for 60 minutes at 80 ° C. to complete the polymerization. It was confirmed by gas chromatography that there were no unreacted monomers, and the polymer [A-
A 50 wt% MEK solution of 1] was obtained.

Number average molecular weight (Mn) of polymer [A-1]
Was 9000 as a result of measurement by a standard polystyrene conversion method using gel permeation chromatography (GPC). The acid value of the polymer [A-1] is 123 mg.
It was KOH / g. Production Example 2 [ Production of Polymer [A-2]] Methyl ethyl ketone (hereinafter abbreviated as MEK) was placed in a flask equipped with a stirrer, a nitrogen introducing tube, a thermometer and a reflux cooling tube.
Was charged in 100 parts, and the inside of the flask was replaced with nitrogen,
The temperature is raised to 80 ° C. while gently blowing nitrogen gas. After the temperature in the reaction vessel has stabilized, AIBN1.2
10% of the mixed solution prepared by dissolving 61 parts of methyl methacrylate in 14 parts of acrylic acid and 14 parts of acrylic acid was initially charged into the reaction vessel, and after the temperature in the reaction vessel was stabilized at 80 ° C., the remaining amount of the mixed solution remained. 90% was added dropwise over 2 hours. After 30 minutes from the completion of the dropping, 0.1 part of AIBN was added and stirring was continued for 60 minutes at 80 ° C. to complete the polymerization. It was confirmed by gas chromatography that there were no unreacted monomers.

Subsequently, 4.5 parts of glycidyl acrylate and 0.25 parts of tetrabutylammonium chloride were added to give 8 parts.
The reaction was carried out at 0 ° C for 3 hours. Glycidyl acrylate and MEK were distilled off under reduced pressure at 80 ° C. It was confirmed by gas chromatography that there was no unreacted glycidyl acrylate, and a 50 wt% MEK solution of the polymer [A-2] was obtained.

Number average molecular weight (Mn) of polymer [A-2]
Was 7800 as a result of measurement by a standard polystyrene conversion method using gel permeation chromatography (GPC). The acid value of the polymer [A-2] is 117 mg.
It was KOH / g. The iodine value of the polymer [A-2] was measured, and it was confirmed that [A-2] had 2.8 double bonds in one molecule.

Production Example 3 [ Production of Resin [D-1]] A flask equipped with a stirrer, a nitrogen inlet tube, and a thermometer was sufficiently replaced with high-purity nitrogen, and then a high-purity nitrogen gas was gently blown into the flask to carry out heavy 20 parts of 50 wt% MEK solution of combined product [A-1], 1 part of ethylene glycol, 40 parts of polyester polyol (Clapol L-2010), 8.4 parts of isophorone diisocyanate (hereinafter abbreviated as IPDI), 190 parts of methyl ethyl ketone and dibutyltin dilaurate. 0.2 part of a 10% toluene solution was charged and well stirred. In this preparation, isocyanate group and O
The ratio of H groups was isocyanate group / OH group = 1.05.

The solution in the flask was transferred to a vat,
It was left for 15 hours in a hot air dryer in a dry state at 0 ° C. Then, it cooled and obtained resin [D-1] was obtained. Resin [D
-1] has a molecular weight of 38,000 and a gel fraction of 6.2 w
It was t%. Production Examples 4 to 6 [ Production of Resins [D-2] to [D-4]] Instead of the polyester polyol of Production Example 3, the oligomers of Table 1 were used, and the polymer [A-1] was replaced with a polymer [A-1]. A-2] was used, and the same operation as in Production Example 3 was performed with the composition shown in Table 1. Generated resin [D-2]
Table 2 shows the molecular weight and gel fraction of [D-4].

[0050]

[Table 1]

[0051]

[Table 2]

Example 1 75 parts of the resin [D-1] prepared in Preparation Example 3, 3 parts of acrylic acid, 10 parts of polyethylene glycol diacrylate (average molecular weight: 508), 10 parts of diacrylic acid-1,6-hexanediol. , Trimethylolpropane triacrylate 2 parts, α, α-dimethoxy-α-phenylacetone 2
Parts and 0.05 parts of methylhydroquinone were sufficiently mixed by a pressure kneader and molded into a thickness of 1 mm by a biaxial extruder to obtain a photosensitive resin composition.

A negative film was brought into close contact with the obtained photosensitive resin composition, exposed for 5 minutes using a chemical lamp, and then the unexposed portion was washed out with a 2 wt% NaOH aqueous solution at 30 ° C. using a brush type elution machine. Then, it was dried at 100 ° C. for 5 minutes and further exposed to a chemical lamp for 5 minutes. The obtained printing plate was examined for alkali solubility, impact resilience and printing characteristics. The results are shown in Table 3. Alkali-soluble: The degree of washing out of the unexposed area by a brush type elution machine was visually inspected.

Sufficient washout: ○, insufficient washout:
It was set to x. Impact resilience: The printing plate thus obtained was visually inspected for cracks when bent 180 °. No cracking: ○, cracking: ×. Printing characteristics: Printing was carried out with flexographic ink for newspapers, and the printed state was visually observed.

Good print condition: ◯, poor print condition: ×
And Examples 2 to 4 Instead of the resin [D-1] used in Example 1, resin [D-
The same operation as in Example 1 was carried out except that 2) to [D-4] were used, and the alkali solubility, impact resilience and printing characteristics of the obtained printing plate were examined. The results are shown in Table 3. Comparative Example 1 Styrene was used instead of the resin [D-1] used in Example 1.
Isoprene-based thermoplastic elastomer JSR SIS 5
The same operation as in Example 1 was carried out except that 000 (manufactured by Japan Synthetic Rubber Co., Ltd.) was used, and the alkali solubility, impact resilience and printing characteristics of the obtained printing plate were examined. The results are shown in Table 3.
Shown in.

[0056]

[Table 3]

[0057]

According to the present invention, it is possible to provide a photosensitive resin composition having water developability, high impact resilience, and easy production. When the resin has a photopolymerizable double bond, the printed image becomes clear and the swelling of the plate by ink is reduced.

When the essential repeating unit of the polymer (a) is at least one selected from the group consisting of methacrylic acid ester-based monomers and aromatic vinyl-based monomers, impact resilience and transparency are further improved. Can be higher. The number average molecular weight of the polymer (a) is 1,000 to 100,00.
When it is 0, the water developability is further enhanced and the elastomer property is improved.

A flexographic printing composition containing a photosensitive resin composition as an essential component can provide a printing plate material having high image clarity, water developability and high impact resilience.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/035 G03F 7/035 (56) References JP-A-5-27435 (JP, A) JP-A-53-1281 (JP , A) JP-A-50-19504 (JP, A) JP-A-50-133005 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/18

Claims (6)

(57) [Claims] 1. A polymer (a) having a carboxyl group having an acid value of 30 mgKOH / g or more and a glass transition temperature of 30 ° C. or more, and a compound (c) having two isocyanate groups in one molecule. , Oh having two hydroxyl groups in one molecule
A small number selected from the group consisting of rigomers and high molecular compounds
At least one compound (b 1 ) and two waters in one molecule
Photosensitive material containing a resin obtained by reacting a low molecular weight compound (b2) having an acid group as an essential component, a photopolymerizable unsaturated monomer (e), and a photopolymerization initiator (f). Resin composition. 2. The photosensitive resin composition according to claim 1 , wherein the resin has a photopolymerizable double bond. 3. The polymer (a), compound (b1), compound
The compounding ratio of the compound (b2) and the compound (c) is a weight ratio.
And polymer (a): [compound (b1) + compound (b2)]
+ Compound (c)] = 5 to 50:50 to 95
Item 3. The photosensitive resin composition according to item 1 or 2. 4. essential repeating units of the polymer (a) is at least one selected from the group consisting of methacrylic acid ester monomer and aromatic vinyl monomer, claims 1 to 3 The photosensitive resin composition according to any one of 1 to 3 above. 5. The number average molecular weight of the polymer (a) is 1,0.
The photosensitive resin composition according to any one of claims 1 to 4 , which is 00 to 100,000. 6. A flexographic printing composition used as an essential component of the photosensitive resin composition according to any one of claims 1 to 5.