JP3225515B2 - Method for producing hydrophilic polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel polymer having a hydrophilic property capable of being polymerized, and has a high water-absorbing gel, a binder, a sealant, a coating agent, a compatibilizer, and a molding material. The present invention relates to a hydrophilic polymer suitable for the composition of a photosensitive resin composition capable of developing with water, a medical polymer material, an industrial material, and an image forming material, particularly, a water-developable photosensitive resin composition.

(Prior Art) There are many known hydrophilic polymers used in image-forming materials, in particular, photosensitive resin compositions capable of aqueous development. For example, there are a natural substance system, a natural substance derivative system, and a synthetic polymer system. Its structure is essential to have a hydrophilic group, for example, a hydroxyl group as a nonionic system, a polyether structure, an amine, an ammonium salt as a cationic system, a phosphate group, a sulfonic acid group as an anionic system,
Having a carboxyl group or the like.

Examples of natural substances or derivatives thereof include cellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, starch, starch-sodium polyacrylate grafted product, starch-polyacrylonitrile grafted product, and cellulose polyacrylic acid grafted product. Synthetic polymer systems include polyvinyl alcohol, partially saponified polyvinyl acetate, vinyl alcohol-sodium acrylate copolymer, vinyl alcohol-sodium methacrylate copolymer, partially cross-linked sodium polyacrylate, polyethylene glycol, and polyethylene glycol derivatives. For polyamides, JP-A-53-141026, 53-36
555, 54-51819, 59-170835, 59-221327, 60-63225
JP-A-49-109104, 49-133104, 53-143401, 59-1116
38, 59-113430, conjugated diene polymers are disclosed in JP-A-52-134655, 53-10648, 5
4-110287, 55-143557, 58-62640, 61-128243, 61-
292635, 64-49036, JP-A No. 1-183651, and those commercially available include carboxyl group-containing polyisoprenes (Kuraprene Kuraray Co., Ltd.) and isobutylene-maleic anhydride copolymer. There are many, including coalesce (Isoban 04 Kuraray Co., Ltd.) and carboxyl group-containing nitrile butadiene copolymer (Nippol 1072 Nippon Zeon Co., Ltd.). Also, as a polyurethane-based hydrophilic polymer, JP-B-49-2199, JP-B-47-15517
No., JP-B-47-22707, JP-B-48-25435, JP-A-54
JP-A-14491, JP-A-61-20939, JP-A-63-113450 and the like.

(Problems to be Solved by the Invention) The hydrophilic polymer has a property of swelling, dispersing and dissolving in water, alkaline water, or mixed water such as alcohol, but does not contain a polymerizable group in the hydrophilic polymer itself. Further, it has a structure having a hydrophilic structure as a main component or a structure close to a homopolymer in which a hydrophilic component is a repeating unit. Further, as described in JP-A-54-144911, when a polymerizable group is contained, the structure of the main chain is limited to a structure containing a hydrophilic component as a main component.

Therefore, the hydrophilic polymer swells, disperses, and dissolves in water or an aqueous alkaline solution, but is polymerized by heat, light, or an active energy ray such as an electron beam, and changes in performance, that is, from hydrophilicity to hydrophobicity. Cannot exhibit functions such as water absorption due to water solubility or water dispersibility, and when used as a compatibilizer, a coating agent or a photosensitive resin composition or the like, the compatibility with other components There is a problem that the range of use is limited in terms of solubility and the like.

(Means for Solving the Problems) The inventors of the present invention have conducted intensive studies and have found that an anionic hydrophilic component, a polyether chain component, a conjugated diene-based hydrocarbon chain component, and a polymerizable (meth) acryloyl group at a polymer terminal. The above problem was solved by obtaining a novel hydrophilic polymer containing

That is, the present invention provides (A) an alkyl ester of a hydroxy group-containing unsaturated carboxylic acid represented by the following general formula (a), and (B) a polyoxyalkylene chain represented by the following general formula (b1) and / or (b2): Polyamine and / or
Or polyols, (C) the following formulas (c1) and / or -CO ₂ M groups and / or -SO ₃ M group-containing polyamine and / or polyol represented by (c2) (where the M
Represents a hydrogen atom, group I, II, or III element, amine or ammonium), (D) the following general formula (d1) and / or
Or a hydrophilic polymer obtained by reacting a polyamine and / or a polyol having a -conjugated diene hydrocarbon chain represented by (d2) and (E) a polyisocyanate represented by the following general formula (e): It is a manufacturing method of.

(In the general formula a, R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents an alkylene group having 1 to 20 carbon atoms.) (In the general formulas b1 and b2, R ³ represents an alkylene group having 1 to 20 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom or an alkylene group having 1 to 20 carbon atoms, and n represents an integer of 1 to 100.) (In the general formulas c1 and c2, Z represents —CO ₂ —, —SO ₃ —, and R ⁶ represents an aliphatic or / and aromatic organic group having 1 to 20 carbon atoms;
R ⁷ and R ⁸ are a hydrogen atom or an aliphatic having 1 to 20 carbon atoms or /
And an aromatic organic group. ) In ^{HO-R 9 -OH (d2)} ( general formula d1, d2, R ⁹ is an organic group having a butadiene chain, which may have an amide bond .R ^10, R ¹¹
Is a hydrocarbon having 1 to 20 carbon atoms, and may form a ring via an oxygen atom and / or a nitrogen atom. ) In ^{OCN-R 12 -NCO (e)} ( general formula e, R ¹² is an aliphatic organic group having 1 to 20 carbon atoms, alicyclic organic group, an aromatic organic group.) The present invention hydrophilic polymer The component (A), which is a raw material at the time of obtaining, is an alkyl ester of an unsaturated carboxylic acid containing a hydroxyl group, and the structures of the hydroxyl group and the ester bonding site are not limited. Examples of compounds having such a structure include aliphatic compounds, alicyclic compounds or derivatives thereof, aromatic compounds or derivatives thereof, and compounds containing unsaturated bonds such as dienes. Specifically, as the component A, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate, Hydroxy t-butyl (meth) acrylate, hydroxypentyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxycyclohexyl (Meth) acrylate, hydroxyisophorone (meth)
Examples include acrylates, such as hydroxybenzyl (meth) acrylate and hydroxybenzoin (meth) acrylate.

Next, the component (B) is a polyamine and / or a polyol containing a polyoxyalkylene chain, and the polyoxyalkylene structure that constitutes between the amine or the hydroxyl group includes an arbitrary one. Glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, polyneopentyl glycol, 1,3 butylene glycol, tetramethylene glycol, polyoxytetramethylene glycol, etc. Can be cited.

In the present invention, the component (C) for imparting hydrophilicity is -CO ₂ M
Group or -CO ₃ M group (M: a hydrogen atom, the periodic table I, II, III group element, amine, ammonium) and a polyamine and / or polyol containing, for example, the general formula (I),
(II), (III), (IV), (V), or (VI), but is not limited thereto.

In the formula, R ¹ represents a hydroxy group, a primary or secondary amine. R ² may contain a hydrogen atom, a substituent, for example, alkyl, alkenyl, aralkyl, aryl, alkoxy, aryloxy group, preferably a hydrogen atom, alkyl or alkenyl having 1 to 20 carbon atoms, It represents an aryl group having 6 to 25 carbon atoms. R ³ , R ⁴ , R ⁵
Represents a divalent aliphatic or aromatic hydrocarbon which may be the same or different and which may have a single bond or a substituent (eg, an alkyl, alkenyl, aralkyl, aryl, alkoxy and halogen group). . It preferably represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 25 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.
Further, if necessary, other functional groups which do not react with the isocyanate group in R ³ , R ⁴ , and R ⁵ , for example, ester, ether, urethane, amide, urea group, and may have a carbon-carbon unsaturated bond. Good. R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring.

Ar represents a trivalent aromatic hydrocarbon which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

M is a hydrogen atom, group I, II, III element of the periodic table,
These are primary, secondary, tertiary amines, and ammonium, and include these alone or in combination, or compounds containing these. Compounds forming such M 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-butoxide, Sodium methoxide, alkali metal alkoxides such as sodium ethoxide, calcium hydroxide, magnesium hydroxide, hydroxides of polyvalent metals such as aluminum hydroxide,
Acetates such as sodium acetate, magnesium acetate, lithium acetate, and potassium acetate; polyvalent metal alkoxides such as aluminum isopropoxide; tertiary amines such as triethylamine and tri-n-propylamine; diethylamine; Secondary amines such as propylamine, primary amines such as ethylamine and n-propylamine, cyclic amines such as morpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate And amino group-containing (meth) acrylates and ammonium salts such as ammonium carbonate. Specific examples of such a compound include 2,2-di (hydroxymethyl) propionic acid, 2,2-
Di (hydroxymethyl) butyric acid, polyhydric alcohol and polycarboxylic acid reactant, bishydroxyethylamine and 1,4 butanedicarboxylic acid reactant, diaminocarboxylic acid amino acids such as lysine, diaminobenzenecarboxylic acid, bishydroxyethyl Ethanesulfonic acid and the like can be mentioned, but not limited thereto.

The component (D) in the hydrophilic polymer of the present invention is a polyamine or a polyol containing a conjugated diene-based hydrocarbon chain, and preferably has a molecular weight of 100 to 50,000.

A conjugated diene-based hydrocarbon chain is a conjugated diene-based hydrocarbon polymer, a copolymer of a conjugated diene-based hydrocarbon and a monoolefinic unsaturated compound or a derivative thereof, for example, an amide,
Compounds containing esters, ethers, urethanes, urea bonds and the like are shown.

As conjugated diene hydrocarbons, 1,3-butadiene,
Isoprene, chloroprene and the like are used, and they can be used alone or as a mixture.

As monoolefinically unsaturated compounds, styrene, α
-Methylstyrene, O-methylstyrene, m-methylstyrene, P-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, acrylic ester, methacrylic ester and the like are used. .

Examples of the conjugated diene hydrocarbon chain include butadiene polymer, isoprene polymer, chloroprene polymer, styrene butadiene copolymer, styrene isoprene copolymer, styrene chloroprene copolymer, acrylonitrile butadiene copolymer, acrylonitrile isoprene copolymer ,
Acrylonitrile-chloroprene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-
Isoprene copolymer, methyl methacrylate-chloroprene copolymer, methyl acrylate-butadiene copolymer,
Examples thereof include a methyl isoprene acrylate copolymer, a methyl acrylate-chloroprene copolymer, an acrylonitrile-butadiene-styrene copolymer, and an acrylonitrile-chloroprene-styrene copolymer.

The molecular weight of the conjugated diene-based hydrocarbon chain-containing polyamine or polyol includes those having a molecular weight of 100 to 50,000, but the reactivity with the polyisocyanate, the molecular weight of the hydrophilic polymer after the reaction, the molecular weight of 500 in terms of the molecular weight distribution, etc. ~ 20,000 are preferred.

Such a polyamine or polyol can be synthesized by any method, and can also be obtained commercially. Specifically, the terminal amino group-containing liquid nitrile butadiene rubber represented by the following general formula d3 is ATBN
(Ube Industries, Goodrich), NISSO-PB (Nisso), R-45HT,
R-15HT, R-45M, PIP (Idemitsu Kosan), NISSO-PB (Nissau) and the like can be mentioned.

The polyisocyanate which is the component (E) in the hydrophilic polymer of the present invention is represented by the general formula (e), and if necessary, other functional groups which do not react with the isocyanate group in R ¹² , for example, ether and ester , Urethane, urea, amide, and carbon-carbon unsaturated bond. Specific examples of such a polyisocyanate include 2,4-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, P-
Xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate and the like. Aromatic diisocyanate compound, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate,
Aliphatic diisocyanate compounds such as lysine diisocyanate, diisocyanate diisocyanate, etc., isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4
(Or 2,6) diisocyanate, alicyclic diisocyanate compound such as 1,3- (isocyanatomethyl) cyclohexane, addition reaction product of 2 mol of hexamethylene diisocyanate and 1 mol of polyethylene glycol Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate.

The hydrophilic polymer of the present invention includes the above-mentioned (A), (B),
It is characterized by containing a structure obtained by subjecting the components (C), (D) and (E) to a polyaddition reaction, and if necessary, as a component (F), a polyamine capable of undergoing an addition reaction with the polyisocyanate. And / or a polyol, and is represented by the following general formula (VIII).

R ₁ -R ₃ -R ₁ (VIII) The hydrophilic polymer of the present invention comprises the above-mentioned (A),
It can be obtained by reacting the components (B), (C), (D) and (E) or, if necessary, the component (F) by a known urethanation or ureaureation method. As the solvent, no solvent or dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. nitrogen-containing solvents, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as acetone, aromatic solvents such as toluene, xylene, benzene, Ether solvents such as tetrahydrofuran, dioxane and diethyl ether; ester solvents such as ethyl acetate, isopropyl acetate and isobutyl acetate; heptane; n
Examples of the catalyst include a non-catalyst, an organic tertiary nitrogen-containing compound such as triethylenediamine, and a tin-based catalyst such as di-n-butyltin dilaurate. Known reaction methods can be employed.

The hydrophilic polymer of the present invention swells, disperses, and dissolves in water or alkaline water, an aqueous solution, or the like, which is a characteristic of the hydrophilic polymer.Heat or light, is polymerized by an active energy ray including an electron beam, and changes in performance. That is, in order to exhibit changes from hydrophilic to hydrophobic, from water-soluble or water-dispersible to water-absorbing properties, compatibility with existing general-purpose resins, and the like, the above-described (A), (B), (C), (D) and The content ratio of the component (E) and, if necessary, the component (F) is 0.1 to 99.9% by weight as the component (A), 0.1 to 99.9% by weight as the component (B), and 0.1 to 99.9% by weight as the component (C). 0.1 to 99.9% by weight as component (E), 0.1 to 99.9% by weight as component (E), 0 to 99.9% by weight as component (F), hydrophilicity, physical properties after polymerization,
Phase it is possible to adjust the point any content ratio, such as soluble and -CO ₂ M group content in the hydrophilic polymer,
It is preferably 0.1 to 5.0 × 10 ⁻³ mol / g.

The molecular weight of the hydrophilic polymer of the present invention is reduced viscosity, GPC
For example, the reduced viscosity is 0.1 to 5.0 (dl / g) and the number average molecular weight is (Mn) 1000 to 1000 in terms of polystyrene.
Preferably, the weight average molecular weight is (Mw) 5,000 to 200,000, and the molecular weight distribution (Mw / Mn) is 1.0 to 30.

Examples of the hydrophilic polymer obtained by the production method of the present invention having the above-mentioned constitution include the above-mentioned raw materials (A) to (E).
Is a bonding group, for example, there are the following combinations, and the components (A) to (E) may be repeated each other, or the combined components may be repeated. However, at least one terminal group is an A component residue.

AEBECEDECEAEABEECECEDEBEBEEBCEECDEE- C-A-E-B-E-C-E-D-E-D-E-D-E-D-E-D-E-D-E-D-C-E-D-E-D-E-D-E-B-E-D (E-E-D-E-D-E (Ebe-E- (E from E-D-E-D-E-B-E (E-D-E-E-D-E-B-E (E) (E))) -B-A-E-CE-D-E-D-E-B-E-C-A-C-E-C-C-D-C-C-C E-A-E-D-E-D-E-B-E-C-E-C-E-B-C-E-D-E-D-E-B-E-C-E-C-E-C-E-C-C-C-C-D (C) -E-D-E-E-CE-B-E-D-E-D-E-A-A-E-C-E-B-E-B-D-E-D-E-B-A-E-C-E-B-E-E- -CO ₂ M group content in the hydrophilic polymer in D-E-C a-E -C-E-B-E-D-E-D present invention is determined by neutralization titration method to be described later, the composition Under the conditions described below Analysis is possible by NMR.

The hydrophilic polymer of the present invention has -CO ₂ M as a hydrophilic component.
Water, surfactant-containing water, alkaline water or alcohol-mixed water because it contains a group or a —SO ₃ M group, a polyoxyalkylene chain component, a conjugated diene-based hydrocarbon chain component, and a polymerizable (meth) acryloyl group at a terminal. Swell, disperse, dissolve in
It changes into a hydrophobic polymer or a water-absorbing polymer by heat or photopolymerization of a (meth) acryloyl group, and has good compatibility with general-purpose resins.

The hydrophilicity of the present invention is a hydrophilic component -CO ₂ M group or-
Due to the SO ₃ M group and the polyoxyalkylene chain component, which is a feature of the present invention, water dispersing or water dissolving is exhibited by the following developing solutions. Specific examples include water containing domestic water in general, and water containing alcohol having 1 to 5 carbon atoms. Examples of the water include sodium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkylsulfonate, A surfactant such as sodium alkyl ether sulfonate, a fatty acid, lithium hydroxide, potassium hydroxide, sodium hydroxide, sodium borate, sodium carbonate, sodium acetate, magnesium acetate or a salt thereof may be contained. Examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, and neopentyl alcohol.

Further, if necessary, an ester-based, ketone-based, amide-based, ether-based solvent or the like can be added to the water or the aqueous developer. Specific examples include ethyl acetate, butyl acetate, isobutyl acetate, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, methyl butyl ketone, formamide, dimethylformamide, dimethylacetamide, tetrahydrofuran, dioxane and the like.

As a feature of the hydrophilic polymer of the present invention, polymerization of a terminal (meth) acryloyl group by an active energy ray such as heat, light, or an electron beam can be mentioned. Polymerization by heat can be performed by a known method. Specifically, there may be mentioned a method of dissolving the hydrophilic polymer of the present invention in an arbitrary solvent, coating and then performing polymerization by drying and heat treatment, or a method of performing melt molding and then performing polymerization by heat treatment. If necessary, a known thermal polymerization initiator, for example, a peroxide compound or the like can be mixed and used in an arbitrary amount according to the physical properties of the polymer. Thermal polymerization,
Temperatures suitable for melt molding include a range of 70 ° C to 200 ° C.

As a particularly preferable polymerization method of the hydrophilic polymer of the present invention, polymerization by active energy rays can be mentioned. In the case of performing polymerization by light, the hydrophilic polymer of the present invention and a known photopolymerization initiator are mixed and dissolved in an arbitrary solvent, and then concentrated, molded, or dried by coating. Unnecessary portions can be removed with a developing solution such as water described above, and can be used for an intended image, sealant, or adhesive application.

As the photopolymerization initiator that can be used in the present invention,
For example, benzophenones, benzoins, acetophenones, benzyls, benzoin alkyl ethers, benzyl alkyl ketals, anthraquinones, thioxanthones and the like can be mentioned. Specifically, 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 Thioxanthone, 2-chlorothioxanthone and the like. These are preferably contained in the composition in an amount of 0.01 to 5% by weight. If the amount is less than 0.01% by weight, the photopolymerization initiating ability is hindered. If the amount is more than 5% by weight, the curing depth cannot be obtained due to natural light, and the image is easily chipped by development, which is not preferable. More preferably, it is 0.1 to 3% by weight.

The ultraviolet ray which is the active energy ray used in the present invention is 15
A light source having a wavelength of 0 to 500 mμ, particularly a wavelength region of 300 to 400 mμ is effective, and low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, ultraviolet fluorescent lamps, chemical lamps, xenon lamps, and zirconium lamps are used as light sources. desirable.

The hydrophilic polymer of the present invention is a copolymer of a hydrophilic component chain and a hydrophobic component chain, which is a characteristic feature thereof, and therefore has excellent compatibility with general-purpose resins. Specifically, those used as general-purpose elastomers having a glass transition temperature of 5 ° C. or less are included.

The hydrophilic polymer of the present invention has hydrophilicity, polymerizability, hydrophobicity after polymerization, and compatibility with general-purpose resins, so that a water-developable image-forming material having water resistance, such as a water-developable flexographic printing plate, It can be used for photoresists and sandblasts, and can also be used as polymers polymerized by light or electron beams, such as adhesives, dispersants, films, paints, sealants, and the like.

(Action) The hydrophilic polymer of the present invention is a polymerizable polymer derived from a (meth) acryloyl group at a molecular terminal, a —CO ₂ M group or a —SO ₃ M group (M is a hydrogen atom, Periodic Tables I, II, and III). Group, acin, ammonium), and compatibility with general-purpose resins due to copolymerization of conjugated diene-based hydrocarbon chains. ,
A trade-off between hydrophobicity after polymerization with active energy rays can be exhibited, and a compatibilized structure with small phase separation can be formed by blending with a general-purpose resin.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

In the examples, “parts” means “parts by weight”, and the measurement of reduced viscosity, GPC measurement, acid value and NMR measurement were performed under the following conditions.

Measurement of reduced viscosity 0.100 g of sample is precisely weighed and dimethylformamide 25 ml (reagent
GR Nacalai Tesque) at 30 ° C and mix for 1 hour.

Measure the relative viscosity (η sel) in a thermostat at 30 ± 0.5 ° C.

Reduced viscosity η sp / c (dl / g) = η sel / c (C = sampled amount g × 4) The above η sp / c (dl / g) is defined as the reduced viscosity.

GPC measurement conditions Column: Shoedex KF804, 803, 802 Solvent: Tetrahydrofuran acid value JIS standard K-0070, K-3504, K-8004JOCS NMR measurement conditions Equipment: XL-300 Measurement frequency: 300 MHz Nuclear spin: 'H Solvent: CDCl ₃ / F ₃ CCO ₂ D (3% by weight) Temperature: 60 ° C. Example 1 29.0 parts of polytetramethylene glycol (G-850, manufactured by Hodogaya Chemical Co., Ltd.) 62.0 parts of dimethylolpropionic acid (Fujii Yoshitsusho) Hexamethylene diisocyanate 119.0
(A product of Nippon Polyurethane Industry Co., Ltd.) and 5.0 parts of n-butyltin dilaurate dissolved in 300.0 parts of tetrahydrofuran were placed in a flask equipped with a stirrer, and the flask was heated to 65 ° C. while stirring was continued. The reaction was continued for hours. Further, 26.0 parts of hydroxyethyl methacrylate was added and the reaction was continued for 2 hours while heating to 65 ° C. In a separate container, a solution prepared by dissolving 184.0 parts of acrylonitrile containing terminal amino group and butadiene oligomer (Hycar ATBN 1300 × 16 Ube Industries) in 270.0 parts of tetrahydrofuran was added to the above one flask with stirring at room temperature.
The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran. The resulting polymer has a reduced viscosity: η sp /
c (dl / g) = 0.22, number average molecular weight (Mn) = 6703, weight average molecular weight (Mw) = 30026, polydispersity (Mw / Mn) = 4.48, acid value: 63.9 (mg KOH), NMR chemical shift : Polytetramethylene chain (-CH _2- : 6.5 ppm (t), butadiene chain (-CH
= CH-: 5.4ppm (t)), methacryloyl group showed that.

Reference Example 1 An aqueous solution in which a predetermined amount of lithium hydroxide-hydrate and magnesium acetate tetrahydrate was dissolved was added to a solution of 100 parts of the hydrophilic polymer obtained in Example 1 in 200 parts of tetrahydrofuran, and the mixture was stirred and neutralized. Post benzoin methyl ether 1.0
Then, stirring was continued to obtain a polymer solution. The obtained polymer solution was dried under reduced pressure to remove tetrahydrofuran and water. The obtained polymer was heated and pressed to obtain a 3 mm sheet. The obtained sheet is heat-pressed to 105
Heated at a pressure of 100 kg / cm ³ for 1 minute between a polyester film having a thickness of 125 μm and a polyester film coated with 2 μm polyvinyl alcohol on one side on the same polyester film so that the polyvinyl alcohol coat layer is in contact with the sheet. Pressure was applied to produce a 2.8 mm thick photosensitive resin plate.

Peel off the polyester film of the top layer, leave the polyvinyl alcohol film on the top, and adhere the negative film with the image on it with a mercury lamp (Dai Nippon Screen Co., Ltd.)
Exposure was performed for 5 minutes at an illuminance of 25 W / m ² . After removing the negative film, development was carried out with a brush at 40 ° C. in neutral water containing 2% by weight of sodium alkylnaphthalenesulfonate, whereby an image pattern having a relief depth of mm was obtained. This image pattern faithfully reproduced the image of the negative film used. Further, the obtained relief had good transferability of the ink and showed a clear image, and no damage of the image area due to water swelling was observed.

Reference Example 2 10 parts of the hydrophilic polymer obtained in Example 1, 45 parts of chlorinated polyethylene (H-135 manufactured by Osaka Soda Co., Ltd.) as a hydrophobic polymer, and styrene-butadiene rubber (SBR1507)
15 parts of Nippon Synthetic Rubber Co., Ltd., 28.5 parts of butadiene oligoacrylate (PB-A Kyoeisha Yushi Co., Ltd.), 1 part of benzyldimethyl ketanol (Irgacure 651, Ciba Geigy Co., Ltd.) and 0.5 part of hydroquinone monomethyl ether After dissolving and dispersing in 40 parts of toluene and 10 parts of water, kneading at 105 ° C. using a heating kneader and defoaming, a transparent sheet having good compatibility was obtained.

When a relief was obtained from the obtained sheet in the same manner as in Reference Example 1, an image pattern having a relief depth of 1.2 mm was obtained. This image pattern faithfully reproduced the image of the negative film used. Further, the obtained relief showed a clear image with good transferability of the ink, and no damage to the image area due to water swelling was observed.

Example 2 In Example 1, the polytetramethylene glycol 29.0 was used.
A hydrophilic polymer was obtained in the same manner as in Example 1 except that 60.0 parts of terminally aminated polyoxypropylene (Diefarne D-2000, Texico Mitsui Chemicals) were used instead of parts. The obtained polymer has a reduced viscosity η sp / c (dl / g) =
0.25, specific gravity 1.0, decomposition point 200 ° C.

Reference Example 3 In Reference Example 1, the polymer obtained in Example 2 was used instead of the polymer obtained in Example 1, and all of Reference Example 2 was used.
1.3m depth of relief
m image patterns were obtained. This image pattern faithfully reproduced the image of the negative film used. In addition, the obtained relief showed a clear image with good ink transferability, and no damage to the image area due to water swelling was observed.

Example 3 In Example 1, the polytetramethylene glycol 29.0 was used.
29.0 parts of polyethylene glycol (PEG # 10)
(H. Nacalai Tesque) in the same manner as in Example 1 except that a hydrophilic polymer was obtained. The obtained polymer had a reduced viscosity of 0.21, a specific gravity of 1.0, and a decomposition point of 200 ° C.

Example 4 A relief was obtained in the same manner as in Reference Example 1 except that the polymer obtained in Example 3 was used instead of the polymer obtained in Example 1, and a depth of the relief was obtained.
A 1.4 mm image pattern was obtained. This image pattern faithfully reproduced the image of the negative film used. In addition, the obtained relief showed a clear image with good ink transferability, and no damage to the image area due to water swelling was observed.

Example 4 A hydrophilic polymer was obtained in the same manner as in Example 1 except that 184.0 parts of liquid polybutadiene having a terminal hydroxyl group (NISSO-PBG-3000 Nissau) was used instead of the acrylonitrile butadiene oligomer having a terminal amino group in Example 1. . The obtained polymer had a reduced viscosity of 0.21 and a specific gravity of 1.0 and a decomposition point of 200 ° C.

Reference Example 5 In Example 1, the polymer obtained in Example 4 was used in place of the polymer obtained in Example 1, and all the reliefs were obtained in the same manner as in Reference Example 1. The relief depth was 1.3 mm.
The following image pattern was obtained. This image pattern faithfully reproduced the image of the negative film used. In addition, the obtained relief showed a clear image with good ink transferability, and no damage to the image area due to water swelling was observed.

(Effect of the Invention) Since the hydrophilic polymer of the present invention has hydrophilicity, polymerizability, hydrophobicity after polymerization, and compatibility with general-purpose resins, it is water-developable image-forming material, particularly water-developable photosensitive. Flexographic printing plates,
It can be suitably used for binders, adhesives, etc., and greatly contributes to the industrial world.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/00-18/87

Claims (1)

(57) [Claims] (A) an alkyl ester of a hydroxy group-containing unsaturated carboxylic acid represented by the following general formula (a):
(B) a polyoxyalkylene chain-containing polyamine and / or polyol represented by the following general formula (b1) and / or (b2); and (C) -CO _{2 represented by the following} general formula (c1) and / or (c2) M group and / or —SO ₃ M group-containing polyamine and / or polyol (wherein M represents a hydrogen atom, a group I, II, or III element, an amine or ammonium), (D) a compound represented by the following general formula (d1) And / or (d2) a polyamine and / or a polyol having a conjugated diene hydrocarbon chain and (E) a polyisocyanate represented by the following general formula (e). This is a method for producing a hydrophilic polymer. (In the general formula a, R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents an alkylene group having 1 to 20 carbon atoms.) (In the general formulas b1 and b2, R ³ represents an alkylene group having 1 to 20 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom or an alkylene group having 1 to 20 carbon atoms, and n represents an integer of 1 to 100.) (In the general formulas c1 and c2, Z represents —CO ₂ —, —SO ₃ —, and R ⁶ represents an aliphatic or / and aromatic organic group having 1 to 20 carbon atoms;
R ⁷ and R ⁸ are a hydrogen atom or an aliphatic having 1 to 20 carbon atoms or /
And an aromatic organic group. ) In ^{HO-R 9 -OH (d2)} ( general formula d1, d2, R ⁹ is an organic group having a butadiene chain, which may have an amide bond .R ^10, R ¹¹
Is a hydrocarbon having 1 to 20 carbon atoms, and may form a ring via an oxygen atom and / or a nitrogen atom. ^{) OCN-R 12 -NCO (e} ) ( in the formula e, R ¹² represents an aliphatic organic group having 1 to 20 carbon atoms, alicyclic organic group, an aromatic organic group.)