JP2000321764A - Photosetting resin composition and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous development type photosetting resin composition capable of aqueous development and superior in the water and solvent resistances of the photosetting product having elasticity and to provide the pattern forming method using this composition. SOLUTION: This resin composition is obtained by reaction of reactants containing (a) polylactonediol, (b) diols selected from alkylenediol and polyalkylenediol and bisphenols or their hydrogenated alkyleneoxide adduct type diols, (c) polyisocyanate, and (d) compounds having ethylenically unsaturated groups, and further, an urethane compound having a carboxyl group in the molecule. The pattern is formed by using this photosetting resin composition to form a film and imagewise exposing it and removing the unexposed parts with an aqueous alkaline solution or an organic solvent containing an alkali or its mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition which can be cured by irradiation with ultraviolet rays or electron beams and which can be subjected to aqueous development, and a method for producing a pattern using the same. In particular, the present invention relates to a water-based development-type photocurable resin composition in which the cured product has excellent water resistance and solvent resistance, and furthermore, the cured product has an elastic property, and a method for producing a pattern using the same.

[0002]

2. Description of the Related Art As a water-based photo-curable resin, a functional group capable of forming an ion with an alkali metal such as carboxylic acid or sulfonic acid or an amine is introduced into a side chain or an ion such as an amine is formed with an acid. Urethane (meth) acrylate [(meth) acrylate means methacrylate and acrylate, in which a functional group is introduced into a side chain or a main chain.
The same applies hereinafter), and (meth) acrylate compounds such as polyester (meth) acrylate, polyether (meth) acrylate, and epoxy (meth) acrylate are known. Among them, urethane (meth) acrylate is excellent in flexibility, toughness, chemical resistance, etc., and is used in various applications such as photocurable coating agents, photoresist materials, photocurable inks, and materials for photosensitive printing plates. Applications are being made.

However, in the case of a water-based developable resin, not only an uncured part but also a cured part is swollen or partially applied to a cured pattern by an aqueous solvent, an organic solvent, or a mixture thereof, which causes a problem in product production. There was a problem that efficiency and yield were reduced. In addition, due to the low strength and brittleness, which are general properties of urethane (meth) acrylate, there are many disadvantages in applications where a cured product requires flexibility.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a water-based development type photocurable resin composition which is capable of aqueous development, has excellent water resistance and solvent resistance of the cured product, and has a cured product having an elastic property. As a result of diligent research and effort to obtain the above, the present inventors have succeeded in finding such an aqueous development type photocurable resin composition, and have completed the present invention.

[0005]

That is, the present invention provides:
(A) diols selected from polylactone diols, (b) alkylene diols, polyoxyalkylene diols and diols of alkylene oxide addition of bisphenols or hydrogenated products thereof, (c) polyisocyanates, (d) ethylenic The present invention relates to a photocurable resin composition obtained by reacting a reaction component containing a compound having a saturated group and containing a urethane compound having a carboxyl group in its molecule. The present invention also relates to the photocurable resin composition further containing a photopolymerization initiator. The present invention also relates to a photocurable resin composition wherein the urethane compound has an ethylenically unsaturated group at both ends.

The present invention also relates to a photocurable resin composition wherein the carboxyl group of the urethane compound is obtained by using (e) a diol having a carboxyl group as a reaction component. The present invention also relates to a photocurable resin composition wherein the carboxyl group of the urethane compound is obtained by using a polylactone diol obtained by reacting a carboxylic acid-containing diol with a lactone as the component (a). In the present invention, the component (a) is a polylactone diol having a number average molecular weight of 300 to 5000, and the component (b) is a polylactone diol having a number average molecular weight of 62 to
The present invention relates to a photocurable resin composition which is a diol selected from 3,000 alkylene diols, polyoxyalkylene diols, and alkylene oxide addition type diols of bisphenols or hydrogenated products thereof.

The present invention also relates to a photocurable resin composition wherein the component (c) is an aliphatic diisocyanate.
Further, the present invention also forms a film using the photocurable resin composition, imagewise exposes the film to light, and exposes an unexposed portion with an alkaline aqueous solution, an alkali-containing organic solvent, or a mixture thereof. The present invention relates to a method for producing a pattern characterized by being removed.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The urethane compound used in the present invention includes: (a) a diol selected from polylactone diol, (b) an alkylene diol, a polyoxyalkylene diol and an alkylene oxide addition type diol of a bisphenol or a hydrogenated product thereof, and (c) a polyisocyanate. Nart,
(D) It is obtained by reacting a reaction component containing a compound having an ethylenically unsaturated group, and has a carboxyl group in the molecule.

Although the presence of a carboxyl group in the molecule can provide good aqueous developability,
The method for introducing a carboxyl group is not particularly limited. For example, in addition to the above-mentioned components (a) and (b) as a diol component, (e) a diol having a carboxyl group may be used in combination, or the (a) component may be used as the (a) component. And a method using a polylactone diol obtained by reacting a diol having a carboxyl group with a lactone.

As the polylactone diol of the component (a), ring-opening polymers of lactones such as γ-butyrolactone, ε-caprolactone, δ-valerolactone and having hydroxyl groups at both ends, and the above-mentioned lactones And ethylene glycol, polyethylene glycol, propylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, poly1,2-butylene glycol, 1,4- Those obtained by reacting with a diol such as cyclohexane dimethanol are exemplified. A commercially available product may be used as such a polylactone diol. Examples of the commercially available product include Praxel 205, 205A, which is a reaction product of ε-caprolactone and a diol.
L, 208, 208AL, 212, 212AL, 22
0, 220AL (both trade names are Daicel Chemical Industries)
Co., Ltd.).

Further, as the polylactone diol having a carboxyl group, a copolymer of a (poly) lactone having a hydroxyl group and a diol having a carboxyl group described below can be used. It can be obtained by ring-opening polymerization with an appropriate catalyst or the like. Commercially available products may be used, and commercially available products include Plaxel 205A, 210A, 220A, 205B
A, 210BA, 220BA (trade names, all manufactured by Daicel Chemical Industries, Ltd.) and the like.

The number average molecular weight of the component (a) is preferably from 300 to 5,000, more preferably from 500 to 2,000, in view of the strength of image formation and the cured product. The number average molecular weight can be determined by gel permeation chromatography in terms of standard polystyrene or by calculation from the reaction charge ratio and hydroxyl value (the same applies hereinafter).

The component (a) is preferably used in an amount of 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the solid content of the photocurable resin composition. If the amount is less than 10 parts by weight, the strength and the anti-rubbing elasticity of the cured product tend to be inferior. If the amount is more than 30 parts by weight, the crystallinity of the resin becomes strong, causing turbidity or exposure of the cured product before exposure. Tend.

In the present invention, the diol selected from the alkylene diols, polyoxyalkylene diols and the alkylene oxide addition type diols of bisphenols or hydrogenated bisphenols as the component (b) include ethylene glycol, polyethylene glycol, propylene glycol, and the like. Tetramethylene glycol, polytetramethylene glycol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, neopentyl glycol, poly1,2-butylene glycol, 1,4-cyclohexanedimethanol, methylpentanediol-modified polytetramethylene glycol, propylene glycol-modified polytetramethylene glycol,
Ethylene glycol-propylene glycol block copolymer, ethylene glycol-tetramethylene glycol copolymer, 2-methyl-1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-
Pentanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, ethylene oxide adduct of bisphenol F, bisphenol Examples thereof include a propylene oxide adduct of F, hydrogenated bisphenol F, an ethylene oxide adduct of hydrogenated bisphenol F, and a propylene oxide adduct of hydrogenated bisphenol F, but are not particularly limited thereto.

The number average molecular weight of the component (b) is preferably from 62 to 3,000 from the viewpoint of the strength of the cured product, the anti-rubbing property, and the like.
2-1000 is more preferable, and 100-500 is still more preferable.

The component (b) is preferably used in an amount of 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the solid content of the photocurable resin composition. If this amount is less than 10 parts by weight, the anti-rubbing elasticity tends to be inferior, and if it exceeds 90 parts by weight, the strength of the cured product tends to be inferior.

In the urethane compound of the present invention,
One of the methods for introducing a carboxyl group is (e)
As a component, there is a method in which a diol having a carboxyl group is used in combination with the components (a) and (b). Examples of the diol having a carboxyl group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, 2,3-Dihydroxy-2-methylpropionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid 2,3-dihydroxybutanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxyhexadecanoic acid, bis (hydroxymethyl) acetic acid, 4,4-bis (4-hydroxyphenyl) acetic acid , 4,4-bis (4-hydroxyphenyl) pentanoic acid, 3,5-dihydroxybenzoic acid, tartaric acid and the like; Maleic anhydride, phthalic anhydride, and a polybasic acid such as trimellitic anhydride, glycerin,
Compounds obtained by an esterification reaction with a polyol such as pentaerythritol can also be used.

When the diol (e) having a carboxyl group is used in combination with the components (a) and (b), the amount of the diol having a carboxyl group is 10 to 200 mgKOH / acid as an acid value in the solid content of the resin composition. g, more preferably 20 to 100 mgKOH / g. If this amount is less than 10 mgKOH / g, the alkali developability tends to be poor, and 200 mgKOH / g
If it exceeds g, the water resistance and solvent resistance of the cured product tend to decrease.

In the present invention, the polyisocyanate (c)
Examples include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate Examples include, but are not limited to, isocyanates and hydrogenated diphenylmethane diisocyanate.

Among these, especially isophorone diisocyanate, norbornene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Are preferred. Aliphatic diisocyanates and mixtures thereof.

The amount of the component (c) is preferably 5 to 70 parts by weight based on the solid content of the resin composition.
It is more preferable to use 50 parts by weight. If the amount is less than 5 parts by weight, the cured product tends to have poor chemical resistance and strength, and if it exceeds 70 parts by weight, the varnish viscosity is too high and the handling properties tend to decrease.

In the present invention, (d) compounds having an ethylenically unsaturated group include compounds having an ethylenically unsaturated group and a hydroxyl group, compounds having an ethylenically unsaturated group and an isocyanate group, and ethylenically unsaturated groups. Compounds having a saturated group and a carboxyl group are exemplified.

Examples of the compound having an ethylenically unsaturated group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, ethylene glycol-propylene glycol block copolymer mono (meth) acrylate, ethylene glycol -Tetramethylene glycol copolymer mono (meth) acrylate and the like.

The compounds having an ethylenically unsaturated group and an isocyanate group include isocyanatomethyl (meth) acrylate, isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, and various diisocyanates. And a reaction product of the aforementioned compound having an ethylenically unsaturated group and a hydroxyl group, and a commercially available product can also be used. Commercial products include Karenz MOI (manufactured by Showa Denko KK). Examples of the compound having an ethylenically unsaturated group and a carboxyl group include acrylic acid and methacrylic acid.

As the compound (d) having an ethylenically unsaturated group of the present invention, a compound having the above-mentioned ethylenically unsaturated group and a hydroxyl group is preferable, and among them, acrylate is particularly preferable from the viewpoint of photosensitivity.

The amount of the component (d) is preferably 0.5 to 90 parts by weight based on the solid content of the resin composition.
It is more preferable to use 50 to 50 parts by weight. If this amount is 0.
If it is less than 5 parts by weight, the photocurability tends to be impaired,
If the amount exceeds 90 parts by weight, the stability and the like of the cured product tend to decrease.

The urethane compound of the present invention can be produced by mixing each reaction component and reacting at 40 to 120 ° C. for about 1 to 120 hours. In the above reaction, a solvent that does not inhibit the reaction between the isocyanate group and the hydroxyl group such as methyl ethyl ketone toluene and ethyl acetate can be used, and a catalyst such as dibutyltin dilaurate can be used.

The weight average molecular weight of the urethane compound obtained by reacting each of the above components is from 1,000 to 50,000.
0 is preferable, and 2,000 to 30,000 is more preferable. Here, if the molecular weight is less than 1,000, the properties of the elastic body tend to be lost, and if the molecular weight is less than 50,
If it exceeds 000, the photosensitivity is deteriorated, and the water resistance and solvent resistance of the cured product tend to decrease. The molecular weight is 5
When it exceeds 000, the photosensitivity is increased by using a monofunctional or polyfunctional acrylate compound in combination as a photopolymerizable monomer, and the water resistance and solvent resistance of the cured product are increased. The decline can be compensated for. The molecular weight can be measured by gel permeation chromatography and calculated in terms of standard polystyrene.

The acid value of the urethane compound is preferably 10
~ 200mgKOH / g, more preferably 20 ~ 100m
gKOH / g. If the acid value is less than 10 mgKOH / g, the alkali developability tends to be inferior, and if it exceeds 200 mgKOH / g, the water resistance and solvent resistance of the cured portion tend to decrease.

The aqueous developing photocurable resin composition of the present invention may further contain a photopolymerizable monomer, if necessary. As the photopolymerizable monomer, a monofunctional or polyfunctional (meth) acrylate-based compound can be preferably used. Examples of the photopolymerizable monomer include methyl acrylate, ethyl acrylate, and n. -Propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, ethylhexyl acrylate, isodecyl acrylate, n-hexyl acrylate, stearyl acrylate, lauryl acrylate, tridecyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, Butoxyethyl acrylate, 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-methoxyethoxy acrylate, 2-ethoxyethoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, octafluoropentyl acrylate, N, N-dimethylaminoethyl Acrylate,
N, N-diethylaminoethyl acrylate, allyl acrylate, 1,3-butanediol acrylate,
1,4-butanediol acrylate, 1,6-hexanediol acrylate, polyethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, hydroxypivalic acid ester neopentyl glycol Diacrylate, trimethylolpropane diacrylate, 1,3-bis (hydroxyethyl)
-5,5-dimethylhydantoin, 3-methylpentanediol acrylate, α, ω-diacrylbisdiethylene glycol phthalate, trimethylolpropane triacrylate, pentaerythritol acrylate, pentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate Α, ω-tetraallylbistrimethylolpropane tetrahydrophthalate, 2-hydroxyethylacryloyl phosphate, trimethylolpropane trimethacrylate,
Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Pentyl glycol dimethacrylate, diacryloxyethyl phosphate, N-vinylpyrrolidone and the like can be mentioned, and among them, an acrylate derivative is preferable.

When these photopolymerizable monomers are used, the amount is preferably 1 to 400 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the urethane compound. If this amount exceeds 400 parts by weight,
The property as an elastic body tends to be lost.

The photocurable resin composition of the present invention further comprises
Depending on the purpose, unsaturated polyester resin, vinyl ester resin, vinyl urethane resin, vinyl ester urethane resin, polyisocyanate, polyepoxide, epoxy-terminated polyoxazolidone, acrylic resin, alkyd resin, urea resin, melamine resin, polydiene Natural and synthetic, such as elastomers, polyurethane elastomers, saturated polyesters, saturated polyethers, cellulose derivatives such as nitrocellulose, cellulose acetate butyrate, and oils and fats such as linseed oil, tung oil, soybean oil, castor oil, and epoxidized oil A polymer substance can be contained. When these are used, it is preferable to add about 1 to 400 parts by weight to 100 parts by weight of the urethane compound.

The photocurable resin composition of the present invention preferably contains a photopolymerization initiator. Examples of usable photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, carbonyl [benzophenone, diacetyl, benzyl, benzoin, ω-bromoacetophenone, chloroacetone,
Acetophenone, 2,2-diethoxyacetophenone,
2,2-dimethoxy-2-phenylacetone, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, p, p'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzoin isobutyl ether, benzoin -N-butyl ether, benzyldimethyl ketal, methylbenzoyl formate, 2,2-
Diethoxyacetophenone, 4-N, N'-dimethylacetophenones], sulfides (such as diphenyl disulfide and dibenzyl disulfide), quinones (such as benzoquinone and anthraquinone), and azo (azobisisobutyronitrile, 2,2) '-Azobispropane, hydrazine, etc.), sulfochlorides, thioxanthone, etc., peroxides (benzoyl peroxide, di-t-butyl peroxide, etc.), isoamyl o-dimethylaminobenzoate and the like.

The photopolymerization initiator is preferably added in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the urethane compound from the viewpoint of photocurability and mechanical properties of the cured product.

The aqueous developable photocurable resin composition of the present invention contains hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6
A polymerization inhibitor such as -di-t-butyl-4-methylphenol can be added. When these are used, 0.01 to 100 parts by weight of the urethane compound are used.
It is preferable to add about 3 parts by weight.

The photocurable resin composition of the present invention contains ketones such as methyl ethyl ketone, acetone, and methyl isobutyl ketone, and butyl acetate, ethyl acetate, isobutyl acetate and the like for controlling the viscosity of the resin and the efficiency of resin synthesis. Esters, butanol, alcohols such as isobutanol, cellosolves such as ethyl cellosolve, butyl cellosolve,
Glycols such as ethylene glycol and propylene glycol, polyoxyalkylenes such as polyethylene glycol and polypropylene glycol, lactones such as γ-butyrolactone, cyclic ether compounds such as dioxane and tetrahydrofuran, N, N-dimethylformamide; A suitable organic solvent such as an amide compound such as N-dimethylacetamide can be contained. When these are used, they are preferably contained in an amount of 10 to 500 parts by weight based on 100 parts by weight of the urethane compound.

The photocurable resin composition of the present invention can be used as a photocurable coating agent, a photoresist material, a photocurable ink, a material for a photosensitive printing plate, and the like. The photocurable resin composition of the present invention is capable of aqueous development, but the aqueous development is water, an alkaline aqueous solution, an acidic aqueous solution,
It means that an uncured portion can be dissolved or swelled or removed by other methods using a solution containing 50% by weight or more of water, such as an alcoholic aqueous solution, a ketone aqueous solution, a surfactant-containing aqueous solution, and a mixed solution thereof. As the photocurable resin composition of the present invention, it is preferable to use an alkaline aqueous solution, an alkali-containing organic solvent, or a mixed solution of both.

That is, a film is formed using the photocurable resin composition, and this film is imagewise exposed to light, and an unexposed portion is exposed using an alkaline aqueous solution, an alkali-containing organic solvent, or a mixture thereof. The pattern can be manufactured by removing. Ultraviolet light or the like can be used as light for exposure. As a method of imagewise exposing light, a method of exposing through a photomask on which a target pattern is formed can be used. Examples of the aqueous alkali solution used for development include an aqueous solution of 1 to 10% by weight of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like. By dissolving or swelling the unexposed portions with an alkaline aqueous solution and removing them, a pattern of a cured product corresponding to the exposed portions can be produced.

[0039]

Next, the present invention will be described in detail with reference to examples and comparative examples. In the following, "part" and "%"
All are by weight unless otherwise specified.

Synthesis Example 1 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, the following formula was used.

Embedded image (Placcel 205, trade name, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight 5)
00) 211.8 parts, dimethylolbutanoic acid 62.7
Parts, 40.4 parts of diethylene glycol, 93.4 parts of 2-hydroxyethyl acrylate, 0.51 part of p-methoxyphenol, 0.51 part of dibutyltin laurate (trade name L101, manufactured by Tokyo Fine Chemical Co., Ltd.), and 102. Charge 1 part, 6 under air flow
The temperature was raised while stirring to 5 ° C.

In a dropping container, trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan)
(TTMDI) 338.1 parts was charged, and the mixture was uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping vessel was washed with 84.5 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 75
The stirring and warming were continued at ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., 10.3 parts of methanol was added, and the temperature was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 55.7 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 3250 and an acid value of 22.5.

Synthesis Example 2 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, the following formula was used.

Embedded image Carboxylic acid-modified polycaprolactone diol (Placcel 205B, manufactured by Daicel Chemical Industries, Ltd.)
A, number average molecular weight 500) 265.9 parts, diethylene glycol 50.7 parts, 2-hydroxyethyl acrylate 117.2 parts, p-methoxyphenol 0.54 parts,
Dibutyltin laurate (Tokyo Fine Chemical Co., Ltd.
0.54 parts of trade name L101) and 108.5 parts of methyl ethyl ketone were charged, and the mixture was heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan)
(TTMDI) 312.7 parts were charged, and the mixture was uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping container was washed with 78.2 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction container. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 75
The stirring and warming were continued at ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., 9.5 parts of methanol was added, and the temperature was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.2 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 2790 and an acid value of 28.3.

Synthesis Example 3 An air gas was introduced into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, and then carboxylic acid-modified polycaprolactone diol (Daicel Chemical Industries, Ltd.)
250.8 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG20)
0, number average molecular weight 200) 90.3 parts, 2-hydroxyethyl acrylate 110.6 parts, p-methoxyphenol 0.56 parts, dibutyltin laurate (trade name L101, manufactured by Tokyo Fine Chemical Co., Ltd.) 0.56 parts And 112.9 parts of methyl ethyl ketone, and the mixture was heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, trimethylhexamethylene diisocyanate (VESTANA manufactured by Huls Japan) is used.
(TTMDI) 295.0 was charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ± 3
C. After the completion of the dropping, the dropping vessel was washed with 73.7 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, 75 ± until the peak derived from the isocyanate in the infrared absorption spectrum disappears.
The stirring and warming were continued at 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., and 9.0 parts of methanol was added.
It was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.6 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 2,970 and an acid value of 26.7.

Synthesis Example 4 An air gas was introduced into a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and an air gas introduction pipe, and then carboxylic acid-modified polycaprolactone diol (Daicel Chemical Industries, Ltd.)
223.8 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG40)
0, number average molecular weight 400) 161.1 parts, 2-hydroxyethyl acrylate 98.7 parts, p-methoxyphenol 0.60 parts, dibutyltin laurate (trade name L101, manufactured by Tokyo Fine Chemical Co., Ltd.) 0.60 parts And 120.9 parts of methyl ethyl ketone, and the mixture was heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan)
(TTMDI) 263.2 was charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ± 3
C. After the completion of the dropping, the dropping vessel was washed with 65.8 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, 75 ± until the peak derived from the isocyanate in the infrared absorption spectrum disappears.
The stirring and warming were continued at 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., and 8.0 parts of methanol was added.
It was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 57.3 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 3350 and an acid value of 23.8.

Synthesis Example 5 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, carboxylic acid-modified polycaprolactone diol (Daicel Chemical Industries, Ltd.)
202.0 parts of polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG60)
0, number average molecular weight 600) 218.2 parts, 2-hydroxyethyl acrylate 89.1 parts, p-methoxyphenol 0.64 parts, dibutyltin laurate (trade name L101, manufactured by Tokyo Fine Chemical Co., Ltd.) 0.64 parts And 127.3 parts of methyl ethyl ketone, and the mixture was heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan)
(TTMDI) 237.6 was charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ± 3
C. After the completion of the dropping, the dropping vessel was washed with 59.4 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, 75 ± until the peak derived from the isocyanate in the infrared absorption spectrum disappears.
The stirring and warming were continued at 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., and 7.2 parts of methanol was added.
It was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 57.8 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 3,730, and an acid value of 22.6.

Comparative Synthesis Example 1 After air gas was introduced into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, polycaprolactone diol (Placcel 205, trade name, manufactured by Daicel Chemical Industries, Ltd.) ) 344.7 parts, dimethylolbutanoic acid 5
1.0 part, 2-hydroxyethyl acrylate 76.0
Parts, p-methoxyphenol 0.59 parts, dibutyltin laurate (trade name: L1 manufactured by Tokyo Fine Chemical Co., Ltd.)
01) 0.59 part and 117.9 parts of methyl ethyl ketone were charged and heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan)
(TTMDI) 275.1 parts were charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping vessel was washed with 68.8 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 75
The stirring and warming were continued at ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming the disappearance of this peak, the temperature was lowered to 60 ° C., 8.4 parts of methanol was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 57.0 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 2470 and an acid value of 18.3.

Comparative Synthesis Example 2 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, carboxylic acid-modified polycaprolactone diol (Daicel Chemical Industries, Ltd.)
369.9 parts, manufactured by Plaxel 205BA)
81.5 parts of hydroxyethyl acrylate, 0.56 parts of p-methoxyphenol, 0.56 parts of butyltin laurate (trade name: L101, manufactured by Tokyo Fine Chemical Co., Ltd.) and 112.9 parts of methyl ethyl ketone, and 65 ° C. in an air stream. The temperature was raised while stirring.

In a dropping vessel, add trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan).
(TTMDI) 295.2 parts were charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping vessel was washed with 73.8 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 75
The stirring and warming were continued at ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., 9.0 parts of methanol was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.6 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 2190, and an acid value of 41.4.

COMPARATIVE SYNTHESIS EXAMPLE 3 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, 114.7 parts of diethylene glycol and 80.1 parts of dimethylolbutanoic acid were used.
Parts, 119.3 parts of 2-hydroxyethyl acrylate,
0.39 parts of p-methoxyphenol, dibutyltin laurate (trade name: L10, manufactured by Tokyo Fine Chemical Co., Ltd.)
1) 0.39 parts and 117.9 parts of methyl ethyl ketone were charged and heated to 65 ° C. while stirring in an air stream.

In a dropping container, add trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan).
(TTMDI) 431.8 parts were charged and uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping vessel was washed with 108.0 parts of methyl ethyl ketone, and the washed solution was directly charged into the reaction vessel. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 7
The stirring and warming were continued at 5 ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., 13.2 parts of methanol was added, and the temperature was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 53.7 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 2320 and an acid value of 28.8.

Comparative Synthesis Example 4 After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, polyethylene glycol (PEG400, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight) 400) 303.7 parts, dimethylolbutanoic acid 5
6.2 parts, 2-hydroxyethyl acrylate 83.7
Parts, p-methoxyphenol 0.55 parts, dibutyltin laurate (trade name L1 manufactured by Tokyo Fine Chemical Co., Ltd.)
01) 0.55 parts and 110.9 parts of methyl ethyl ketone were charged, and the mixture was heated to 65 ° C. while stirring in an air stream.

In a dropping vessel, add trimethylhexamethylene diisocyanate (VESTANA, manufactured by Huls Japan).
(TTMDI) 303.0 parts were charged, and the mixture was uniformly dropped into the reaction vessel over 3 hours. At that time, the reaction vessel temperature was set to 65 ±
It was kept at 3 ° C. After the completion of the dropping, the dropping container was washed with 75.7 parts of methyl ethyl ketone, and the solution after the washing was directly charged into the reaction container. After keeping the temperature for 2 hours with further stirring, the temperature was raised to 75 ° C. Thereafter, until the peak derived from the isocyanate in the infrared absorption spectrum disappears, 75
The stirring and warming were continued at ± 3 ° C. The peak derived from the isocyanate disappeared in about 6 to 8 hours. After confirming disappearance of this peak, the temperature was lowered to 60 ° C., 9.2 parts of methanol was added, and the mixture was kept at 60 ± 3 ° C. for 30 minutes. Thereafter, 56.4 parts of methyl ethyl ketone was added to prepare a urethane acrylate solution having a resin solid content of 75%, a weight average molecular weight of 3440 and an acid value of 20.2.

Examples 1 to 5 and Comparative Examples 1 to 4 Irgacure 6 was added as a photoinitiator to 50 parts of the urethane acrylate solution of the above Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 4.
Add 1 part or 0.25 part of 51 (manufactured by Ciba Geigy),
The mixture was stirred well to produce a photocurable resin composition.

Evaluation Example 1 The above photocurable resin composition (1 part of Irgacure 651)
Was applied on a glass plate with a thickness of 300 μm using an applicator and set at 80 ° C. for 30 minutes. The glass plate is fed under a high-pressure mercury lamp of 80 W / m at a conveyor speed of 5 m / min.
It was passed twice to obtain a cured coating film. 5 × 1.5cm
After being cut into corners, 1.5 cm from both ends were cut off by an autograph, and the breaking strength and elongation were measured.

Evaluation Example 2 The above photocurable resin composition (1 part for Irgacure 651)
Was placed in a Petri dish of 10 cmφ × 1.5 cm, and the solvent was evaporated at 80 ° C. under slightly reduced pressure (700 mmHg). Conveyor speed is 5m under 80W / m high pressure mercury lamp.
The mixture was passed three times at a time per minute to obtain a cured product. The rebound resilience and surface hardness were measured.

Evaluation Example 3 The photocurable resin composition (Irgacure 651 was 0.2
5 parts) using an applicator on a copper plate to a thickness of 300 μm.
And set at 80 ° C. for 30 minutes. A Mylar film (manufactured by Teijin Limited) was placed on this copper plate, and a 21-step tablet was placed on the Mylar film, and exposure was performed while changing the amount of light irradiation. The exposure required for curing the eighth stage of the 21-step tablet was taken as the light sensitivity.

Evaluation Example 4 The above photocurable resin composition (Irgacure 651 was 0.2
5 parts) using an applicator on a copper plate to a thickness of 300 μm.
And set at 80 ° C. for 30 minutes. A mylar film (manufactured by Teijin Limited) was placed on the copper plate, and a negative and a positive pattern were placed thereon. The exposed amount of the light sensitivity value of Evaluation Example 3 was irradiated to examine the developability.

Experimental Results The results of Evaluation Examples 1 to 4 are shown below.

[0064]

[Table 1]

[0065]

The photocurable resin composition of the present invention is capable of aqueous development, has good developability, is excellent in sensitivity, has excellent water resistance and solvent resistance of the cured product, and has an elastic cured product. It has the properties of the body. Further, according to the method for producing a pattern of the present invention, a pattern which can be favorably developed by alkali development, has excellent water resistance and solvent resistance of a cured product, and has a cured product having properties of an elastic body is obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 2H025 AA01 AA04 AA06 AB02 AB15 AB16 AB17 AC01 AC06 AD01 BC14 BC32 BC42 BC66 BC85 BJ07 CA01 CA18 CA23 CA27 CA31 FA03 FA17 2H096 AA00 AA02 AA25 AA26 AA27 BA05 BA04 BA20 EA02 EA02EA06 BA08 CA04 CA22 CA24 CB03 CB04 CB07 CB08 CC03 CC08 CC12 CC23 CC26 CC45 CC52 CC61 CC62 CC65 CC67 CD04 CD06 DA01 DB04 DB07 DF11 DG03 DG04 DG06 DG08 DG12 DG14 DG15 DG16 FA02 FB01 FB04 FC01 HC04 HC03 HC04 HC61 HC64 HC67 HC71 HC73 JA21 KA01 KB02 KD03 KD06 KD08 KD11 KD12 KD21 KD24 KD25 LA13 LA23 LA33 QA05 QB11 RA07 RA13 5E339 CC01 CC02 CD01 CE12 CF16 CF17 DD02

Claims (8)

[Claims] 1. A diol selected from (a) a polylactone diol, (b) an alkylene diol, a polyoxyalkylene diol and an alkylene oxide addition type diol of a bisphenol or a hydrogenated product thereof.
(C) a photocurable resin obtained by reacting a reaction component containing a polyisocyanate and (d) a compound having an ethylenically unsaturated group and containing a urethane compound having a carboxyl group in its molecule; Composition. 2. The photocurable resin composition according to claim 1, further comprising a photopolymerization initiator. 3. The photocurable resin composition according to claim 1, wherein the urethane compound has an ethylenically unsaturated group at both ends. 4. The photocurable resin composition according to claim 1, wherein the carboxyl group of the urethane compound is obtained by further using (e) a diol having a carboxyl group as a reaction component. 5. A carboxyl group of a urethane compound,
The method according to claim 1, wherein a carboxyl group-containing polylactone diol obtained by reacting a carboxyl group-containing diol with a lactone is used as the component (a).
4. The photocurable resin composition according to 2 or 3. 6. The component (a) having a number average molecular weight of 300 to 5
000 polylactone diol, wherein the component (b) is
A diol selected from alkylene diols having a number average molecular weight of 62 to 3,000, polyoxyalkylene diols, and alkylene oxide addition diols of bisphenols or hydrogenated products thereof.
Or the photocurable resin composition according to 5. 7. The photocurable resin composition according to claim 1, wherein the component (c) is an aliphatic diisocyanate. 8. A film is formed using the photocurable resin composition according to claim 1, and the film is exposed imagewise to light, and an alkaline aqueous solution, an alkali-containing organic solvent or a mixture thereof. A method for producing a pattern, comprising removing unexposed portions with a mixture of the two.