JP2002062644A - Photosensitive resin composition, covering material and matrix material for frp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition free of gelling and the phase separation of a solid resin component and a diluent component in storage, excellent in photo-curability and low odor emitting property, giving a homogeneous transparent cured body and excellent in profitableness. SOLUTION: The photosensitive resin composition contains a resin obtained by mixing 90-10 wt.% unsaturated polyester (A) with 10-90 wt.% polymerizable monomers including a (meth)acrylic ester (B) having an oligoalkylene glycol unit and 0.1-30 wt.% photo radical polymerization initiator (C) based on 100 wt.% of the resin. The (meth)acrylic ester (B) is, e.g. a polymerizable monomer of formula (1) (where R1 and R3 are each H or methyl; R2 is H, alkyl, aryl or benzyl; and (n) is an integer of 2-30).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive resin composition, and more particularly, to a composition having excellent stability upon storage, which is free from gelation, and a polymerizable monomer. The present invention relates to a photosensitive resin composition which has no phase separation between a resin solid content dissolved in water and a reactive diluent component as its polymerizable monomer, and is excellent in photocurability and low odor. Further, the present invention relates to a photosensitive resin composition which can be cured to obtain a homogeneous and transparent cured product and is economically excellent.

[0002]

2. Description of the Related Art It is well known that a resin obtained by diluting an unsaturated polyester with a styrene monomer is used as a photosensitive resin. However, the coating film has a slow curing speed and sometimes releases toxic styrene into the atmosphere during curing, and thus improvement is awaited.

On the other hand, oligomers having a (meth) acryl group such as urethane (meth) acrylate, epoxy (meth) acrylate and polyester (meth) acrylate are generally used for the photosensitive resin. In general, it is expensive, and has a so-called anaerobic curability in which the surface of a cured coating film becomes uncured when cured in the air.

[0004] In addition, various (meth)
Various resin compositions containing an acrylate ester have been disclosed. Specifically, JP-A-53-92888, JP-A-59-174611, and JP-A-5-27
9430, JP-A-7-216040, JP-A-8-217837, JP-A-9-157336, JP-A-10-87770 and the like, all of which use peroxide. Uses a curing method. However, peroxide curing generally requires a longer curing time than light curing, so that the polymer component and monomer / oligomer components generated during the curing process undergo phase separation, resulting in non-uniform curing. There was a major drawback of giving things. Also, in these publications,
There is no suggestion to devise a specific resin structure for solving the above problems. Particularly disclosed as unsaturated polyester resins are unsaturated polyester resins having a normal structure.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, the present invention has excellent stability during storage, and as a result, there is no concern about gelation, and it is in a state of being dissolved in a polymerizable monomer. An object of the present invention is to obtain a photosensitive resin composition which is free from phase separation between a resin solid content and a reactive diluent component as a polymerizable monomer, and is excellent in photocurability and low odor.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies in view of the above problems, and have completed the present invention. Specifically, it can be achieved by specifying the component amount ratio to be used, devising the structure of the unsaturated polyester, judging the compatibility, selecting the resin composition, and the like. That is, the present invention relates to an unsaturated polyester (A) 90 to 10% by weight.
And a (meth) acrylate (B) having 10 to 90% by weight having an oligoalkyleneylene glycol unit, wherein the (meth) acrylate (B) comprises Equation (1):

[0007]

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Wherein R ₁ and R ₃ independently represent hydrogen or a methyl group, R ₂ represents hydrogen, an alkyl group, an aryl group or a benzyl group, and n represents an integer of 2 to 30 ), General formula (2):

[0009]

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(Wherein R ₄ , R ₅ and R ₆ independently represent hydrogen or a methyl group, and n represents an integer of 2 to 30) and a general formula (3):

[0011]

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(Wherein, R ₇ represents a residue of a polyol having (x + y) hydroxyl groups, R ₈ and R ₉ independently represent hydrogen or a methyl group, and n is an integer of 1-30. Where x is an integer of 2 or more, y is an integer of 1 or more,
x + y represents an integer of 3 to 30), and is at least one or more polymerizable monomers selected from (meth) acrylates (B) having oligoalkylene glycol units, and the resin composition The present invention provides a photosensitive resin composition comprising 0.1 to 30% by weight of a photo-radical polymerization initiator (C) based on 100% by weight of a product. More preferably, of the above resin composition,
The total light transmittance measured according to JIS-K-7105 (1994) is 50% or more. More preferably, the resin composition has a loss on heating measured according to JIS-K-5407 (1990) of less than 20%. Specific applications of the photosensitive resin composition include a coating material and a base material for FRP.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
The present invention relates to an unsaturated polyester (A) 90 to 10% by weight.
And a (meth) acrylate (B) having 10 to 90% by weight having an oligoalkyleneylene glycol unit, wherein the (meth) acrylate (B) comprises Equation (1):

[0014]

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(Wherein R ₁ and R ₃ independently represent hydrogen or a methyl group, R ₂ represents hydrogen, an alkyl group, an aryl group or a benzyl group, and n represents an integer of 2 to 30) ), General formula (2):

[0016]

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(Wherein R ₄ , R ₅ and R ₆ independently represent hydrogen or a methyl group, and n represents an integer of 2 to 30) and a general formula (3):

[0018]

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Wherein R ₇ represents a residue of a polyol having (x + y) hydroxyl groups, R ₈ and R ₉ independently represent hydrogen or a methyl group, and n is an integer of 1 to 30 Where x is an integer of 2 or more, y is an integer of 1 or more,
x + y represents an integer of 3 to 30), and is at least one or more polymerizable monomers selected from (meth) acrylates (B) having oligoalkylene glycol units, and the resin composition A photosensitive resin composition comprising 0.1 to 30% by weight of a photo-radical polymerization initiator (C) based on 100% by weight of a product.

The unsaturated polyester (A) used in the present invention comprises: an acid component essentially comprising an unsaturated polybasic acid;
It means a polymer obtained by subjecting a component composed of a polyhydric alcohol and / or an epoxy compound (hereinafter referred to as a polyhydric alcohol component) to an essential alcohol component by polycondensation or ring-opening polymerization by a conventionally known method. Of course, a monovalent acid may be used instead of a part of the polybasic acid, or a monohydric alcohol may be used instead of the polyhydric alcohol.
As for the alcohol component, it is preferable to use an oligoalkylene glycol for part or all of the alcohol component, as described later.

The acid value and molecular weight of the unsaturated polyester are not particularly limited, but are generally 40 or less,
The number average molecular weight is preferably 500 to 20,000, more preferably 800 to 10,000, and most preferably 1,000.
０００4000.

The polybasic acid used for the acid component may be a compound having two or more substituents capable of forming an ester bond by reacting with a hydroxyl group or an epoxy group contained in the polyhydric alcohol component. Require polybasic acid,
A saturated polybasic acid may be used in combination with a part of the acid component. Specific examples of the unsaturated polybasic acids include, for example, α, β- such as maleic acid, fumaric acid, aconitic acid, and itaconic acid.
Unsaturated polybasic acids; β, γ-unsaturated polybasic acids such as dihydromuconic acid; anhydrides of these acids; halides of these acids; alkyl esters of these acids.
These exemplified compounds may be used alone or in combination of two or more.

The saturated polybasic acids include malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, hexylsuccinic acid,
Glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3,3-diethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid And aliphatic saturated polybasic acids such as sebacic acid; phthalic acid, isophthalic acid,
Aromatic saturated polybasic acids such as terephthalic acid, trimellitic acid and pyromellitic acid; hetonic acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, tran
alicyclic saturated polybasic acids such as s-1,4-cyclohexanedicarboxylic acid; anhydrides of these acids; halides of these acids; alkyl esters of these acids. These exemplified compounds may be used alone or in combination of two or more.

As the alcohol component, ethylene glycol, 1,3-propanediol, 2-methyl-
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, 2,3-butanediol,
1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1,4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4
-Dimethylolcyclohexane, 2,2-diethylpropane-1,3-diol, 3-methylpentane-1,4
-Diol, 2,2-diethylbutane-1,3-diol, 4,5-nonanediol, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like.
These exemplified compounds may be used alone or in combination of two or more.

In addition, from the viewpoint of compatibility with the (meth) acrylic acid ester (B) having an oligoalkylene glycol unit used in the present invention, the unsaturated polyester (A) used in the present invention is used in the production. It is preferable to use an oligoalkylene glycol for part or all of the starting alcohol component. That is, the unsaturated polyester (A) used in the present invention preferably employs an unsaturated polyester resin obtained by using an oligoalkylene glycol for part or all of the raw material alcohol component. . This unsaturated polyester resin is a resin having a structural unit derived from oligoalkylene glycol used as a raw material.

More specifically, the introduction ratio of ether oxygen introduced into the unsaturated polyester (A) by using the oligoalkylene glycol is less than 100% by weight based on the amount of the unsaturated polyester (A). 3% by weight or more
It is preferably in the range of 20% by weight, more preferably in the range of 5% to 15% by weight, and more preferably 5% by weight.
More preferably, it is in the range of 10 to 10% by weight. If the amount exceeds this range, the water resistance and heat resistance of the cured product may be sacrificed. If the amount is below this range, the type and amount of the (meth) acrylic ester (B) having an oligoalkylene glycol unit to be used may vary. May be at the expense of compatibility.

The above-mentioned ether oxygen introduction rate is determined by calculating the molar amount of oligoalkylene glycol and the number of ether oxygens among the raw materials for producing the unsaturated polyester (A). To determine. Next, the total weight of ether oxygen is divided by the weight of the resin after production, and the result is multiplied by 100 to obtain the ether oxygen introduction rate referred to herein. Specifically, for example, when an unsaturated polyester is produced by removing 70 g of condensed water from 4 mol (392 g) of maleic anhydride, 3 mol (450 g) of triethylene glycol, and 2 mol (240 g) of methoxydiethylene glycol, Since 1 mole of ethylene glycol contains 2 moles of ether oxygen and 1 mole of methoxydiethylene glycol contains 2 moles of ether oxygen, the total weight of ether oxygen contained in the oligoalkylene glycol is 16 (molecular weight of oxygen). × (2 × 3 + 2 ×
2) = 160 g. The weight of the resin after production is determined by subtracting the amount of condensed water from the total weight of the resin raw materials,
Resin weight after production in the above case = (392 + 45)
(0 + 240) -70 = 1012 g. Therefore, the introduction rate of ether oxygen = 160/1012 × 100 = 15.8.
%.

That is, in the present invention, the introduction ratio of ether oxygen is obtained by multiplying the ratio of the amount of ether oxygen derived from oligoalkylene glycol in the raw material / the total amount of unsaturated polyester used by 100, and the unit is (%). Can be indicated by

The unsaturated polyester (A) of the present invention is an unsaturated polyester obtained by using a part or all of the raw material alcohol component by using an oligoalkylene glycol. It is preferable that the unsaturated polyester is obtained by determining the amount of the oligoalkylene glycol so that the amount of ether oxygen becomes 3% by weight to 20% by weight and reacting the same. More preferably, the amount is from 5% by weight to 1%
0% by weight.

The unsaturated polyester (A) of the present invention includes (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group, (meth) acrylate having a carboxylic acid group, and (meth) acrylate having an amino group. And / or a low molecular weight unsaturated compound having a structure in which an alkylene oxide and an unsaturated polybasic acid anhydride and / or a saturated polybasic acid anhydride are successively ring-opened and added to a (meth) acrylate having a phosphoric acid group as a starting material. It is also possible to use polyester. Such compounds are described, for example, in JP-A-8-73577 and JP-A-56-150.
No. 044 or JP-A-57-59834, and the composition of the present invention using the above compound can reduce the ratio of the polymerizable monomer. It is preferable because odor and environmental pollution due to volatilization of the monomer can be further suppressed.

The unsaturated polyester (A) of the present invention may be two or more unsaturated polyesters having different compositions. In this case, it is preferable to appropriately set a combination that does not affect the curability of the photosensitive resin described later and the compatibility of the resin composition.

Examples of the oligoalkylene glycol which can be used for the unsaturated polyester (A) of the present invention include methoxydiethylene glycol, ethoxydiethylene glycol, propoxydiethylene glycol, butoxydiethylene glycol, phenoxydiethylene glycol, diethylene glycol monobenzyl ether, diethylene glycol monoacetate, diethylene glycol monoacetate. Benzoate, methoxydipropylene glycol, ethoxydipropylene glycol, propoxydipropylene glycol, butoxydipropylene glycol, phenoxydipropylene glycol, dipropylene glycol monobenzyl ether, dipropylene glycol monoacetate, diproleneglycol monobenzoate, methoxytriethylene Glycol, ethoxytriethylene glycol, propoxytriethylene glycol, butoxytriethylene glycol, phenoxytriethylene glycol, triethylene glycol monobenzyl ether, triethylene glycol monoacetate, triethylene glycol monobenzoate, methoxytripropylene glycol, ethoxytripropylene glycol , Propoxytripropylene glycol, butoxytripropylene glycol, phenoxytripropylene glycol, tripropylene glycol monobenzyl ether, tripropylene glycol monoacetate, tripropylene glycol monobenzoate, methoxytetraethylene glycol, ethoxytetraethylene glycol, propoxytetraethylene glycol Lumpur, butoxy tetraethylene glycol, phenoxy tetraethylene glycol, tetraethylene glycol monobenzyl ether, tetraethylene glycol monoacetate, tetraethylene glycol mono benzoate, methoxy tetraethylene glycol, ethoxy tetrapropylene glycol, propoxy tetrapropylene glycol,
Butoxytetrapropylene glycol, phenoxytetrapropylene glycol, tetrapropylene glycol monobenzyl ether, tetrapropylene glycol monoacetate, tetrapropylene glycol monobenzoate, methoxy polyethylene glycol, ethoxy polyethylene glycol, propoxy polyethylene glycol, butoxy polyethylene glycol, phenoxy polyethylene glycol, polyethylene Glycol monobenzyl ether, polyethylene glycol monoacetate, polyethylene glycol monobenzoate, methoxy polypropylene glycol, ethoxy polypropylene glycol, propoxy polypropylene glycol, butoxy polypropylene glycol, phenoxy polypropylene glycol Monoalcohols such as polypropylene glycol monobenzyl ether, polypropylene glycol monoacetate, and polypropylene glycol monobenzoate; diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetraethylene glycol, tetrapropylene glycol, polyethylene glycol, polypropylene glycol, bisphenol Diols such as ethylene oxide adduct of A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide oxide adduct of hydrogenated bisphenol A; ethylene oxide adduct of trimethylolpropane; Propylene oxa of trimethylolpropane Triols such as chloride adducts, ethylene oxide adducts of trimethylolethane, propylene oxide adducts of trimethylolethane, ethylene oxide adducts of glycerin, and propylene oxide adducts of glycerin; and other pentaerythritol ethylene oxide adducts, pentane Polyols such as erythritol propylene oxide adduct, dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, phenol resin ethylene oxide adduct, and phenol resin propylene oxide adduct. These exemplified compounds may be used alone or in combination of two or more.

Examples of the epoxy compound include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, 3,4-epoxy-1-butene, glycidyl acrylate, glycidyl methacrylate, and diglycidyl ether of bisphenol A. These exemplified compounds may be used alone or in combination of two or more. In addition, the oligoalkylene glycol can be introduced into the unsaturated polyester (A) by selecting reaction conditions when these epoxy compounds are used and continuously performing ring-opening polymerization of the epoxy compound.

In the photosensitive resin composition of the present invention, in order to further improve the compatibility of the resin composition described below,
The unsaturated polyester (A) of the present invention produced using the above-described oligoalkylene glycol and the (meth) acrylate (B) having an oligoalkylene glycol unit used in the photosensitive resin composition of the present invention. It is a preferred embodiment to set the kind of the oligoalkylene glycol-derived structural unit to be possessed by the unsaturated polyester or the amount of the structural unit to be introduced in consideration of the compatibility. Alternatively, on the contrary, it is a preferred embodiment to select the (meth) acrylate (B) having an oligoalkylene glycol unit to be used according to the structure in the unsaturated polyester (A) to be used.

The criterion for judging the above-mentioned compatibility is the total light transmittance of the resin composition measured in JIS-K-7105 (1994) described later. In measuring the total light transmittance, as described later, the total light transmittance of a specific composition of the unsaturated polyester (A) and the (meth) acrylate (B) having an oligoalkylene glycol unit is measured. This serves as a standard for judging the compatibility of the resin composition. Therefore, in the present invention, when defining the compatibility of the resin composition, it is one of the preferred embodiments to measure the total light transmittance of the resin composition using this measuring method.

The so-called air-curable unsaturated polyester can be produced by replacing the whole or a part of the above-mentioned unsaturated polyester raw material with a compound having an unsaturated bond such as an allyl group shown below. it can.
Specifically, at least the whole or a part of the above-mentioned ordinary acid component is replaced with an unsaturated polybasic acid having an unsaturated bond such as an allyl group shown below, or the entire amount of the above-mentioned ordinary polyhydric alcohol component. Alternatively, a part thereof may be replaced with a polyhydric alcohol having an unsaturated bond such as an allyl group shown below.

The polybasic acid component having an unsaturated bond includes tetrahydrophthalic anhydride, α-terpinene-
Maleic anhydride adduct, maleic anhydride cyclopentadiene adduct, dicyclopentadiene maleic half ester adduct, rosin, ester gum, drying oil fatty acid,
Semi-dry oil fatty acids and the like. These exemplified compounds may be used alone or in combination of two or more.

Examples of the polyhydric alcohol having an unsaturated bond include trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, pentaerythritol monoallyl ether, Examples include pentaerythritol diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, and glycerin diallyl ether. Examples of the epoxy compound having an unsaturated bond include allyl glycidyl ether. These exemplified compounds may be used alone or in combination of two or more.

Used in the photosensitive resin composition of the present invention,
(Meth) acrylic acid ester (B) having an oligoalkylene glycol unit is preferably a compound having a (meth) acryloyl group as essential and having an oligoethylene glycol and / or oligopropylene glycol residue in the molecule. . That is, the following general formula (1):

[0040]

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(Wherein R ₁ and R ₃ each independently represent hydrogen or a methyl group, R ₂ represents hydrogen, an alkyl group, an aryl group, or a benzyl group, and n represents an integer of 2 to 30) ), General formula (2):

[0042]

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(Wherein R ₄ , R ₅ , and R ₆ independently represent hydrogen or a methyl group, and n represents an integer of 2 to 30) and a general formula (3):

[0044]

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Wherein R ₇ represents a residue of a polyol having (x + y) hydroxyl groups, R ₈ and R ₉ independently represent hydrogen or a methyl group, and n is an integer of 1 to 30 Where x is an integer of 2 or more, y is an integer of 1 or more,
x + y represents an integer of 3 to 30), and is at least one polymerizable monomer or a polymerizable monomer composition.

In a more preferred embodiment of the present invention, in the above formula (3), the number x + y is 3 to 25.
Is an integer. More preferably, the number is from 3 to 20, even more preferably from 3 to 15, and most preferably from 3 to 10.

Specific examples of the (meth) acrylate (B) having an oligoalkylene glycol unit include diethylene glycol mono (meth) as the polymerizable monomer (B) represented by the general formula (1). Acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, propoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, phenoxysidiethylene glycol (meth) acrylate, (meth) acrylate of diethylene glycol monobenzyl ether, diethylene glycol mono Acetate (meth) acrylate, diethylene glycol monobenzoate (meth) acrylate, dipropylene glycol mono Meth) acrylate, methoxy dipropylene glycol (meth) acrylate, ethoxy dipropylene glycol (meth) acrylate, propoxy dipropylene glycol (meth) acrylate, butoxy dipropylene glycol (meth) acrylate,
Phenoxysidipropylene glycol (meth) acrylate, (meth) acrylate of dipropylene glycol monobenzyl ether, (meth) acrylate of dipropylene glycol monoacetate, (meth) acrylate of dipropylene glycol monobenzoate, triethylene glycol mono (meth) acrylate Acrylate, methoxytriethylene glycol (meth) acrylate, ethoxytriethylene glycol (meth) acrylate, propoxytriethylene glycol (meth) acrylate,
Butoxytriethylene glycol (meth) acrylate, phenoxycitriethylene glycol (meth) acrylate, (meth) acrylate of triethylene glycol monobenzyl ether, (meth) acrylate of triethylene glycol monoacetate, (meth) acrylate of triethylene glycol monobenzoate Acrylate, tripropylene glycol mono (meth) acrylate, methoxytripropylene glycol (meth) acrylate, ethoxytripropylene glycol (meth) acrylate, propoxytripropylene glycol (meth)
Acrylate, butoxytripropylene glycol (meth) acrylate, phenoxy citripropylene glycol (meth) acrylate, (meth) acrylate of tripropylene glycol monobenzyl ether, (meth) acrylate of tripropylene glycol monoacetate, (tripropylene glycol monobenzoate) (Meth) acrylate, tetraethylene glycol mono (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, butoxytetraethylene glycol (meth) acrylate, phenoxy Cytetraethylene glycol (meth) acrylate, tetraethylene glyco (Meth) acrylate of monomonobenzyl ether, (meth) acrylate of tetraethylene glycol monoacetate, (meth) acrylate of tetraethylene glycol monobenzoate, tetrapropylene glycol mono (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxy Tetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, butoxytetrapropylene glycol (meth) acrylate, phenoxysitetrapropylene glycol (meth) acrylate, (meth) acrylate of tetrapropylene glycol monobenzyl ether, tetrapropylene Glycol monoacetate (meth) acrylate, tetrapropylene glycol Monomethacrylate (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, propoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, phenoxy (Meth) of polyethylene glycol (meth) acrylate and polyethylene glycol monobenzyl ether
Acrylate, polyethylene glycol monoacetate (meth) acrylate, polyethylene glycol monobenzoate (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, propoxy polypropylene glycol ( Meth) acrylates,
Such as butoxy polypropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, (meth) acrylate of polypropylene glycol monobenzyl ether, (meth) acrylate of polypropylene glycol monoacetate, and (meth) acrylate of polypropylene glycol monobenzoate. Functional (meth) acrylates are mentioned, and are at least one or more polymerizable monomers selected from the above examples.

The polymerizable monomer (B) represented by the general formula (2) includes diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol. Di (meth) acrylate,
Di (meth) acrylate of ethylene oxide adduct of trimethylolpropane, di (meth) acrylate of ethylene oxide adduct of trimethylolethane, di (meth) acrylate of ethylene oxide adduct of glycerin, di (meth) acrylate of bisphenol A ethylene oxide adduct A) acrylates, di (meth) acrylates of polyester polyols synthesized from ether glycols, dipropylene glycol di (meth) acrylates,
Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) acrylate of propylene oxide adduct of trimethylolpropane, and propylene oxide adduct of trimethylolethane Bifunctional (meth) acrylates, such as di (meth) acrylate, di (meth) acrylate of propylene oxide adduct of glycerin, and di (meth) acrylate of propylene oxide adduct of bisphenol A, are selected from the above examples. It is at least one or more polymerizable monomers.

Examples of the polymerizable monomer (B) represented by the general formula (3) include tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane and tri (meth) acrylate of ethylene oxide adduct of trimethylolethane. Tri (meth) acrylate of ethylene oxide adduct of glycerin, tri (meth) acrylate of ethylene oxide adduct of pentaerythritol, tri (meth) acrylate of propylene oxide adduct of trimethylolpropane, and propylene oxide adduct of trimethylolethane Trifunctional (meth) such as tri (meth) acrylate, tri (meth) acrylate of propylene oxide adduct of glycerin, and tri (meth) acrylate of propylene oxide adduct of pentaerythritol
Acrylates: tetra (meth) acrylate of ethylene oxide adduct of pentaerythritol, tetra (meth) acrylate of propylene oxide adduct of pentaerythritol, penta (meth) acrylate of ethylene oxide adduct of dipentaerythritol, propylene oxide of dipentaerythritol Adduct penta (meth) acrylate, dipentaerythritol ethylene oxide adduct hexa (meth) acrylate, dipentaerythritol propylene oxide adduct hexa (meth) acrylate, phenol resin ethylene oxide adduct poly (meth) acrylate And polyfunctional acrylates such as poly (meth) acrylate of a propylene oxide adduct of a phenol resin,
It is at least one or more polymerizable monomers selected from the above examples.

The number of (meth) acryloyl groups contained in one molecule of the above polymerizable monomer is not particularly limited.
When particularly excellent photocurability is required, it is preferable to use two or more, so-called polyfunctional (meth) acrylates. The monomer molecular weight per acryloyl group molecule, that is, the double bond equivalent of the acryloyl group is preferably 100 to 100 from the viewpoint of photocurability and physical properties of the cured product.
0, more preferably 140 to 500.

A component of the photosensitive resin composition of the present invention,
The mixing ratio of the polymerizable monomer containing the unsaturated polyester (A) and the (meth) acrylic acid ester (B) having an oligoalkylene glycol unit (B), or the mixing ratio of the polymerizable monomer composition is not particularly limited. From the viewpoints of viscosity and material properties, (A) :( B) = 90: 10-1 by weight ratio.
0:90 is preferred, 70:30 to 30:70 is more preferred, 65:35 to 35:65 is still more preferred,
0:40 to 40:60 is most preferred.

Specifically, the content of the unsaturated polyester (A) is 90 to 10% by weight based on 100% by weight of the resin component used in the photosensitive resin composition of the present invention. It is preferable that the content of the polymerizable monomer containing the (meth) acrylate (B) having the formula (I) or the polymerizable monomer composition is 10 to 90% by weight. More preferably, the content of the unsaturated polyester (A) is 70 to 30% by weight, and a polymerizable monomer containing a (meth) acrylate (B) having an oligoalkylene glycol unit, or a polymerizable monomer. The content of the body composition is 30 to 70% by weight.

More preferably, the content of the unsaturated polyester (A) is 65 to 35% by weight, and a polymerizable monomer containing a (meth) acrylate (B) having an oligoalkylene glycol unit, or The content of the polymerizable monomer composition is 35 to 65% by weight.

More specifically, in the present invention, the resin component (the sum of the polymerizable polymer component and the polymerizable monomer component used as needed) of the photosensitive resin composition of the present invention is referred to as the resin component. ) As 100% by weight of the polymerizable monomer containing the unsaturated polyester (A) and the (meth) acrylate (B) having an oligoalkylene glycol unit, or the polymerizable monomer composition. The content of the total amount is
50 to 100% by weight is preferred. More preferably, 60
-100% by weight, more preferably 70-100% by weight, more preferably 80-100% by weight, even more preferably 90-100% by weight, most preferably 95% by weight.
-100% by weight. The polymerizable resin other than the unsaturated polyester (A) used in the present invention described below is
As long as it is within the above range, and it does not interfere with the effects of the present invention, it can be used in combination. Specifically, the content of the other polymerizable resin component is in the range of 0 to 50% by weight, more preferably in the range of 0 to 40% by weight, with the photosensitive resin composition of the present invention being 100% by weight. It is preferably in the range of 0 to 30% by weight, more preferably in the range of 0 to 20% by weight, still more preferably in the range of 0 to 10% by weight, and most preferably in the range of 0 to 5% by weight.
In addition, other polymerizable resin components of the photosensitive resin of the present invention,
It is preferable to use within the above range for better compatibility or better curability.

The photopolymerization initiator (C) is not particularly limited as long as it has a capability of generating a radical species by the action of light and initiating the copolymerization of the unsaturated polyester with the polymerizable monomer. Specific examples of the photopolymerization initiator that can be used include 4-phenoxydichloroacetophenone,
4-t-butyldichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-phenyl-1-phenylpropan-1-one, 1- (4-dodecylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-
(4-isopropylphenyl) -2-hydroxy-2-
Methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl)
Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]
Acetophenone compounds such as -2-morpholinopropane-1; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate , 4-Phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl 4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone , 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone-based compounds; Rochiokisanton, 2
-Methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 2,
Thioxanthone compounds such as 4-dichlorothioxanthone; α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ′ Ketone compounds such as '-diethylisophthalophenone; imidazole compounds such as 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-imidazole;
Acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and other carbazole compounds.

These photopolymerization initiators (C) may be used alone or in combination of two or more. Further, an unsaturated polyester (A) and a (meth) acrylate (B) having an oligoalkylene glycol unit
The amount of the photopolymerization initiator (C) to be added is usually 0.1 to 30% by weight based on 100% by weight of the total amount of the polymerizable monomer containing. From the viewpoint of the balance between excellent photocurability and coloring of the cured product, the addition amount of the photopolymerization initiator (C) is 0.5 to 1
0 wt% is preferred, and 1-5 wt% is most preferred.

In order to further improve the curability of the resin composition of the present invention, if necessary, triethylamine, diethylamine, diethanolamine, ethanolamine,
Sensitizers such as dimethylaminobenzoic acid, methyl dimethylaminobenzoate, thioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and acetylacetone; and thermal radicals represented by benzoyl peroxide, azobisisobutyronitrile, and the like A generator can be further added.

In addition, a polymerizable monomer other than the (meth) acrylate (B) having an oligoalkylene glycol unit may be used in combination within a range not sacrificing the excellent effects of the resin composition of the present invention. Is also possible.

Examples of the polymerizable monomer that can be used include styrene, vinyltoluene, p-tert-butylstyrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene, p-chloromethylstyrene, divinylbenzene Styrene monomers such as diallyl phthalate, diallyl isophthalate, triallyl cyanurate and triallyl isocyanurate;
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, ethylene glycol diacrylate , Acrylic acid derivatives such as diacrylic acid adduct of bisphenol A diglycidyl ether, trimethylolpropane triacrylate, trimethylolethane triacrylate, glycerin triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; Methacrylic acid monomers and the like can be mentioned. Further, in order to exhibit air curability, a compound having a specific unsaturated bond shown below may be used as a polymerizable monomer component. That is, allyl ether of methylol melamine, adipic acid ester of glycerin diallyl ether, allyl acetal, allyl ether of methylol glyoxal urein, etc. can be used alone or in combination of two or more as a polymerizable monomer. is there.

100% by weight of the photosensitive resin composition of the present invention
The amount of the polymerizable monomer other than the (meth) acrylate (B) having an oligoalkylene glycol unit is preferably 0 to 30% by weight. More preferably, it is 0 to 20% by weight. More preferably, 0
-10% by weight. Most preferably, it is 0 to 5% by weight. Thus, as long as the effect of the photosensitive resin composition of the present invention is not impaired, it is preferable to use the other polymerizable monomer in the above-mentioned range, for example. When the use amount of the other polymerizable monomer increases, the effect derived from the (meth) acrylic acid ester (B) having an oligoalkylene glycol unit, which is the polymerizable monomer used in the present invention, becomes difficult to appear. There is. The effect is the compatibility of the photosensitive resin composition of the present invention and the curability. Further, there is a possibility that the low odor derived from the (meth) acrylate (B) having an oligoalkylene glycol unit may be inhibited. Therefore, when using other polymerizable monomers,
It is preferable to keep the amount within the above range.

Further, the photosensitive resin composition of the present invention includes:
As long as the photocurability is not significantly reduced, various thermal polymerization inhibitors, leveling agents, thickeners, thickeners, thixotropic agents, antihalation agents, matting agents, ultraviolet absorbers,
It may contain a coloring pigment, a diluent, a filler, a reinforcing agent, a thermoplastic resin, and the like. Further, it may be mixed with another photosensitive resin, for example, an epoxy (meth) acrylate resin, a urethane (meth) acrylate resin, a polyester (meth) acrylate resin, an epoxy resin, an oxetane compound, or the like at an arbitrary ratio.

The compatibility of the resin composition of the present invention is determined according to JIS.
It can be defined by measuring the total light transmittance of the resin composition measured according to -K-7105 (1994). That is, 30% by weight of the unsaturated polyester (A) and (meth) acrylic acid ester (B) having an oligoalkylene glycol unit used in the present invention were used in an amount of 30%.
% By weight of the resin composition obtained by mixing
mm, and the total light transmittance is 50% or more based on the total light transmittance measured using the cell (space is air) before the resin is poured. Is defined as If the total light transmittance is less than 50%, the cured product after photocuring may be non-uniform. More preferably, the total light transmittance is 60% or more. More preferably, it is at least 70%. Most preferably, 8
0% or more.

In order to realize excellent low odor of the resin composition of the present invention, JIS-K-5407 (1990)
) Is preferably less than 20%. More preferably, the photosensitive resin composition of the present invention is used if the weight loss of the photosensitive resin composition after being left in a dryer adjusted to 105 ° C. for 3 hours is less than 20%. Excellent low odor in various painting and molding operations. More preferably, the above-mentioned heat loss is less than 18%. More preferably, it is less than 15%. More preferably less than 13%, most preferably less than 10%.

The photosensitive resin composition of the present invention can be photocured by a conventionally known method. For example, in the case of curing by ultraviolet rays, the resin composition is first coated or impregnated on a substrate, and is contained in the resin. After evaporating and drying the solvent and volatile components, it is general to cure by exposing for a certain period of time using a medium pressure mercury lamp or the like as a light source. The atmosphere during photo-curing can be sufficiently cured in dry air to obtain a tack-free cured coating film in a short time, but when cured in an inert gas such as nitrogen or argon, water resistance and chemical resistance etc. In some cases, the performance of the cured coating film may be further improved, and may be appropriately selected depending on the application. The method of coating / impregnating the substrate, the type of light source, the exposure method, and the like are not particularly limited. In order to further enhance the physical properties of the coating film after photocuring, a so-called post-baking step of reheating to an appropriate temperature can be performed.

The photosensitive resin composition of the present invention thus obtained can be used as a coating material for various base materials such as wood, paper, particle board, metal, plastic, glass, concrete, asphalt, and ceramic, a resin for paint, FRP ( It can be used as a substrate for fiber-reinforced plastics, putty, sealing agent, adhesive, printing ink binder, resin for stereolithography, resin for solder resist, resin for photoresist, resin for printing plate, and the like. A more preferred embodiment is a coating material comprising the photosensitive resin composition of the present invention. Further, a substrate for FRP, which contains the photosensitive resin composition of the present invention, is also a preferred embodiment.

The coating material in the present invention is, for example, a resin or a resin composition applied to the surface of glass, wood, plastic, metal, concrete or asphalt to protect the surface or improve the design. .
In addition, the FRP substrate in the present invention refers to a resin or a resin composition for impregnating the glass fiber with the resin using, for example, a glass mat together with the glass fiber.

The content of the photosensitive resin composition of the present invention in the coating material or the FRP substrate is not particularly limited as long as the effect of the photosensitive resin composition of the present invention is not hindered. The amount can be appropriately set under various desired conditions. Specifically, a filler, a filler, glass fiber, a pigment, or a paint may be blended as the coating material or the FRP base material. The content of the photosensitive resin composition of the present invention is, for example, in the range of 5 to 95% by weight based on 100% by weight of the coating material or the FRP substrate of the present invention. More preferably, it is in the range of 10 to 90% by weight. More preferably, the content is 20 to 80% by weight. In addition, examples of a base material for FRP and the like in which a covering material for concrete and a glass fiber were applied together were also shown in the examples described later.

Also, for example, by appropriately selecting a photopolymerization initiator, it is possible to design so that photocuring can be performed even with sunlight or ordinary light (such as room light). Specific applications include civil engineering and architectural coatings and waterproof coatings. In a preferred embodiment of the present invention, the photosensitive resin composition of the present invention can be designed into a composition having a low odor, and when used at the time of construction outside or indoors (for example, underground parking lot, etc.), Will be useful. Examples of working on concrete base materials are shown in Examples, and it can be said that the method of working on various base materials using the photosensitive resin of the present invention is one of preferred embodiments. Various substrates are not particularly limited,
For example, concrete, metal, wood, plastic, etc. For plastics and the like, primer treatment and surface sanding may be performed as necessary.

Further, by providing a coating layer using the photosensitive resin composition of the present invention on a tape or film-like base material such as PET, polyolefin or nylon (if necessary, filler, glass fiber or magnesium oxide). And the like, and can also be used as a photosensitive repair tape and a photosensitive repair material, and can be cited as a preferred embodiment of the photosensitive resin composition of the present invention. In this case, it is preferable to use a photopolymerization initiator that cures with sunlight or ordinary light. Further, in the case of this tape base material, in the use embodiment, a product form in which the outside is covered with a light shielding material so that the photosensitive resin layer of the present invention is not exposed to light is preferable.

Such a tape base material can be easily photo-cured by ultraviolet rays or the like by removing the light-shielding layer by the light-shielding material at the time of use. If desired, a primer can be applied on the adhered object, if necessary, in order to ensure adhesion to the substrate. Providing a pressure-sensitive layer on a substrate such as PET is also one of the preferred embodiments. The photosensitive resin composition of the present invention,
As shown in the examples, the adhesiveness to the concrete base material was also good, and it was found that such a tape was also suitable for use as a photosensitive repair tape and repair base material.

[0071]

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the examples, “parts” means “parts by weight” unless otherwise specified.

<Resin Synthesis Example 1> In a 5-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube, 2320 parts of fumaric acid, 3150 parts of triethylene glycol and a polymerization inhibitor were added. Was added thereto, followed by dehydration condensation at 210 ° C. for 14 hours under a nitrogen stream according to a conventional method to obtain 4,800 parts of an unsaturated polyester having an acid value of 13 and a number average molecular weight of 3,800 (in terms of polystyrene) by GPC. Let the obtained resin be resin (I).

<Resin Synthesis Example 2> 1110 parts of phthalic anhydride, 1715 parts of maleic anhydride, and propylene glycol were placed in a 5-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube. 950 parts, 780 parts of neopentyl glycol, ethylene glycol 465
And 0.5 parts of hydroquinone as a polymerization inhibitor were added, followed by dehydration condensation at 210 ° C. for 8 hours under a nitrogen stream according to a conventional method to obtain 4,600 parts of an unsaturated polyester having an acid value of 16 and a number average molecular weight of 2,100. The obtained resin is converted into resin (II)
And

<Resin Synthesis Example 3> 1110 parts of phthalic anhydride, 1715 parts of maleic anhydride, and propylene glycol were placed in a 5-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube. 570 parts, 1340 parts of dipropylene glycol, 1040 parts of neopentyl glycol and 0.5 of hydroquinone as a polymerization inhibitor
8 parts were added and dehydration-condensed at 210 ° C. for 10 hours under a nitrogen stream according to a conventional method to obtain 5300 parts of an unsaturated polyester having an acid value of 13 and a number average molecular weight of 2,500. Let the obtained resin be resin (III).

<Resin Synthesis Example 4> A 5-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube was charged with 996 parts of isophthalic acid, 1372 parts of maleic anhydride, and dipropylene glycol. 1072 parts, 620 parts of ethylene glycol, 960 parts of methoxydiethylene glycol and 0.5 of hydroquinone as a polymerization inhibitor
The resulting mixture was dehydrated and condensed at 210 ° C. for 8 hours under a nitrogen stream according to a conventional method to obtain 4,600 parts of an unsaturated polyester having an acid value of 13 and a number average molecular weight of 1,300. Let the obtained resin be resin (IV). <Resin Synthesis Example 5> 86 parts of methacrylic acid and 3.6 parts of triethylbenzylammonium chloride were added to a four-necked flask equipped with a stirring rod, a thermometer, a gas inlet tube, a dropping funnel, and a cooling tube, and the mixture was placed under an air stream. Heated to 100 ° C.
Next, propylene oxide (58 parts) was added dropwise from the dropping funnel at the same temperature over 1 hour, and 148 parts of phthalic anhydride was added thereto while paying attention to heat generation, followed by stirring for 1 hour. Further, by the same operation, 58 parts of propylene oxide, 100 parts of succinic anhydride, 58 parts of propylene oxide, and 98 parts of maleic anhydride are added in this order.
The mixture was added dropwise at the same temperature over 1 hour, and reacted for 3 hours. After the completion of the reaction, the internal temperature of the flask was lowered to 80 ° C., and the internal pressure was reduced to 50 hp while bubbling a small amount of air with stirring.
a, and devolatilized for 1 hour in that state. After the devolatilization, 7 parts of morpholine was added at the same temperature and reacted for an additional 1 hour. The acid value was 1, the number average molecular weight was 650, and the number of maleic acid to fumaric acid was determined by NMR. There was obtained 670 parts of an unsaturated polyester having a methacryloyl group at the molecular terminal and having a transfer rate of 94%. Let the obtained resin be resin (V). <Examples 1 to 8 and Comparative Examples 1 to 11> Resin Production Example 1
A resin composition is prepared by mixing a polymerizable monomer and a photopolymerization initiator with the resins (I) to (V) obtained by the methods (1) to (5),
The resin appearance, loss on heating, photocurability, and appearance of the cured product of each resin composition were measured. Tables 1 to 5 show the results of the examples and comparative examples. In addition, the measuring method of various characteristics of the resin composition in the following Examples and Comparative Examples is as follows.

[Resin Appearance] After mixing each component by heating using a mortar at the ratios shown in the table, 20 ml of the obtained resin composition was added.
About 15 ml was placed in a transparent sample bottle and left in a dark place for one day. One day later, the appearance of the resin was visually judged. If the resin was homogeneously dissolved, it was evaluated as 、. If some stiffening occurred, it was evaluated as △. Also, significant slag or polymerizable monomer and phase separation between the resin solids Those in which occurred were evaluated as x.

[Heating Loss] JIS K-5407 (19
90) Measured according to the method described.

[ Photocuring] A composition was applied on a glass substrate (150 mm × 100 mm) to a wet thickness of 200 μm using a film applicator, and then irradiated with ultraviolet light equipped with one 80 W / cm high-pressure mercury lamp. Exposure was performed using the apparatus. 10cm distance from light source, conveyor speed 15m / min, effective exposure length 60cm
(With respect to the traveling direction of the conveyor), the number of passes until the tackiness disappeared from the coating film surface by finger touch was measured. Incidentally, when exposure is performed under the above conditions using this ultraviolet irradiation apparatus, the amount of ultraviolet irradiation energy per pass is 150 mJ / cm ² (converted to 365 nm). In each of the measured values in the table, it means that a composition having a smaller number of passes is more excellent in photocurability.

[Cured Product Appearance] The composition was applied on a glass substrate (size: 150 mm × 100 mm) so as to have a wet thickness of 200 μm using a film applicator, and then irradiated with ultraviolet light equipped with one 80 W / cm high-pressure mercury lamp. Exposure was performed using the apparatus. The distance from the light source is 10cm,
Conveyor speed 15m / min, effective exposure length 60c
Exposure for 20 passes was performed as m (relative to the traveling direction of the conveyor), and the cured coating film obtained was visually evaluated.も の indicates that a uniform cured coating film was obtained, and X indicates that the cured coating film had clouding.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

Table 1 shows that the resin composition of the present invention has a uniform and transparent resin appearance and is rapidly photocured to give a transparent photocured coating film.

From Table 2, it can be seen that the resin composition of the present invention has a small loss on heating and is excellent in low odor. Surprisingly, from the results of Example 3 and Comparative Example 7, the high-boiling point 2EH-A (boiling point 215 ° C.) has a larger heating loss than DEG-DA (boiling point 162 ° C.) having a lower boiling point. The result was obtained. This result is an effect firstly exhibited by the combination of the unsaturated polyester and the polymerizable monomer, and is difficult to predict from common general knowledge in the art.

Further, from Tables 3 and 4, it can be seen that when ether glycol is used as the unsaturated polyester for the resin composition of the present invention as a raw material, there is a remarkable heat loss reduction effect.

From Table 5, it can be seen that the amount of the polymerizable diluent can be reduced by using the polyester oligomer having a specific structure, and accordingly, the weight loss on heating can also be reduced. The decrease in photocurability predicted by the use of the low molecular oligomer was not observed in the resin composition of the present invention.

<Comparative Examples 14 to 17> The resins (I) to (IV) obtained in the above resin production examples 1 to 4 were polymerized with a polymerizable monomer, a thermal polymerization initiator (organic peroxide) and A resin composition was prepared by mixing a curing accelerator (metal organic acid salt), and the pot life, resin appearance, cured product appearance, and surface dryness of each resin composition were measured. Table 6 shows the results of these comparative examples. In addition, the measuring method of the various characteristics of the resin composition in the following comparative examples is as follows. [Pot life] JIS K-69 with the composition shown in the table
01. [Resin Appearance] Among the components shown in the table, each component other than the thermal polymerization initiator was heated and mixed using a mortar, and then about 15 ml of the obtained resin composition was placed in a 20 ml transparent sample bottle and placed in a dark place. Left for one day. One day later, the appearance of the resin was visually judged. If the resin was homogeneously dissolved, it was evaluated as 、. If some stiffening occurred, it was evaluated as △. Also, significant slag or polymerizable monomer and phase separation between the resin solids Those in which occurred were evaluated as x. [Cured product appearance] Wet thickness 2 on a glass substrate (size: 150 mm x 100 mm) using a film applicator
Each composition containing a thermal polymerization initiator was applied so as to have a thickness of 00 μm, and was allowed to stand overnight. The obtained cured coating film was visually evaluated, and the case where a uniform cured coating film was obtained was evaluated as ○, and the case where clouding occurred in the cured coating film was evaluated as ×. [Surface Drying Property] The film prepared at the time of measuring the appearance of the cured product was evaluated for its surface drying property by finger touch evaluation.

[0090]

[Table 6]

From Table 6, it can be seen that, even when the resin composition of the present invention is cured at room temperature with an organic peroxide instead of photocuring, the cured product becomes non-uniform in appearance and does not exhibit surface drying properties. It has been clarified that the excellent effects of the present invention are exhibited.

<Examples 12 to 15> Further, the resins (I) to (IV) 70 obtained by the above resin production examples 1 to 4
The resin composition was prepared by mixing 30 parts of the polymerizable monomer with the resin composition, and the total light transmittance of each resin composition at a thickness of 3 mm was measured. Table 7 shows the results of Examples and Comparative Examples. The methods for measuring various characteristics of the resin composition in the following examples are as follows.

[0093]

[Table 7]

Table 6 shows that the resin composition of the present invention has good compatibility with (meth) acrylic acid ester having an oligoalkylene glycol unit and high total light transmittance.

An example of the application will be described in more detail below.

Using the resin compositions of Examples 1 to 11, Darocur 1173 was used as a photoradical polymerization initiator.
Was applied on a concrete base material (150 × 100 mm plate) in which the same amount as above was blended. Further, a glass fiber (No. 450, glass fiber mat manufactured by Nitto Bo Co., Ltd.) was applied thereon. Again, apply and impregnate the photosensitive resin composition, under the same curing conditions as above,
UV irradiation was performed. After curing, the peelability of the coating film and the hardness of the coating film were verified, and all were good. For example, it is also possible to select a photo-radical polymerization initiator so as to be cured by irradiation of outdoor sunlight for half a day or the like, and in construction, partially apply light to cure a desired portion. It is possible.

[0097]

According to the present invention, a homogeneous and transparent cured product having excellent photocurability, low odor, and no gelation during storage or phase separation between a resin solid content and a diluent component can be obtained, and It is possible to provide a photosensitive resin composition excellent in economical efficiency, and a coating material for various base materials such as wood, paper, particle board, metal, plastic, glass, concrete, asphalt, and ceramic, a resin for paint, It can be used as a substrate for FRP (fiber reinforced plastic), putty, sealing agent, adhesive, printing ink binder, resin for stereolithography, resin for solder resist, resin for photoresist, resin for printing plate, and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 4/02 C09D 4/02 5/00 5/00 Z 167/06 167/06 171/00 171/00 // C08L 67:06 C08L 67:06 F term (reference) 2H025 AA11 AA13 AB14 AB15 AB17 AB20 AD01 BC13 BC64 BC83 CA00 FA17 4F072 AA04 AA07 AB09 AB29 AD09 AD38 AD40 AD55 AG03 AH21 AJ04 AK05 AL01 4J027 AB02 AB06 AB07 AB19 AB23 AB24 AB25 AB26 AC02 AC03 AC04 AC06 AC07 BA03 BA04 BA07 BA19 BA20 BA21 CB10 CC03 CC05 4J038 DD191 DD192 DD201 DD202 FA061 FA062 FA151 FA152 FA261 FA262 GA03 GA07 JA32 JB27 JB32 JC18 JC26 KA03 KA12 NA02 PC04 PCB PC06 PC08

Claims (7)

[Claims] 1. A resin composition comprising 90 to 10% by weight of an unsaturated polyester (A) and 10 to 90% by weight of a (meth) acrylate (B) having an oligoalkylene glycol unit. A photosensitive resin composition comprising 0.1 to 30% by weight of a photo-radical polymerization initiator (C). 2. The method according to claim 1, wherein the (meth) acrylic acid ester (B) having an oligoalkyleneylene glycol unit is as follows:
General formula (1): (Wherein, R ₁ and R ₃ independently represent hydrogen or a methyl group, R ₂ represents hydrogen, an alkyl group, an aryl group, or a benzyl group, and n represents an integer of 2 to 30),
General formula (2): (Wherein R ₄ , R ₅ , and R ₆ independently represent hydrogen or a methyl group, and n represents an integer of 2 to 30) and a general formula (3): (Wherein, R ₇ represents a residue of a polyol having (x + y) hydroxyl groups, R ₈ and R ₉ independently represent hydrogen or a methyl group, n is an integer of 1 to 30, x
Is an integer of 2 or more, y is an integer of 1 or more, and x + y is 3 to
The photosensitive resin composition according to claim 1, wherein the integer represents 30). 3. The unsaturated polyester (A) 70% by weight
And a resin composition obtained by mixing 30% by weight of the above (meth) acrylate (B) having an oligoalkylene glycol unit with a total light transmittance of 50 measured according to JIS-K-7105 (1994). % Of the photosensitive resin composition according to claim 1. 4. The photosensitive resin composition according to claim 1, wherein a loss on heating measured according to JIS-K-5407 (1990) is less than 20%. 5. The unsaturated polyester (A) is produced by using an oligoalkylene glycol for a part or all of a raw alcohol component used in the production thereof. Any one of
Item 6. The photosensitive resin composition according to item 1. 6. A coating material comprising the photosensitive resin composition according to claim 1. 7. A substrate for FRP, comprising the photosensitive resin composition according to any one of claims 1 to 5.