JP2001151832A - Curable resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition having slight odor, excellent in air drying properties, heat resistance and water resistance, having sufficient toughness and low viscosity and therefore having good balance as a material for coating a concrete, a mortar, a steel sheet, a glass, a timber, etc., especially as a topcoating material for an FRP waterproof lining and to provide a method for producing the curable resin composition. SOLUTION: This curable resin composition comprises (A) 25-50 wt.% of a polyester (meth)acrylate containing a structural unit derived from tetrahydrophthalic acids in the structure, (B) 15-55 wt.% of an epoxy (meth) acrylate and (c) 15-45 wt.% of a monomer containing 50-100 wt.% of a monofunctional (meth)acrylate monomer and a bifunctional (meth)acrylate monomer and having >=90 deg.C boiling point under 6.7×103 Pa.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a curable resin composition and a method for producing the same. More specifically, the present invention relates to a curable resin composition having low odor, excellent air drying properties and heat resistance, sufficient toughness, and low viscosity, and a method for producing the same.

[0002]

2. Description of the Related Art Unsaturated polyester resins, epoxy (meth) acrylates ("(meth) acrylate" means methacrylate and / or acrylate; the same applies hereinafter), urethane (meth) acrylate, and polyester (meth) acrylate. The resulting radically polymerizable resin is excellent in water resistance, heat resistance, mechanical strength and the like, and can be handled in a low-viscosity liquid state by containing a radically polymerizable monomer as a reactive diluent. Therefore, these radically polymerizable resins are widely used as coating materials for concrete, mortar, steel plate, glass, wood, etc. due to their good workability. Especially recently,
It is expected to be used as a roof waterproof material, a coated floor material, a coating of a steel plate structure, and a top coat material such as an FRP waterproof lining.

Styrene is conventionally used as a reactive diluent for these radically polymerizable resins because of its excellent physical properties. However, styrene has an odor and is harmful. Is required. For example, Japanese Patent Application Laid-Open No. Hei 10-87770 discloses oligoethylene glycol di (meth) as a low odor monomer.
Acrylate and oligopropylene glycol di (meth)
Acrylates have been proposed, but when this monomer is used, the toughness (elongation) of the cured product is lowered, and it is impossible to follow the movement of the base material as the base. Also, Japanese Patent Laid-Open No. 7-2
Japanese Patent No. 16040 proposes oligoethylene glycol monoalkyl ether (meth) acrylate as a low odor monomer.
The heat resistance, the strength of the coating film, the water resistance, and the like are reduced.

Further, since the curing reaction of the radically polymerizable resin is inhibited by oxygen in the air, when it is applied to a substrate for curing such as a waterproof lining and cured, the curing is delayed on the contact surface with air, Poor drying property, stickiness remains for a long period of time, which may hinder work. It is widely performed to add paraffin to improve the air drying property, but the addition of paraffin alone does not sufficiently improve the drying property, and the drying property becomes insufficient depending on the thickness of the film, Strict control of the thickness of the coating film is required. It is also known to introduce an allyl ether group or a cyclopentadiene skeleton into the resin skeleton as an air-drying component, but the stability of the resin is poor, and gelation may occur during the synthesis reaction.

[0005]

As described above, in the prior art, the curability is low in odor, excellent in air drying, heat resistance, water resistance, sufficient toughness, and low viscosity. No resin composition has been obtained. In particular, although these properties are required for the curable resin composition as a whole, the balance is slightly different in each application.

Accordingly, an object of the present invention is to provide a low-odor,
Excellent in air drying, heat resistance and water resistance, and has sufficient toughness and low viscosity, and is used as a topcoat material for concrete, mortar, steel plate, glass, wood, etc., especially for FRP waterproof lining. To provide a curable resin composition and a method for producing the same.

[0007]

In order to solve the above-mentioned problems, the present invention employs the following configuration. First of the present invention
The curable resin composition contains the following components (A) to (C) in the following proportions. (A) Polyester (meth) acrylate having a structural unit derived from tetrahydrophthalic acid in the skeleton 25 to 50% by weight (B) Epoxy (meth) acrylate 15 to 55% by weight (C) Monofunctional (meth) acrylate monomer and 15 to 45% by weight of a monomer having a boiling point of 90 ° C. or more at 6.7 × 10 ³ Pa containing 50 to 100% by weight of a bifunctional (meth) acrylate monomer, The second curable resin composition of the present invention is: The following (A ') ~
The cured product has a heat distortion temperature (HDT) of 50 ° C. or more, a cured product having a tensile elongation of 3% or more, and a composition having a viscosity of 1500 mPa · s or less.

(A ') Air-dryable unsaturated group-containing resin (B') Epoxy (meth) acrylate (C ') Monomer whose boiling point at 6.7 × 10 ³ Pa is 90 ° C. or more

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The first curable resin composition of the present invention will be described. To summarize the constitution of the first curable resin composition of the present invention, the mechanical properties (strength, toughness) and heat resistance of the cured product can be obtained by using the component (A) and the component (B) in a specific ratio. The balance of water resistance and the like is maintained.
By using a specific monomer at a specific ratio as the component (C), a resin composition having a low odor and a low viscosity can be obtained, and both high heat distortion temperature (HDT) and high toughness can be achieved. The component (A) and the component (D) used as required provide sufficient air drying properties.

The polyester (meth) acrylate having a skeleton containing a structural unit derived from tetrahydrophthalic acid as the component (A) is subjected to an esterification reaction of an acid component containing tetrahydrophthalic acid and glycol, and simultaneously or subsequently ( It can be produced by reacting (meth) acrylic acid. The acid component essentially contains tetrahydrophthalic acids. Examples of the tetrahydrophthalic acids include tetrahydrophthalic acid, anhydrides thereof, tetrahydrophthalic acid having a substituent, and anhydrides thereof.
The acid component may contain a dibasic acid other than tetrahydrophthalic acids as long as the air drying property of the present invention is not impaired, but is preferably 20% by weight or less of the acid component.

Examples of the glycol include ethylene glycol, diethylene glycol, and triethylene glycol.
, Polyethylene glycol, propylene glycol,
Dipropylene glycol, polypropylene glycol,
2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, bisphenol A
And propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexaneglycol, 1,3-cyclohexane Glycol, 1,4-cyclohexaneglycol, 1,4-cyclohexanedimethanol, para-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decaling glycol, 2,7-decaling alcohol and the like can be mentioned. Of these, oligoethylene glycol is preferred, and diethylene glycol is particularly preferred.

As (meth) acrylic acid, methacrylic acid and acrylic acid can be used, but methacrylic acid is preferred from the viewpoint of irritation and odor when remaining. The esterification reaction (including the case of simultaneously reacting (meth) acrylic acid) with the acid component and glycol can be performed at a temperature of 70 to 140 ° C. under normal pressure or reduced pressure, and the presence of an esterification catalyst Can be done below. Further, in order to smoothly proceed the esterification reaction, xylene azeotropic with condensed water,
Solvents such as toluene and cyclohexane may be used. In addition, in order to prevent gelation during the reaction, it is preferable to add a radical polymerization inhibitor under air or a mixed gas stream of oxygen and an inert gas.

When (meth) acrylic acid is reacted after the acid component and glycol are reacted,
The reaction can be performed at a temperature of 140 ° C. under normal pressure or reduced pressure. In addition, in order to prevent gelation during the reaction, it is preferable to add a radical polymerization inhibitor under air or a mixed gas stream of oxygen and an inert gas. As the esterification catalyst, known catalysts can be used. For example, p-toluenesulfonic acid, methanesulfonic acid, sulfophthalic acid,
Organic sulfonic acids such as -acrylamido-2-methyl-1-propanesulfonic acid. As the radical polymerization inhibitor, known radical polymerization inhibitors can be used, for example, phenols such as methoquinone, butylated hydroxytoluene, hydroquinone, t-butylhydroquinone, hydroquinones such as monomethylhydroquinone, and quinones such as benzoquinone. And sulfur compounds such as phenothiazine.

The content of the tetrahydrophthalic acid in the component (A) is preferably from 35 to 80% by weight, more preferably from 40 to 75% by weight. When the proportion is less than 35% by weight, the air drying property is insufficient,
If it exceeds 80% by weight, the resin composition has a high viscosity and gelation is likely to occur. When producing the component (A), it does not contain a structural unit derived from tetrahydrophthalic acid.
Glycol di (meth) acrylate (a bifunctional (meth) acrylate monomer used as a part of the component (C)) is by-produced. Therefore, it is assumed that the remainder of the entire product excluding the by-produced di (meth) acrylate is the generated polyester (meth) acrylate (component (A)). The content of the tetrahydrophthalic acid in the component (A) is defined as the weight of the used tetrahydrophthalic acid (in terms of anhydride) with respect to the weight of the produced polyester (meth) acrylate.

The most preferable method for synthesizing the component (A) is to use tetrahydrophthalic acid or its anhydride, diethylene glycol, and methacrylic acid in the range of 1-6: 1 to 6: 1.
(Molar ratio), and a mixture of polyester (meth) acrylate and glycol di (meth) acrylate can be obtained. The ratio of the component (A) in the first curable resin composition of the present invention is from 25 to 50.
%, Preferably 30 to 45% by weight. When the proportion is less than 25% by weight, the air drying property is insufficient, and when it exceeds 50% by weight, the resin composition becomes too high in viscosity and cannot be adjusted by adding a monomer.

The epoxy (meth) acrylate as the component (B) is obtained by reacting an epoxy resin with (meth) acrylic acid in the presence of an esterification catalyst. Examples of the epoxy resin include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A ethylene oxide addition type epoxy resin, bisphenol A propylene oxide addition type epoxy resin, bisphenol F type epoxy resin, and 1,6-naphthalene type epoxy resin. Bisphenol-type epoxy resins such as resins; and novolak-type epoxy resins such as epoxy resins obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin. Among them, an epoxy resin obtained by reacting bisphenol A with epichlorohydrin is preferable.

As (meth) acrylic acid, one or a mixture of methacrylic acid and acrylic acid can be used.
When the component (A) and the component (B) are successively produced by batch synthesis as described below, the same component used for the synthesis of the polyester (meth) acrylate of the component (A) may be used. preferable. Therefore, methacrylic acid is preferred.

As the esterification catalyst, known esterification catalysts can be used. For example, various esterification catalysts such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline and diazabicyclooctane can be used. Secondary amines; and diethylamine hydrochloride. The proportion of the component (B) in the first curable resin composition of the present invention is 15 to 55% by weight, and preferably 20 to 50% by weight. When the proportion is less than 15% by weight, mechanical properties, heat resistance and water resistance are inferior, and 55% by weight.
When it exceeds, the liquid viscosity of the resin composition becomes too high and the workability is inferior.

The monomer of component (C) contains 50 to 100% by weight of a monofunctional (meth) acrylate monomer and a difunctional (meth) acrylate monomer.
It has a boiling point of 90 ° C. or more at 10 ³ Pa. When the boiling point of the monomer at 6.7 × 10 ³ Pa is 90 ° C. or higher, a low-odor (almost odorless) resin composition can be obtained. In the production of the component (A), a part of the monomer of the component (C) can be by-produced. In this case, the monomer must be left when the solvent (such as a hydrocarbon solvent) is distilled off in the final step. In this sense, the boiling point at 6.7 × 10 ³ Pa must be 90 ° C. or more.

The monofunctional (meth) acrylate monomer is necessary for lowering the viscosity of the resin composition and achieving high toughness (elongation). As the monofunctional (meth) acrylate monomer satisfying the above boiling point condition, for example, oligoalkylene glycol monoalkyl ether (meth) acrylate can be preferably used. Specifically, diethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) Acrylate, tetraethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monopropyl ether (meth) acrylate, triethylene glycol monopropyl ether (meth) acrylate,
Tetraethylene glycol monopropyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, triethylene glycol monobutyl ether (meth) acrylate, tetraethylene glycol monobutyl ether (meth) acrylate; the ethylene group of these oligoethylene glycol skeletons is Those substituted with an alkylene group having a branching or non-branching (a propylene group or the like) (for example, oligopropylene glycol monoalkyl ether (meth) acrylate such as dipropylene glycol monomethyl ether (meth) acrylate) are mentioned. Species or two or more can be used. Preferably, it is an oligoalkylene glycol monomethyl ether (meth) acrylate, and particularly preferably, it is diethylene glycol monomethyl ether (meth) acrylate.

As the monofunctional (meth) acrylate monomer, in addition to the above-mentioned oligoalkylene glycol monoalkyl ether (meth) acrylate, polyethylene glycol monoalkyl ether such as polyethylene glycol (n = 9) monomethyl ether (meth) acrylate (Meth) acrylates; phenoxy (oligo or poly) alkylene glycol (meth) acrylates such as phenoxy polyethylene glycol (meth) acrylate and nonylphenol EO adduct (meth) acrylate;
Isodecyl (meth) acrylate, n- lauryl (meth) acrylate, alkyl (C ₁₂ -C ₁₃₎ (meth) acrylate, tridecyl (meth) acrylate, alkyl (C ₁₂ -C ₁₅₎ (meth) acrylate, n- stearyl ( Long-chain alkyl (meth) acrylates such as meth) acrylates; alkoxyalkyl (meth) acrylates such as n-butoxyethyl (meth) acrylate; phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; dimethylaminoethyl (meth) )
Amino group-containing (meth) acrylates such as acrylate and diethylaminoethyl (meth) acrylate; and hydroxyl group-containing (meth) acrylates such as 3-chloro-2-hydroxypropyl (meth) acrylate can be used.
These can be used alone or in combination of two or more.

[0022] The bifunctional (meth) acrylate monomer is for providing the crosslink density necessary to achieve a high heat distortion temperature (HDT). Examples of the bifunctional (meth) acrylate monomer satisfying the above boiling point conditions include ethylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate;
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (molecular weight 60
0 or less) (PEG # 200 di (meth) acrylate, P
EG # 400 di (meth) acrylate, PEG # 600
(Oligo or poly) ethylene glycol di (meth) acrylate; propylene glycol di (meth) acrylate; dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene (Oligo or poly) alkylene glycol di (meth) acrylate such as glycol di (meth) acrylate (molecular weight of 600 or less), polytetramethylene glycol di (meth) acrylate (provided that (oligo or poly)
Excluding ethylene glycol di (meth) acrylate);
1,3-butylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, 1,9
-Nonanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, glycerin (meth) acrylate, EO adduct of bisphenol A di (meth) acrylate, PO adduct of bisphenol A di (meth) acrylate, dimethylol tri Cyclodecane di (meth) acrylate and the like can be mentioned, and one or more of these can be used. Particularly preferred is oligoethylene glycol di (meth) acrylate, and among them, diethylene glycol di (meth) acrylate is preferred.

The component (C) contains 50 to 100% by weight of a monofunctional (meth) acrylate monomer and a bifunctional (meth) acrylate monomer in order to balance the top coat material for the FRP waterproof lining. Is required, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, and still more preferably 80 to 100% by weight.
１００100% by weight. As monomers other than the monofunctional and bifunctional (meth) acrylate monomers that can be contained as the component (C), trifunctional or higher-functional (meth) acrylate monomers (trimethylolpropane tri (meth) acrylate, EO-modified trimethylol propane) Tri (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.) and monomers other than (meth) acrylate monomers (vinylpyrrolidone, diallyl phthalate,
Diallyl isophthalate, triallyl isocyanurate, etc.), but the above (meth) acrylate monomers are preferred. These can be used alone or in combination of two or more.

As the monomer of the component (C), monofunctional oligoethylene glycol monomethyl ether (meth)
It is preferable to use a combination of an acrylate and a bifunctional oligoethylene glycol di (meth) acrylate, and it is particularly preferable to use a combination of a monofunctional diethylene glycol monomethyl ether (meth) acrylate and a bifunctional diethylene glycol di (meth) acrylate. preferable.

In order to balance the top coat material for the FRP waterproof lining, the weight ratio of the monofunctional (meth) acrylate monomer to the bifunctional (meth) acrylate monomer is 2/1 to 1/3. It is preferred that As described above, the bifunctional (meth) acrylate monomer of the component (C) is used as a by-product during the synthesis of the component (A), and can be used. Further, all the monomers of the component (C) may be synthesized at the same time, or may be added later.

The proportion of the component (C) in the first curable resin composition of the present invention is 15 to 45% by weight. When the proportion is less than 15% by weight, the liquid viscosity of the resin composition becomes too high, resulting in poor workability. When the proportion exceeds 45% by weight, mechanical properties (strength, toughness) and water resistance are deteriorated. It is preferable that the first curable resin composition of the present invention further contains a wax as the component (D). By including wax,
The air drying property is further enhanced. As the wax, it is preferable to use at least one selected from paraffin wax, microcrystalline wax, and other polar waxes. These include, for example, paraffin wax 150F (trade name; manufactured by Nippon Seiro Co., Ltd., melting point 66 ° C.), paraffin wax 130F
(Trade name; manufactured by Nippon Seiwa Co., Ltd., melting point: 55 ° C.), paraffin wax 115F (trade name: manufactured by Nippon Seirasu Co., Ltd., melting point: 47 ° C.), Hi-Mic-2065 (trade name: Nippon Seirowa ( Hi-Mic-2045 (trade name; Nippon Seiro Co., Ltd., melting point 64 ° C.), Nonipol 1
60 (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.), Emulmin 2
00 (trade name; manufactured by Sanyo Chemical Industry Co., Ltd.), NPS-91
25, NPS-9210, NPS-6010, HAD-
5080, NPS-8070, OX-020T, OX-
1949 (trade names; all manufactured by Nippon Seiro Co., Ltd.), diamond wax (trade name; manufactured by Shin Nippon Rika Co., Ltd.), Ceramer 67 (trade name; manufactured by Toyo Petro Riro Co., Ltd.), Ceramer 1608 (trade name) And Toyo Petro Riro Co., Ltd.).

The proportion of the component (D) in the first curable resin composition of the present invention is preferably 0.0001 to 1% by weight, more preferably 0.001 to 0.5% by weight. preferable. In the first curable resin composition of the present invention,
If necessary, a polymerization inhibitor can be used.
Although it is preferable to use a polymerization inhibitor also at the time of synthesizing the component (A), it is preferable to use a polymerization inhibitor in the curable resin composition for adjusting the curing time and maintaining the life of the resin composition. preferable. Examples of the polymerization inhibitor include phenols such as methoquinone and butylated hydroxytoluene; hydroquinones such as hydroquinone, t-butylhydroquinone and monomethylhydroquinone; quinones such as benzoquinone; and sulfur compounds such as phenothiazine. The amount of the polymerization inhibitor to be used is 10 to 10 with respect to the resin composition.
1000 ppm is preferred.

In the first curable resin composition of the present invention, a curing agent can be used if necessary. As the curing agent, those which generate radicals at room temperature or by heating to cure the first curable resin composition of the present invention are preferable. For example, peroxides, azo compounds and the like can be used.
As peroxides, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; hydroperoxides such as cumene hydroperoxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and t-butylcumyl peroxide. Peroxide, 1,
Alkyl peresters such as 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, and bis (4-t- Butyl cyclohexyl) percarbonate such as peroxydicarbonate can be used.
2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile and the like can be used. These can be used alone or in combination of two or more. The amount of the curing agent used should be a gel time suitable for molding applications.
Although it can be determined as appropriate, it is desirable to use 0.2 to 10.0 parts by weight with respect to 100 parts by weight of the resin composition.

Further, in combination with a curing agent, a known curing accelerator can be used as a curing accelerator.
Metal soaps such as cobalt octylate and manganese octylate; metal chelate compounds such as cobalt acetylacetonate and vanadium acetylacetonate; amine compounds such as dimethylaniline and dimethyltoluidine; ethyl acetoacetate and acetylacetone can be used.
These can be used alone or in combination of two or more. Particularly, it is preferable to use a metal soap and an amine compound in combination, since rapid curing with an amine and improvement in drying properties with a metal dryer can be achieved.

The first curable resin composition of the present invention can be cured by light or ultraviolet light using a photopolymerization initiator as a curing agent. The photopolymerization initiator is not particularly limited as long as it has the ability to cure the curable composition of the present invention by the action of light or ultraviolet light. Since the curing speed is particularly improved by using the radical polymerization initiator, it can be suitably used. 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-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- Acetophenone-based compounds such as benzoin, benzoin methyl ether,
Benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate,
4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 3,3 ', 4,4'-tetra (t-butyl Benzophenone compounds such as oxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4
Thioxanthone compounds such as -diisopropylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and 2,4-dichlorothioxanthone; α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone , Camphorquinone, dibenzosuberone, 2
Ketone compounds such as -ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone;2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2 ' Imidazole compounds such as imidazole; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and other carbazole compounds.

One or more of these photopolymerization initiators can be used. Moreover, the usage-amount of a photoinitiator is 0.1-30 weight% normally with respect to the 1st curable resin composition of this invention, Preferably it is 0.5-10%. When the use amount of the photopolymerization initiator is less than 0.1% by weight, the photocurability becomes extremely slow, which is not practical. On the other hand, if the amount of the photopolymerization initiator exceeds 30% by weight, coloring of the photopolymerization initiator itself may not be ignored.

In order to further improve the photocurability of the first curable composition of the present invention, if necessary, triethylamine,
Sensitizers such as diethylamine, diethanolamine, ethanolamine, dimethylaminobenzoic acid, methyl dimethylaminobenzoate, thioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and acetylacetone; benzoyl peroxide; azobisisobutyronitrile For example, peroxides and azo compounds which are the above-mentioned thermal radical curing agents, such as the above-described thermal radical curing agents, can be further added.

In the case where the first curable resin composition of the present invention is used as a coating material, when a thixotropy is required when the composition is applied, a thixotropy agent and a thixotropy auxiliary for imparting thixotropy are used. Can be added. Examples of the thixotropic agent include ordinary fine particle silica typified by Aerosil, surface-treated fine particle silica, amine-treated clay, and the like. The use amount thereof is preferably 0.01 to 20 parts by weight in the composition. 1
-10 parts by weight is more preferred. Examples of the thixotropic auxiliary include polyamide-based thixotropic auxiliary, and the amount of the auxiliary is preferably 0.001 to 5 parts by weight in the composition, and 0.01 to 3 parts by weight.
Parts by weight are more preferred.

When coloring the first curable resin composition of the present invention, a coloring agent such as a pigment or a dye can be used, and the amount used is 0.001 to 50% by weight in the composition. Parts by weight, more preferably 0.01 to 30 parts by weight. Furthermore, the first curable resin composition of the present invention contains an antifoaming agent, a leveling agent, a filler (aluminum hydroxide, talc,
Silica sand, calcium carbonate, antimony oxide, etc.), UV absorber, thickener (metal oxide such as magnesium oxide, calcium oxide, zinc oxide, etc.), low shrinkage agent, anti-aging agent, plasticizer, aggregate, flame retardant , Stabilizers, reinforcing agents and the like can be used as appropriate.

The first curable resin composition of the present invention has a low odor, is excellent in air drying property, heat resistance and water resistance, has sufficient toughness, and has a low viscosity. Materials for coating steel plates, glass, wood, etc., especially FR
It is a well-balanced top coat material for P waterproof lining. Specifically, the first curable resin composition of the present invention can easily achieve a heat distortion temperature (HDT) of 50 ° C. or higher, which is related to heat resistance and water resistance of a cured product, and preferably 50 to 150 ° C. , More preferably 60 to 150
° C, more preferably 70 to 150 ° C. The higher the heat deformation temperature, the better, but 130 ° C. is sufficient for applications used as a coating film. If the heat distortion temperature is less than 50 ° C,
Heat resistance is insufficient, and water resistance also deteriorates. The heat distortion temperature (HDT) can be measured according to JIS K6911.

Further, regarding the toughness of the first curable resin composition of the present invention, the tensile elongation of the cured product (JIS K71)
13 tensile test) 3% or more can be easily achieved, more preferably 3 to 20%, further preferably 4% to 10%, and still more preferably 5 to 10%. When the tensile elongation is less than 3%, the coating film does not follow the substrate. If it exceeds 20%,
The film is too soft, adversely affecting practical strength and water resistance.

Further, the viscosity of the first curable resin composition of the present invention can easily attain 1500 mPa · s or less, more preferably 1000 mPa · s or less, further preferably 900 mPa · s or less, and further preferably 80 mPa · s or less.
0 mPa · s or less. Considering workability and the like, the viscosity is preferably 100 mPa · s or more. Also,
By adding a thixotropic agent and an auxiliary thixotropic agent, the first aspect of the present invention can be obtained.
Even when the degree of rocking change of the curable resin composition is 1.5 or more, the viscosity with a Brookfield viscometer (measured at 60 rpm) can easily be 6000 mPa · s or less, so that concrete, mortar, It has sufficient workability to be applied as a material for coating a steel plate, glass, wood, or the like, particularly as a top coat material for FRP waterproof lining. In addition, the degree of rocking can be measured according to JIS K6911.

In the case where the first curable resin composition of the present invention is imparted with rocking change, the rocking change is preferably from 1.5 to 5, more preferably from 2 to 4. If the degree of fluctuation is less than 1.5, the liquid drips during application. If the degree of rocking change exceeds 5, the viscosity of the liquid will increase too much, resulting in poor workability. When the first curable resin composition of the present invention is imparted with shaking changeability, the viscosity (60 rpm viscosity) measured with a Brookfield viscometer (measured at 60 rpm) is 1000 to 6000 mPa · s.
s is preferable, and more preferably 2000 to 4000 mP
a · s. When the viscosity at 60 rpm is less than 1000 mPa · s, it is related to the degree of fluctuation, but the viscosity after the application is too low, so that it can be applied only to the horizontal surface. On the other hand, if the 60 rpm viscosity exceeds 6000 mPa · s, the viscosity is too high and the workability of coating is poor.

The method for producing the first curable resin composition of the present invention is not particularly limited, and may be a method in which the respective components are separately synthesized and mixed.
The following batch synthesis is also possible. In the batch synthesis, as a first step, an acid component containing at least tetrahydrophthalic acids, a glycol, and an excess amount of (meth) acrylic acid are reacted to form a polyester (meth) acrylate (( Component (A)) and a difunctional (meth) acrylate monomer (part of component (C)) which is a reaction product of glycol and (meth) acrylic acid
And a reaction mixture containing unreacted (meth) acrylic acid, and then, as a second step, an epoxy compound is reacted with the reaction mixture to obtain an epoxy (meth) acrylate (component (B)). Things. Other components (C) and (D) may be appropriately added at an appropriate time.

The second curable resin composition of the present invention will be described. The second curable resin composition of the present invention comprises:
(A ′) an air-drying unsaturated group-containing resin, (B ′) epoxy (meth) acrylate and (C ′) 6.7 × 10 ³
A material containing a monomer with a boiling point of 90 ° C or higher in Pa and having a well-balanced physical properties and properties as a material for coating concrete, mortar, steel plate, glass, wood, etc., particularly as a top coat material for FRP waterproof lining. It is.

Specifically, the heat distortion temperature (HD
T) is 50 ° C. or higher, preferably 50 to 150 ° C., more preferably 60 to 150 ° C., and still more preferably 70 to 15 ° C.
0 ° C., the cured product has a tensile elongation of 3% or more, preferably 3 to 20%, more preferably 4 to 10%, and still more preferably 5 to 10%, and the composition has a viscosity of 1500 mP.
a · s or less, preferably 1000 mPa · s or less, more preferably 900 mPa · s or less, still more preferably 8 mPa · s or less.
It is 100 mPa · s or less and 100 mPa · s or more. When the degree of thixotropy of the composition is adjusted to 1.5 or more by adding a thixotropy agent and a thixotropy aid, the viscosity with a Brookfield viscometer (measured at 60 rpm) is 6%.
It is preferable to be 000 mPa · s or less from the viewpoint of application workability as a top coat material for FRP waterproof lining. When the second curable resin composition of the present invention is imparted with thixotropy, the degree of thixotropy of the composition is preferably 1.5 to 5, more preferably 2 to 4, and 60 rpm.
The viscosity is preferably from 1,000 to 6,000 mPa · s, more preferably from 2,000 to 4,000 mPa · s.

Examples of the air-drying unsaturated group-containing resin of the component (A ') include unsaturated polyester resins and vinyl ester resins (for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate and the like). )), In which an air drying component is introduced into the unsaturated group-containing resin. As a method of introducing air dry ingredients, (1) a glycol component to -O-CH ₂ -CH = C
Using a compound containing an allyl ether group represented by H _2, (2) using the cyclic aliphatic unsaturated polybasic acid or derivative thereof to the acid component, using a compound containing (3) dicyclopentadiene , (4) using a drying oil or an epoxy-reactive diluent.

As the compound having an allyl ether group of (1), known compounds can be used. Typical examples thereof include ethylene glycol monoallyl ether,
Diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether,
Polypropylene glycol monoallyl ether, 1,2
-Butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, glycerin Allyl ether compounds of polyhydric alcohols such as diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether and pentaerythritol triallyl ether; allyl ether compounds having an oxirane ring such as allyl glycidyl ether;

The compound (1) containing an allyl ether group can be used in combination with another glycol component. Other glycol components that can be used in combination include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butynediol, 2-methylpropane-
1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-
Pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di (4-hydroxypropoxydiphenyl) propane, and the like. Other oxides such as ethylene oxide and propylene oxide can be used as well. Further, as a part of the glycol component and the acid component, a polycondensate such as polyethylene terephthalate can be used.

Examples of the cycloaliphatic unsaturated polybasic acid (2) or its derivative include tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-terphine-maleic anhydride adduct, rosin Or ester gum. The cycloaliphatic unsaturated polybasic acid (2) or a derivative thereof can be used in combination with another acid component. Other acid components that can be used in combination include, for example, α, β-ethylenically unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid or esters thereof, and the like. Anhydrides and derivatives thereof; aromatic saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, halogenated phthalic anhydride or esters thereof, their anhydrides and Derivatives: aliphatic or alicyclic saturated dibasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, aceleic acid, glutaric acid, hexahydrophthalic anhydride or esters thereof, and their acid anhydrides And their derivatives.

Examples of the compound containing dicyclopentadiene (3) include hydroxylated dicyclopentadiene. Examples of the drying oil of (4) include fatty oils such as linseed oil, soybean oil, cottonseed oil, coconut oil and peanut oil, and reaction products of these fatty oils with polyhydric alcohols such as glycerin. Examples of the epoxy reactive diluent (4) include a monoepoxy compound and a polyepoxy compound. As the monoepoxy compound, allyl glycidyl ether, n-butyl glycidyl ether,
Examples include phenyl glycidyl ether, glycidyl methacrylate, "Kajura E" (manufactured by Shell, The Netherlands), and polyepoxy compounds such as "UNOX 206" (manufactured by Union Carbide, USA) and "Epicoat 812". [Manufactured by Dainippon Ink and Chemicals, Inc.] and diglycidyl ether.

In these listings, the component (A ') includes, as the component (A) of the first curable resin composition of the present invention, a polyester (meta) having a skeleton containing a structural unit derived from tetrahydrophthalic acids. ) Acrylates are preferred.
As the epoxy (meth) acrylate of the component (B ′), the epoxy (meth) acrylate that is the component (B) of the first curable resin composition of the present invention can be used.

The monomer having a boiling point of not less than 90 ° C. at 6.7 × 10 ³ Pa of the component (C ′) is not particularly limited, but from the viewpoint of achieving a high heat distortion temperature (HDT) and a high toughness at the same time, 50% by weight of a monofunctional (meth) acrylate monomer and a difunctional (meth) acrylate monomer, which are the component (C) of the first curable resin composition of the present invention.
It is preferable to use a monomer having a boiling point at 6.7 × 10 ³ Pa and containing 90 ° C. or more.

The ratio of the components (A ') to (C') in the second curable resin composition of the present invention and the ratios of (A ') to (C')
Components that can be blended in addition to the components are the same as in the first curable resin composition of the present invention. The first and second curable resin compositions of the present invention cover concrete, mortar, steel plate, glass, wood, and the like as paints, coating materials, marking materials, rooftop waterproof materials, painted floor materials, and the like. It can be used as a material to be used. Further, it can be used as a resin for FRP molding. In particular, a pigment or the like is preferably used as a top coat material, and among them, a top coat material such as an FRP waterproof lining is particularly preferable.

[0050]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Production Example 1)-Preparation of polyester methacrylate resin-608 g of tetrahydrophthalic anhydride, 848 g of diethylene glycol, 13 g of paratoluenesulfonic acid, and 350 g of toluene were heated and dehydrated and condensed at 140 to 120 ° C for 4 hours under a nitrogen gas stream. The ester diol was obtained as an intermediate. Thereafter, under an air flow of nitrogen / air = 2/1, 0.5 g of phenothiazine and 0.25 of methylhydroquinone were added.
g and 516 g of methacrylic acid.
Heat dehydration condensation was carried out for hours. Thereafter, the solvent toluene was distilled off at 90 ° C. under reduced pressure to obtain a resin (A).

When the obtained resin (A) was analyzed by gas chromatography, it contained 29% by weight of diethylene glycol dimethacrylate. (Production Example 2) -Preparation of epoxy methacrylate resin- 1,228 g of bisphenol type epoxy resin (Epototo YD-128, epoxy equivalent 186 manufactured by Toto Kasei), 0.18 g of phenothiazine, 0.18 of methylhydroquinone
The mixture was heated to 115 ° C. under an air flow of nitrogen / air = 2/1, 567.6 g of methacrylic acid and 5.39 g of triethylamine were added dropwise over 3 hours, and then heated and reacted for 4 hours to obtain epoxy methacrylate (B ) Got. (Examples 1 to 3 and Comparative Examples 1 to 3) Resin (A), epoxy methacrylate (B), diethylene glycol dimethacrylate, diethylene glycol monomethyl ether methacrylate were blended as shown in Table 1, and resin blends (1) to ( 3) and Comparative resin formulations (1) to (3) were obtained. (Measurement of physical properties) Table 1 shows the physical properties of each of the obtained resin blends. Tensile strength, tensile modulus and tensile elongation are measured by JI
It was measured according to SK7113. Heat distortion temperature (HDT)
Was measured according to JIS K6911. The water boiling resistance was determined by immersing a test piece having a thickness of 3 mm in boiling ion-exchanged water, and measuring the time until the surface appearance was impaired by visual observation.

The method of preparing the test piece used for the measurement is as follows. To each of the obtained resin compositions, cobalt octylate containing a metal content of 8% by weight and dimethylaniline were added as curing accelerators, and a curing agent 328E (manufactured by Kayaku Akzo) was added.
Was added to obtain a resin composition of the present invention, which was poured into a glass casting mold and left overnight. The next day, after heating at 110 ° C. for 2 hours, a test piece was cut out from the cured product obtained by removing the mold. (Air drying) The pot life of each of the obtained resin formulations was 15
After adjusting to ~ 30 minutes, 100 parts by weight of each resin formulation,
0.5 parts by weight of cobalt octylate containing 8% by weight of metal, 0.5 parts by weight of dimethylaniline, curing agent 328E
1 part by weight (manufactured by Kayaku Akzo), paraffin wax 130
F (manufactured by Nippon Seiro Co., Ltd., melting point 55 ° C.) 0.1 part by weight, N
Add PS-9125 (product of the company) 0.01 parts by weight,
The composition was coated on a glass plate by adjusting the thickness with a spacer, and the state after 3 hours was evaluated by finger touch. The sample was completely dried and had no tack on the film, and the sample having tack on the surface was rated as Δ. (Adjustment of pot life) 100 parts by weight of each resin composition was collected in a plastic beaker, and 0.5 parts by weight of dimethylaniline and 0.5% by weight of cobalt octylate containing 8% by weight of metal were placed in a water bath at 25 ° C. By weight, 1 part by weight of a curing agent 328E (manufactured by Kayaku Akzo) was mixed to determine the time until gelation, and this was defined as the pot life.

Before adding a curing accelerator and a curing agent to each resin composition, tertiary butyl catechol 0.01 to
The pot life was adjusted by adding 0.1 parts by weight. Example 4 456 g of tetrahydrophthalic anhydride, 636 g of diethylene glycol, paratoluenesulfonic acid 1
0 g, toluene 406 g, methacrylic acid 864 g, phenothiazine 1.0 g, methylhydroquinone 0.5 g,
Was heated and dehydrated and condensed at 120 ° C. for 10 hours in a stream of nitrogen / air = 2/1 to obtain a reaction mixture containing ester methacrylate and remaining methacrylic acid. Subsequently, phenothiazine 0.5 g, methylhydroquinone 0.25 g
Is added, the mixture is heated to 115 ° C. in an air flow of nitrogen / air = 2/1, and bisphenol-type epoxy resin (Epototo YD-128, epoxy equivalent 186, manufactured by Toto Kasei) 76
Then, 0 g and 16 g of triethylamine were added dropwise over 1 hour, followed by a heating reaction for 4 hours to obtain a resin mixture (C). Thereafter, 230 g of diethylene glycol monomethyl ether methacrylate was added to obtain a resin composition (4).

The physical properties of this resin compound (4) were determined in Examples 1 to
Physical properties were measured in the same manner as in No. 3 and shown in Table 1. (Example 5) A resin compound (5) was prepared in the same manner as in Example 4 except that the amount of diethylene glycol monomethyl ether methacrylate added to the resin compound (C) was changed from 230 g to 460 g. Obtained.
Physical properties of this resin composition (5) were measured in the same manner as in Examples 1 to 3, and the results are shown in Table 1.

[0055]

[Table 1]

Examples 1 to 5 have excellent air drying properties and heat resistance, have sufficient toughness, and have low viscosity.
On the other hand, in Comparative Example 1, since the amount of the epoxy (meth) acrylate of the component (B) is small, the heat resistance is inferior. Comparative Example 2
However, since no monofunctional (meth) acrylate monomer is blended, the toughness is insufficient. In Comparative Example 3,
Since the polyester (meth) acrylate of the component (A) is not blended, there is no problem in physical properties, but the air drying property is insufficient. In the resin composition of Comparative Example 3, 2
Even after 4 hours, tack remained for a 1 mm thickness. (Example 6) To 100 parts by weight of the resin composition (1) of Example 1, 0.02 parts by weight of tertiary butyl catechol and 0.1 of paraffin wax 130F (manufactured by Nippon Seiro Co., Ltd.)
Parts by weight, 0.01 parts by weight of NPS-9125 (product of the company) and 0.2 parts by weight of BYK R-605 (manufactured by BYK-Chemie) were added and mixed, and then 2 parts by weight of Aerosil 200 (manufactured by Nippon Aerosil) was added. In addition, the mixture was dispersed and mixed with a homomixer.

The obtained mixture was filtered through a 100 mesh wire net and defoamed, and the degree of fluctuation was measured with a Brookfield viscometer according to JIS K6911. The viscosity measured at 60 rpm was 3,300 mPa · s, and the degree of fluctuation was 2.7. To 100 parts by weight of the obtained resin composition, 0.5 parts by weight of dimethylaniline, 0.5 parts by weight of cobalt octylate containing 8% by weight of metal, and 1 part by weight of a curing agent 328E (manufactured by Kayaku Akzo) were added. Then, it was applied on a glass plate with a brush so as to have a thickness of about 0.3 mm. It dried completely in 2 hours and the surface appearance was very good. Example 7 10 parts by weight of titanium oxide was added to 100 parts by weight of the resin composition obtained in Example 6 after measuring the degree of shaking change, and the mixture was adjusted to white.
0.5 parts by weight of cobalt octylate containing a metal component by weight
Add 1 part by weight of curing agent 328E (manufactured by Kayaku Akzo),
It was applied on a glass plate with a brush so as to have a thickness of about 0.3 mm. It dried completely in 2 hours and the surface appearance was very good.

[0058]

The curable resin composition of the present invention has a low odor, excellent air-drying properties, heat resistance, and water resistance, has sufficient toughness, and has a low viscosity. For coating glass, glass, wood, etc., especially FRP
It is a well-balanced topcoat material for waterproof linings.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Souki Yoshimune 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4H020 BA02 BA05 4J011 PA56 PB40 PC02 QA03 QA07 QA12 QA13 QA19 QA20 QA23 QA24 QA31 QB13 QB16 QB19 4J027 AB26 AC02 AE02 AE03 BA07 CA10 CC01 CD08

Claims (7)

[Claims] 1. A curable resin composition containing the following components (A) to (C) in the following proportions. (A) Polyester (meth) acrylate having a structural unit derived from tetrahydrophthalic acid in the skeleton 25 to 50% by weight (B) Epoxy (meth) acrylate 15 to 55% by weight (C) Monofunctional (meth) acrylate monomer and 15 to 45% by weight of a monomer having a boiling point of 90 ° C. or more at 6.7 × 10 ³ Pa containing 50 to 100% by weight of a bifunctional (meth) acrylate monomer 2. The component (C) includes a monofunctional oligoalkylene glycol monomethyl ether (meth) acrylate and a bifunctional oligoethylene glycol di (meth) acrylate.
The curable resin composition according to claim 1, comprising an acrylate. 3. The weight ratio of the monofunctional (meth) acrylate monomer to the bifunctional (meth) acrylate monomer is as follows:
The curable resin composition according to claim 1, wherein the ratio is from 2/1 to 1/3. 4. The curable resin composition according to claim 1, wherein the content of the tetrahydrophthalic acid in the component (A) is 35 to 80% by weight. 5. The curable resin composition according to claim 1, further comprising a wax as the component (D). 6. It comprises the following components (A ′) to (C ′),
The cured product has a heat distortion temperature (HDT) of 50 ° C. or more, the cured product has a tensile elongation of 3% or more, and the composition has a viscosity of 1500 mPa.
-The curable resin composition which is s or less. (A ′) Air-drying unsaturated group-containing resin (B ′) Epoxy (meth) acrylate (C ′) Monomer whose boiling point at 6.7 × 10 ³ Pa is 90 ° C. or more 7. The method for producing a curable resin composition according to claim 1, wherein the acid component contains at least tetrahydrophthalic acid, glycol, and an excess amount of (meth) acrylic acid. And a polyester (meth) acrylate containing tetrahydrophthalic acid in the skeleton, a difunctional (meth) acrylate monomer which is a reaction product of glycol and (meth) acrylic acid, and an unreacted (meth) acrylic acid. A method for producing a curable resin composition, comprising: a first step of obtaining a reaction mixture containing: and a second step of reacting an epoxy compound with the reaction mixture to obtain an epoxy (meth) acrylate.