JP2002179748A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition with low viscosity and low smell, suffering little inhibition of cure by air, and exhibiting excellent strength and waterproofness of the cured product. SOLUTION: This curable resin composition comprises (a) an unsaturated polyester having a norbornene skeleton, (b) a polyester(meth)acrylate and (c) a polymerizable monomer, and more in detail, the introduction rate of the norbornene skeleton is 5 to 100 mol% based on the total polybasic acid component constituting the unsaturated polyester (a). The polyester(meth)acrylate (b) is preferably a polyester(meth)acrylate (b-1) obtained by reacting an alkyleneoxide with an unsaturated polybasic acid anhydride and/or saturated polybasic acid, using as a starting material one or more compounds selected from the group consisting of (meth)acrylic acid, (meth)acrylate having an alcoholic hydroxy group, and (meth)acrylate having a carboxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a low viscosity and a low odor, hardly inhibits curing by air, and has a high strength and a cured product.
The present invention relates to a curable resin composition having excellent water resistance.

[0002]

2. Description of the Related Art Radical curable resins represented by unsaturated polyester resins, epoxy (meth) acrylate (vinyl ester) resins, urethane (meth) acrylate resins, and polyester (meth) acrylate resins are easy to handle in liquid form. Quickly cures to strength, heat resistance,
Excellent in various properties such as water resistance
It is widely used as a base material for P, a coating material, a paint, and an adhesive. However, since the radical-curable resin uses a polymerizable monomer represented by styrene or the like as a diluent, it generates an unpleasant odor, particularly in molding work by open mold, and releases toxic vapor into the atmosphere. It has the disadvantage of volatilizing inside. Therefore, at present, measures regarding the use of these volatile solvents have become increasingly severe.

As conventional measures, there are a method of adding a volatilization inhibitor such as paraffin, a method of using a polymerizable monomer having a high boiling point, and a method of reducing the resin solid content to a low molecular weight to reduce the use ratio of the polymerizable monomer. Although a method for reducing the amount is disclosed, a material satisfying all of workability, physical properties of a cured product and cost has not yet been developed.

By the way, unsaturated polyesters having a norbornene skeleton are easily produced from, for example, inexpensive dicyclopentadiene as a raw material and are particularly excellent in air curability and low shrinkage, so that they are widely used in the above fields. . However, as a drawback, the strength of the cured product is slightly inferior, so that its use is limited in applications requiring high strength such as structural materials.

On the other hand, polyester (meth) acrylate is obtained, for example, by dehydration condensation of polyester polyol and (meth) acrylic acid, and is known to give a cured product having low viscosity and good strength and water resistance. Its disadvantage is that it has a remarkable poor curing on the air contact surface, and has a sticky surface even after being left for a long time after molding, so that its use is limited.

[0006]

The problem to be solved by the present invention is to provide a cured product which has a low viscosity and low odor, has excellent surface drying properties upon curing, and is excellent in water resistance and strength. It is to provide a resin composition.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in view of the above-mentioned problems of the conventional radical-curable resin composition, and as a result, completed the present invention. That is, the present invention relates to a curable resin composition which has a low viscosity and a low odor, has excellent surface drying properties upon curing, and is excellent in water resistance and strength, and more specifically relates to an unsaturated polyester having a norbornene skeleton (a ), A curable resin composition containing a polyester (meth) acrylate (b) and a polymerizable monomer (c).

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The unsaturated polyester (a) having a norbornene skeleton (hereinafter referred to as unsaturated polyester (a)) used in the present invention comprises a polybasic acid component (d) containing an unsaturated polybasic acid as an essential component and a glycol component. The unsaturated polyester obtained by dehydration-condensation of (e) and / or the epoxy compound component (f) is obtained by introducing a norbornene skeleton represented by the general formula 1 into a part of the molecular terminal.

[0009]

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[0010]

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Of course, a monovalent acid may be used for a part of the polybasic acid component, and a monohydric alcohol may be used for a part of the glycol component.

The acid value and molecular weight of the unsaturated polyester (a) are not particularly limited, but are generally 40 or less, generally have a number average molecular weight of 500 to 5,000 and a weight average molecular weight of 1,000 to 50,000. The number average molecular weight is preferably in the range of 600 to 2500 and the weight average molecular weight is 150 from the viewpoint of the balance between low viscosity and physical properties of the cured product.
More preferably, it is in the range of 0 to 15000. These molecular weights can be easily measured using a general-purpose gel permeation chromatography (GPC) apparatus, using polystyrene having a known molecular weight as a standard substance, and a differential refractometer as a detector.

The polybasic acid component (d) used in the unsaturated polyester (a) reacts with the hydroxyl group and / or epoxy group contained in the glycol component (e) and / or the epoxy compound component (f) to form an ester bond. Any compound having two or more substituents capable of producing
An unsaturated polybasic acid is essential, and a part thereof may be replaced with a saturated polybasic acid before use. Specific examples of the unsaturated polybasic acid include α, β-unsaturated polybasic acids of maleic acid, fumaric acid, aconitic acid, and itaconic acid; β, γ-unsaturated polybasic acids such as dihydromuconic acid Acids; anhydrides of these acids; halides of these acids; alkyl esters of these acids, and the like. These exemplified compounds may be used alone or in combination of two or more.

The above-mentioned 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 and dimer 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 glycol component (e) used in the unsaturated polyester (a) includes ethylene glycol, diethylene glycol, 1,3-propanediol,
Methyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, dipropylene glycol, 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, triethylene glycol, hydrogenated bisphenol A, an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of hydrogenated bisphenol A, glycerin, trimethylolpropane, Examples include pentaerythritol and dipentaerythritol. These exemplified compounds may be used alone or in combination of two or more.

The epoxy compound component (f) used in the unsaturated polyester (a) includes ethylene oxide,
Propylene oxide, butylene oxide, styrene oxide, 3,4-epoxy-1-butene, glycidyl acrylate, glycidyl methacrylate, diglycidyl ether of bisphenol A, and the like can be used.
These exemplified compounds may be used alone or in combination of two or more.

A so-called air-curable polyester can be obtained by substituting a part of the raw material of the unsaturated polyester (a) with a compound having an unsaturated bond such as an allyl group shown below. Specifically, at least the whole or a part of the above-mentioned ordinary polybasic acid component (d) is replaced with an unsaturated polybasic acid having an unsaturated bond such as an allyl group shown below, or The whole or a part of the component (f) and / or the epoxy compound component (e) may be replaced with a glycol component and / or an epoxy compound component 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, cyclopentadiene-maleic anhydride adduct (endomethylenetetrahydrophthalic acid), rosin, ester gum, drying oil fatty acid, semi-dry oil fatty acid and the like can be mentioned. These exemplified compounds may be used alone or in combination of two or more.

The glycol component and / or epoxy compound component having an unsaturated bond include trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, trimethylolethane monoallyl ether, trimethylolethanediallyl ether, pentane Erythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, glycerin monoallyl ether, glycerin diallyl ether, allyl glycidyl ether and the like can be mentioned. These exemplified compounds may be used alone or in combination of two or more.

The method of introducing the norbornene skeleton into the unsaturated polyester (a) is not particularly limited, but the method of introducing dicyclopentadiene as a raw material is efficient and economical. Specifically, for example, it can be obtained by replacing a part of the polybasic acid component used in the unsaturated polyester (a) with an unsaturated polybasic acid adduct of dicyclopentadiene. Examples of the unsaturated polybasic acid adduct of dicyclopentadiene include adducts obtained by adding the unsaturated polybasic acids exemplified above to dicyclopentadiene, for example, dicyclopentadiene such as maleic acid adduct of dicyclopentadiene. Unsaturated divalent carboxylic acid adducts can be used.

It can also be obtained by replacing a part of the glycol component used in the unsaturated polyester (a) with glycol adducts of dicyclopentadiene or hydroxydicyclopentadiene.

Of these methods for introducing a norbornene skeleton into an unsaturated polyester (a), in order to effectively bring out the excellent effects of the present invention, an unsaturated divalent carboxylic acid adduct of dicyclopentadiene is used as a raw material. It is preferable to produce unsaturated polyester (a) by using the same, and it is particularly preferable to use a maleic acid adduct of dicyclopentadiene as a raw material.

The maleic acid adduct of dicyclopentadiene can be produced by performing an addition reaction of dicyclopentadiene, maleic anhydride and water, but the method described in JP-A-11-49849, ie, In the step of reacting dicyclopentadiene with the reaction mixture of maleic anhydride and water, a method is finally obtained in which the molar ratio of maleic anhydride to water is less than 1, preferably 0.2 to 0.9. It is particularly preferable because the water resistance of the molded article is improved. In this case, the method for producing the unsaturated polyester (a) includes (1) dicyclopentadiene,
Reacting maleic anhydride and water to obtain a maleic acid adduct of dicyclopentadiene (d); and (2) adding a polybasic acid component (d) and a glycol component (e) to the maleic acid adduct of dicyclopentadiene. ) And / or a step of adding and dehydrating and condensing an epoxy compound (f) to obtain an unsaturated polyester (a).

Further, a polybasic acid component, a glycol component and / or
Alternatively, an unsaturated polyester (a) can be produced by simultaneously adding an epoxy compound component and dicyclopentadiene, heating the mixture, and performing dehydration condensation. In this case, in addition to the polybasic acid adduct of dicyclopentadiene, dicyclopentadiene A norbornene skeleton is introduced into the unsaturated polyester (a) in the form of a glycol adduct of Further, after the polybasic acid component (d), the glycol component (e) and / or the epoxy compound component (f) are dehydrated and condensed, dicyclopentadiene is added, and an addition reaction is caused to a carboxylic acid group and a hydroxyl group at a molecular terminal. To produce the unsaturated polyester (a).

As a method for synthesizing the unsaturated polyester (a) using dicyclopentadiene as a raw material, for example, Technical Procedures, 3
6th Annual Conference, Rein
Forced Plastics / Composite
s Institute, The Society of
the Plastics Industry I
nc. , Session 7-E (1981), and these known methods can be used without sacrificing the excellent effects of the present invention.

In the unsaturated polyester (a), the rate of introduction of the norbornene skeleton depends on the content of the unsaturated polyester (a).
It is preferable to use 5 to 100 mol% of dicyclopentadiene with respect to all polybasic acid components constituting the above. If the amount is less than this range, the appearance of the molded article due to uneven color or color separation occurs, and if it is more than this range, the toughness of the molded article is poor, which causes cracking during molding.

The introduction rate of the norbornene skeleton can be easily calculated from the ratio of the charged raw materials. For example, when the total amount of the polybasic acid component used in the production of the unsaturated polyester (a) is X mol, Assuming that the used amount of cyclopentadiene is Y mol, the introduction ratio of the norbornene skeleton is simply (Y / X × 100)%. In place of dicyclopentadiene, for example, when an ethylene glycol adduct of hydroxydicyclopentadiene or dicyclopentadiene is used, of course, each used mole number is divided by the used mole number of all polybasic acid components to form a norbornene skeleton. What is necessary is just to calculate an introduction rate.

Polyester (meth) used in the present invention
The acrylate (b) refers to a compound having a polyester structure in the main chain skeleton and a structure in which (meth) acrylic acid is introduced into at least one molecular terminal through an ester bond. The addition reaction product of acrylic acid and / or methacrylic acid and a polyepoxy compound, which is generally called an epoxy (meth) acrylate, is structurally similar in that a (meth) acryl group is present at the terminal of the molecule. However, they are clearly distinguished from each other in the present invention. A clear structural difference is that epoxy (meth) acrylate has at least two or more hydroxyl groups in one molecule due to the addition reaction between (meth) acrylic acid and an epoxy group. Acrylate (b)
Is at most 1 or less.
This is a very important factor from the viewpoint of designing a low-viscosity resin. Therefore, in the curable resin composition of the present invention, an excellent low-viscosity (low-viscosity) is only obtained by limiting to the polyester (meth) acrylate (b). Viscosity and good workability).

The generality of these names is as follows:
For example, Eiichiro Takiyama, "Polyester Resin Handbook", p. 178-195 and p. 336, as described in the Nikkan Kogyo Shimbun (1988), which is very commonly used in the art.

The polyester (meth) acrylate (b) to be used is not particularly limited, and the type and proportion of the polybasic acid component, glycol component and / or epoxy compound component in the polyester portion of the main chain can be arbitrarily adjusted. Thus, it can be arbitrarily manufactured according to necessary physical properties. As the above-mentioned polybasic acid component, glycol component and / or epoxy compound component, raw materials used in the production of unsaturated polyester (a) can be used as they are. As the polybasic acid component, known compounds can be used, and the polybasic acid component may be an unsaturated polybasic acid or a saturated polybasic acid. If necessary, it may be a polybasic acid anhydride or a polybasic acid hydrate. If there is no problem in the production conditions of the polyester (meth) acrylate, the above-mentioned various polybasic acid components can be mixed and used.

Polyester (meth) acrylate (b)
The molecular weight of is not particularly limited, but generally has a number average molecular weight of 400 to 10000, and especially when a low-viscosity curable resin composition is required, the number average molecular weight is preferably 4 to 4.
It is desirable to set it to 00 to 1200, more preferably 400 to 800. The molecular weight dispersity of the polyester (meth) acrylate (b), that is, the value obtained by dividing the weight average molecular weight by the number average molecular weight is not particularly limited, but is preferably 1.8 or less from the viewpoint of suppressing an increase in viscosity.
It is more preferably at most 1.5, most preferably at most 1.3.

Polyester (meth) acrylate (b)
The acid value of is not particularly limited, but when the viscosity of the obtained resin composition is reduced or the water resistance of the cured product is required, it is desirable that the acid value be 5 or less. When it is necessary to increase the adhesion to various substrates, it is desirable to set the acid value to about 10 to 100.
The acid value can be adjusted to a desired acid value by arbitrarily setting the charging ratio of the (meth) acrylic acid, polybasic acid component, glycol component and / or epoxy compound component to be used.

As a method for easily producing a polyester (meth) acrylate (b) having high reactivity and excellent strength and water resistance of a cured product, Japanese Patent Application No. 2000-163 is disclosed.
Polyester (meth) by the method described in No. 582
An acrylate production method may be used. That is, (meth) acrylic acid, (meth) having an alcoholic hydroxyl group
Starting from one or more compounds selected from the group consisting of acrylates and (meth) acrylates having a carboxylic acid group, an alkylene oxide and an unsaturated polybasic acid anhydride and / or a saturated polybasic acid anhydride are successively ring-opened. Polyester (meth) acrylate (b-
This is 1). The synthesis of ordinary polyester (meth) acrylate (b) is performed by dehydration condensation using a strong acid catalyst, but the above-mentioned polyester (meth) acrylate (b-1) is successively ring-opened using a weak acid or weak base catalyst. This is an addition reaction, and undesirable side reactions such as transesterification can be significantly reduced. Therefore, although the raw material is restricted, the method for producing the polyester (meth) acrylate (b-1) is the most suitable as a method for obtaining a polyester (meth) acrylate having a uniform molecular weight and a low viscosity. In this case, no purification step is required after the reaction (in a production method using an ordinary strong acid catalyst, a catalyst neutralization / removal step is indispensable), which is extremely economically advantageous. For the above reasons, one of the preferred embodiments of the present invention is to use polyester (meth) acrylate (b-1) as the polyester (meth) acrylate (b).

Polyester (meth) acrylate (b-
Commercially available (meth) acrylic acid that can be used in 1) can be used as it is. Acrylic acid and methacrylic acid may be used alone, or may be used by mixing at an arbitrary ratio.

Polyester (meth) acrylate (b-
(Meth) having an alcoholic hydroxyl group usable in 1)
As the acrylate or (meth) acrylate having a carboxylic acid group, specifically, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, (Meth) acrylates having an alcoholic hydroxyl group such as oligoethylene glycol mono (meth) acrylate, oligopropylene glycol mono (meth) acrylate, methyl- (α-hydroxymethyl) acrylate, ethyl- (α-hydroxymethyl) acrylate;
Hydroxyethyl (meth) acrylate maleic anhydride reactant, hydroxypropyl (meth) acrylate maleic anhydride reactant, hydroxyethyl (meth) acrylate phthalic anhydride reactant, hydroxypropyl (meth) acrylate phthalic anhydride reaction (Meth) acrylate having a carboxylic acid group such as a product. Each of these exemplified compounds may be used alone.
More than one type may be used in combination. Of course, it may be used in combination with (meth) acrylic acid. Further, the use ratio of these exemplified compounds is not particularly limited, and may be appropriately set according to desired physical properties.

Polyester (meth) acrylate (b-
Examples of the unsaturated polybasic acid anhydride usable in 1) include unsaturated polybasic acid anhydrides such as maleic anhydride, aconitic anhydride and itaconic anhydride. These exemplified compounds may be used alone or in combination of two or more.

The saturated polybasic acid anhydrides usable for the polyester (meth) acrylate (b-1) include:
For example, saturated polybasic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, hetanoic anhydride, succinic anhydride and the like Acid anhydrides and halides. These exemplified compounds may be used alone or in combination of two or more.

Polyester (meth) acrylate (b-
The content of the double bond derived from the unsaturated polybasic anhydride contained in 1) is not particularly limited, but is preferably a polyester (meth) acrylate (b-) in consideration of the balance between excellent curability and elongation of the resin. 1) It is preferable to set appropriately within the range of 0.1 to 6 mol, more preferably 1 to 5 mol per kg. Outside this range, the heat resistance of the resin may decrease, or the resulting cured product may become hard and brittle.

The proportion of the unsaturated polybasic acid anhydride component in the total polybasic acid anhydride component is not particularly limited. However, when it is necessary to increase the crosslink density of the cured product to increase heat resistance, hardness, etc. It is preferable that the usage ratio of the unsaturated polybasic acid anhydride component in the total polybasic acid anhydride component is 50 mol% or more. When the unsaturated polybasic acid anhydride and the saturated polybasic acid anhydride are used in combination, the production conditions of the polyester (meth) acrylate (b-1) are selected, and the unsaturated polybasic acid component is introduced at the molecular terminal. It is advantageous to produce the cured product because the toughness of the cured product is improved.

When the curable resin composition of the present invention particularly requires excellent curability, strength properties and heat resistance, the unsaturated polybasic acid component of the polyester (meth) acrylate (b-1) is preferably used. Is 30 mol%, more preferably 5 mol%.
It is desirable that 0 mol%, more preferably 60 mol%, and most preferably 80 mol% or more be fumaric acid ester units. In order to convert the polyester (meth) acrylate (b-1) produced using maleic anhydride as a part of the raw material into a structure containing a fumarate unit,
For example, this can be achieved by using a primary amine or a secondary amine, a thiol, a sulfur, an organic acid or an inorganic acid as a transfer catalyst. Epoxy compounds that can be used for the polyester (meth) acrylate (b-1) include alkylene oxides. Examples of the alkylene oxide include ethylene oxide, propylene oxide,
Examples include butylene oxide, styrene oxide, phenylglycidyl ether, 1,2-epoxybutene, allyl glycidyl ether, glycidyl (meth) acrylate, and the like.

More preferred alkylene oxide is at least one alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and 1,2-epoxybutene. In addition, these exemplified compounds may be used alone or in combination of two or more.

The proportion of the unsaturated polyester (a) and the polyester (meth) acrylate (b) used depends on the viscosity and air drying property of the obtained curable resin composition and the strength and water resistance of the obtained cured product. From the balance, the weight ratio of unsaturated polyester (a): polyester (meth) acrylate (b) is in the range of 80:20 to 20:80. When the use ratio of the unsaturated polyester (a) exceeds this range, the strength and water resistance of the cured product of the curable resin composition may be reduced. If the proportion of the polyester (meth) acrylate (b) used falls below this range, the air drying property during curing may be reduced. In order to obtain good physical properties of the curable resin composition of the present invention, the curable resin composition of the present invention is regarded as 100% by weight and the unsaturated polyester (a) and the polyester (meth) acrylate (b) are used. The content as a total amount is preferably from 50 to 99 parts by weight. Still more preferably, it is 60 to 95 parts by weight, and more preferably 70 to 90 parts by weight. 75 to 90 parts by weight are most preferred.

Examples of the polymerizable monomer (c) are not particularly limited as long as they are co-curable with the unsaturated polyester (a) and the polyester (meth) acrylate (b). Specifically, for example, styrene monomers such as styrene, vinyltoluene, p-tert-butylstyrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene, p-chloromethylstyrene, divinylbenzene; Allyl ester 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, diethylene glycol diacrylate , Hydroxyethyl acrylate, hydroxypropyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, methoxydiethylene glycol acrylate, butoxydiethylene glycol acrylate, phenoxyethyl acrylate, diacrylic acid adduct of bisphenol A diglycidyl ether, trimethylolpropane triacrylate, trimethylol Ethantoria crele Door, glycerol triacrylate,
Acrylic acid derivatives such as pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; and the methacrylic acid monomers of the above compounds; vinyl ethers such as triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, hydroxybutyl vinyl ether and dodecyl vinyl ether Monomer; trimethylolpropane diallyl ether,
Allyl ether monomers such as pentaerythritol triallyl ether, allyl glycidyl ether, allyl ether of methylol melamine, adipic ester of glycerin diallyl ether, allyl acetal, allyl ether of methylol glyoxal urein; diethyl maleate, dibutyl maleate And maleic ester monomers such as dibutyl fumarate and dioctyl fumarate; N-vinylformamide; N-vinylpyrrolidone; vinyl acetate and the like. These exemplified compounds may be used alone or in combination of two or more. When particularly low odor is required among these exemplified compounds, it is desirable to use a so-called high-boiling monomer having a boiling point of 150 ° C. or more at normal pressure. Among the polymerizable monomer components used, the above-mentioned boiling point at normal pressure is 15
By having a high boiling point monomer of 0 ° C. or higher as a main component, the curable resin composition of the present invention can be a low odor resin composition. An optimum resin composition can be obtained for various uses in which odor such as styrene is a problem. More specifically, in order to obtain a low-odor curable resin composition, the polymerizable monomer component to be used is taken as 100 parts by weight, and the boiling point at normal pressure is 150-100 ° C. or more, and the high-boiling monomer is 70-100 parts by weight. It is preferable to use a part. More preferably, 80-10
0 parts by weight, most preferably 90-100 parts by weight.

The mixing ratio of the polymerizable monomer (c) is not particularly limited, but from the viewpoint of the necessity of using a resin having a low odor or a low solvent volatility, and from the viewpoints of good working viscosity and material properties.
The amount of the polymerizable monomer (c) used is preferably 1 to 50 parts by weight, and more preferably 5 to 4 parts by weight, based on 100 parts by weight of the total of the unsaturated polyester (a) and the polyester (meth) acrylate (b).
0 parts by weight is more preferred. 10 to 30 parts by weight is more preferable, and 10 to 25 parts by weight is more preferable. By mixing the components (a) to (c) in the above range, the viscosity at 25 ° C. of the resin composition of the present invention becomes 2 pa · s or less, usually 1 pa · s or less. By appropriately selecting the configurations of (1) to (c), the viscosity can be adjusted to a desired value without sacrificing the workability and the physical properties of the cured product.

The curable resin composition of the present invention can be cured by adding a polymerization initiator such as a radical polymerization initiator or a photopolymerization initiator, or by irradiating an electron beam.

As the radical polymerization initiator, for example, a polymerization initiator generally used for curing an unsaturated polyester resin, epoxy (meth) acrylate, polyester acrylate or the like is used, and specifically, benzoyl peroxide, methyl ethyl ketone Peroxide, cumene hydroperoxide, t-butyl perbenzoate,
Azobisisobutyronitrile and the like can be mentioned. These exemplified compounds may be used alone or in combination of two or more.

As the photopolymerization initiator, specifically,
Benzophenone, benzoin isobutyl ether, benzoin isopropyl ether, benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ethylphenylglyoxylate, 2-chlorothioxanthone, 2,4-diisopropylthioxane, 2, 4,6-trimethylbenzoyldiphenoylphosphine oxide and the like,
Further, various onium salt type photopolymerization initiators can also be used. Each of these exemplified compounds may be used alone,
Two or more types may be used in combination. Moreover, you may use together with a radical polymerization initiator.

The radical polymerization initiator and / or photopolymerization initiator can be appropriately selected according to the intended use, but in order to make effective use of the excellent curability of the present invention, a photopolymerization initiator is required. It is preferable to use as a so-called photocurable resin composition containing an initiator.

The amount of the radical polymerization initiator and / or the photopolymerization initiator can be appropriately determined according to the desired curing time.
0.1 to 30 parts by weight, preferably 0.1 to 30 parts by weight, based on 0 parts by weight.
It may be added in the range of 3 to 10 parts by weight. If the added amount of the radical polymerization initiator and / or the photopolymerization initiator exceeds this range, the unreacted initiator and / or the residue thereof contained in the cured product will remain, deteriorating the properties of the cured product. If the amount of the radical polymerization initiator and / or the photopolymerization initiator is less than this range, the curing speed is reduced, and the working efficiency is sacrificed.

The curable resin composition of the present invention may further contain a polymerization accelerator, for example, metal soaps such as cobalt octylate and manganese octylate, ferrocene,
Metal complexes such as cobalt complex of acetylacetone; aromatic tertiary amines such as dimethylaniline and toluidine; β-diketones such as acetylacetone and methyl acetoacetate;
Phenothiazines, diethanolamine and the like,
Each may be used alone or two or more of them may be used in combination. The amount of the polymerization accelerator to be added can be appropriately determined in accordance with a desired curing time, and for example, may be added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition. .

The curable resin composition of the present invention can be mixed with the above-mentioned polymerization initiator and, if necessary, a polymerization accelerator, and can be cured under any curing conditions and molding methods. Becomes The curing conditions and molding method are not particularly limited as long as a conventionally known technique is used.

The curable resin composition of the present invention further comprises a filler such as aluminum hydroxide, talc, silica sand, crushed stone, calcium carbonate, antimony oxide, glass flake, etc .; anhydrous fine powder silica, asbestos, clay, fatty acid amide compound Thixotropic agents such as paraffins, waxes, drying oils and the like; drying agents such as organic pigments, inorganic pigments and dyes; reinforcing materials such as carbon fiber, glass fiber and aramid fiber; ultraviolet absorbers; Inhibitors; defoamers; leveling agents; flame retardants; low shrinkage agents;

Further, the curable resin composition of the present invention can be used as long as the effect of the curable resin composition of the present invention is not adversely affected, if other curable resins such as a general unsaturated polyester resin and epoxy (meth) acrylate ( (Vinyl ester) resin, urethane (meth) acrylate resin, crosslinkable acrylic resin, epoxy resin, oxetane resin, allyl resin and the like can be used in combination. These amounts are not particularly limited as long as the effects of the curable resin composition of the present invention, that is, the air-drying property of the curable resin composition and the strength of the cured product are not affected. For example, with the curable resin composition obtained by the present invention as 100 parts by weight, 40
The range is preferably from 0 to 0 parts by weight, more preferably from 30 to
It is in the range of 0 parts by weight, and more preferably in the range of 20 to 0 parts by weight. More preferably, it is in the range of 10 to 0 parts by weight,
The range of 5 to 0 parts by weight is more preferable.

The mixing ratio of these various auxiliary materials and other curable resins with the curable resin composition of the present invention depends on the type, combination with the curable resin composition of the present invention, curing conditions, physical properties of the cured product, and the like. What is necessary is just to set arbitrarily according to a use, and it is not specifically limited. The method of mixing them may be appropriately selected according to the form and characteristics of the auxiliary material and other curable resins.

As described above, the curable resin composition of the present invention has low viscosity and low odor, and can be rapidly cured by adding a radical polymerization initiator or a photopolymerization initiator. Furthermore, since the obtained cured product is excellent in strength and water resistance, various FRP base materials, adhesives, paints, linings, coating materials such as coatings, coated flooring materials, casting, resin concrete, putty, bolt fixing materials, It can be suitably used for various applications such as printing inks, solder resists, photoresists, resins for stereolithography, etc. In particular, applications that can effectively exhibit the above features include open molds for FRP ships, bathtubs, septic tanks, etc. It is suitable as a molding resin composition. It is also suitable for a resin composition for civil engineering and building materials such as a waterproof lining material, a painted floor material, an outer wall paint and the like mainly for indoor and outdoor site construction. Also SM
A molding material containing a reinforcing material such as glass fiber such as C or BMC may be used.

[0056]

The present invention will be described in detail with reference to the following examples. Note that the present invention is not limited to the following embodiments. In the examples, “parts” means “parts by weight” unless otherwise specified.

<Resin Synthesis Example 1> 465 parts of maleic anhydride was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower and a nitrogen gas inlet tube, and heated to 125 ° C under a nitrogen stream. After warming, 54 parts of deionized water were added dropwise at the same temperature over 0.5 hour. Next, 264 parts of dicyclopentadiene was added dropwise at the same temperature over 1.5 hours, and the mixture was further stirred at the same temperature for 1.5 hours. Thereafter, 129 parts of propylene glycol, 177 parts of neopentyl glycol and 54 parts of trimethylolpropane were added, and the mixture was added under nitrogen flow.
The temperature was gradually raised to 00 ° C., and the mixture was further reacted at the same temperature for 10 hours. After confirming that 103 parts of condensed water had distilled out, the mixture was cooled, and the acid value was 25, the number average molecular weight was 1,400, and the weight average molecular weight was 33,000. Was obtained having a norbornene skeleton. The resulting unsaturated polyester was (p
-1).

In the above molecular weight measurement, Tosoh G
The PC system 8120 series was used. Detailed analysis and measurement conditions are as follows.

Column used: TSK gel SUPER HM-H (6 mm id.
X 150mm) 4 in series Solvent: Tetrahydrofuran Measurement temperature: 40 ° C Detector: Differential refractive index (RI) detector Standard substance: Polystyrene (Mn = 500, 2500, 9800, 37200,
<1899000, 707000, 1110000) <Resin Synthesis Example 2> A reaction was performed in the same manner as in Resin Production Example 1 except that 136 parts of propylene glycol and 186 parts of neopentyl glycol were used, and an acid value of 27 and a number average molecular weight of 1 were obtained.
An unsaturated polyester having a norbornene skeleton having a weight average molecular weight of 14,000 was obtained. Let the obtained unsaturated polyester be (p-2).

<Resin Synthesis Example 3>
Parts, the reaction was carried out in the same manner as in Resin Production Example 1 except that 52 parts by weight of dicyclopentadiene were used, to obtain an unsaturated polyester having a norbornene skeleton having an acid value of 28, a number average molecular weight of 2,100, and a weight average molecular weight of 13,000. . Let the obtained unsaturated polyester be (p-3).

<Resin Synthesis Example 4> 323 parts of maleic anhydride was added to a 1-liter four-necked flask equipped with a stirrer, a thermometer, a rectification column, and a nitrogen gas inlet tube, and heated to 125 ° C under a nitrogen stream. After warming, 54 parts of deionized water were added dropwise at the same temperature over 0.5 hour. Next, 396 parts of dicyclopentadiene were added dropwise at the same temperature over 1.5 hours, and the mixture was further stirred at the same temperature for 1.5 hours. Thereafter, 297 parts of triethylene glycol were added, the temperature was gradually raised to 200 ° C. in a nitrogen stream, and the reaction was continued at the same temperature for 10 hours. 2
0, number average molecular weight is 700, weight average molecular weight is 1900
Was obtained having a norbornene skeleton. Let the obtained unsaturated polyester be (p-4).

<Resin Synthesis Example 5> 172 parts of methacrylic acid and phthalic anhydride were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping funnel, and a Dean-Stark type still. 296 parts, 318 parts of diethylene glycol, 200 parts of toluene and 16 parts of paratoluenesulfonic acid were added, and the mixture was heated to 110 to 125 ° C. in an air stream, and water produced was removed by azeotropic dehydration. Reaction start 1
Five hours later, after confirming that 72 parts of produced water had distilled off, the mixture was cooled, and the content was washed once with 500 ml of saturated sodium bicarbonate and twice with 500 ml of deionized water. The internal pressure was reduced to 50 hpa with stirring while bubbling a small amount of air, and devolatilized in that state for 3 hours and further at 10 hpa for 5 hours, acid number 2, number average molecular weight 700, weight average 930 molecular weight
Was synthesized. Let the obtained polyester methacrylate be (a-1).

<Comparative Resin Synthesis Example 1> 392 parts of maleic anhydride, 129 parts of propylene glycol, and neopentyl glycol were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube. Add 177 parts and 54 parts of trimethylolpropane, and add
The temperature was gradually raised to 00 ° C., and the mixture was further reacted at the same temperature for 10 hours. After confirming that 75 parts of condensed water had been distilled off, the mixture was cooled, and the acid value was 22, the number average molecular weight was 3,200, and the weight average molecular weight was 53,000. Was obtained. Let the obtained unsaturated polyester be (p-5).

<Comparative Resin Synthesis Example 2> A liter of maleic anhydride, 129 parts of propylene glycol, and 129 parts of neopentyl glycol were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a rectification tower, and a nitrogen gas inlet tube. Add 177 parts and 54 parts of trimethylolpropane, and add
The temperature was gradually raised to 00 ° C., and the reaction was continued at the same temperature for 10 hours. After confirming that 70 parts of condensed water had been distilled off, the mixture was cooled, and the acid value was 25, the number average molecular weight was 2,400, and the weight average molecular weight was 14,000. Was obtained. Let the obtained unsaturated polyester be (p-6).

Examples 1 to 12 and Comparative Examples 1 to 6 Using the unsaturated polyesters and polyester methacrylates obtained in Resin Synthesis Examples 1 to 5 and Comparative Resin Synthesis Examples 1 and 2, various polymerizable monomers were used. A resin composition was prepared by mixing a resin, a radical polymerization initiator and a polymerization accelerator, and the resin viscosity, room temperature pot life, dryness to the touch, cast plate tensile strength and low odor were measured. The results are shown in Tables 1 to 3. In addition, the measuring method of various physical properties is shown below.

(Resin Viscosity) The resin compositions mixed except for the radical polymerization initiator were measured at 25 ° C. using a Brookfield viscometer according to JIS K-6901.

(Normal Temperature Pot Life)
The pot life at room temperature (25 ° C.) was measured according to IS K-6901.

(Dry to the touch) Glass plate (150 m in size)
m × 100 mm) using a bar coater.
Each resin composition was applied so as to have a thickness of 0 μm, and allowed to stand at room temperature. Six hours after the completion of the application, the adhesiveness of the coating film surface was confirmed by finger touch, and the results were as follows. And

(Tensile Strength of Casting Plate) Each resin composition was cast into a glass casting container (thickness: 3 mm), cured at room temperature, left to stand all day and night, and then subjected to after-curing at 110 ° C. for 2 hours. For the cast plate, the tensile strength and the tensile elongation were measured according to JIS K-7113.

(Low odor) Bottom area 625 cm ² , height 3
A semiconductor odor sensor (New Cosmos Electric Model XP329) having an intake pipe and an exhaust pipe was mounted on the top of a 0 cm rectangular transparent transparent acrylic container. Next, 10 g of each resin composition was measured in a cylindrical open container having a bottom area of 80 cm ² and a height of 1 cm, left at the bottom of the closed container for 90 minutes at room temperature, and the odor intensity at that time was measured. Was. The odor sensitivity (mV) in the table means that the smaller the number is, the less the volatilization of the substance generating the odor is. In general, when the odor sensitivity is several tens of mV, the odor is perceived clearly at 100 mV, although there is an odor, but when the odor sensitivity is several hundred mV, a strong odor is felt.

[0071]

[Table 1]

From the results shown in Table 1, when the unsaturated polyester containing no norbornene skeleton of Comparative Example was used, the drying property of the air contact surface was reduced. As shown in Comparative Example 1,
When the weight average molecular weight of the unsaturated polyester is extremely large, the viscosity of the resin composition increases, which may have an adverse effect on workability. It is also found that the tensile strength of the cured product is greatly improved by adding the polyester methacrylate (b).

[0073]

[Table 2]

From Examples 6 and 7 in Table 2, it can be seen that the resin composition of the present invention maintains the working viscosity and has good tensile strength even when the content of the polymerizable monomer is reduced. In addition, as shown in Comparative Example 5, only the unsaturated polyester containing a norbornene skeleton increases the resin viscosity and decreases the tensile strength of the cured product. As shown in Comparative Example 6, when only the polyester methacrylate is used, the drying property of the air contact surface is clearly reduced. Further, Examples 7 and 8 show that even when the unsaturated polyester (a) having a norbornene skeleton and the polyester methacrylate (b) are mixed in a wide range, the excellent effects of the present invention can be sufficiently maintained.

[0075]

[Table 3]

From the results in Table 3, it can be seen that even when a polymerizable monomer other than styrene is used as the polymerizable monomer (c), the polymer has low viscosity and low odor, and has excellent surface drying properties upon curing. It is clear that the cured product has excellent tensile strength. In particular, by using the polymerizable monomer having a high boiling point shown in Examples, the odor of the resin composition can be significantly suppressed.

<Resin Synthesis Example 7> 172 parts of methacrylic acid and phthalic anhydride were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping funnel, and a Dean-Stark type still. 148 parts, 212 parts of diethylene glycol, 150 parts of toluene, and 10 parts of paratoluenesulfonic acid were added, and the mixture was heated to 110 to 125 ° C. in an air stream, and water produced was removed by azeotropic dehydration. Reaction start 1
Five hours later, after confirming that 54 parts of produced water had distilled off, the mixture was cooled, and the contents were washed once with 500 ml of saturated sodium hydrogen carbonate and twice with 500 ml of deionized water. The internal pressure was reduced to 50 hpa with stirring while bubbling a small amount of air, and devolatilized in that state for 3 hours and further at 10 hpa for 5 hours. The acid value was 2, the number average molecular weight was 480, and the weight averaged. 580 molecular weight
Was synthesized. Let the obtained polyester methacrylate be (a-2).

<Resin Synthesis Example 8> 172 parts of methacrylic acid and phthalic anhydride were placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping funnel, and a Dean-Stark type still. 444 parts, 424 parts of diethylene glycol, 250 parts of toluene and 21 parts of paratoluenesulfonic acid were added, and the mixture was heated to 110 to 125 ° C. in an air stream, and the produced water was removed by azeotropic dehydration. Reaction start 1
Five hours later, after confirming that 90 parts of produced water had distilled off, the mixture was cooled, and the content was washed once with 500 ml of saturated sodium bicarbonate and twice with 500 ml of deionized water. The internal pressure was reduced to 50 hpa with stirring while bubbling a small amount of air, and devolatilized in that state for 3 hours and further at 10 hpa for 5 hours, and the acid value was 2, the number average molecular weight was 1020, and the weight averaged. Molecular weight 15
30 polyester methacrylates were synthesized. Let the obtained polyester methacrylate be (a-3).

<Resin Synthesis Example 9> 172 parts of methacrylic acid and phthalic anhydride were placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping funnel, and a Dean-Stark type still. 740 parts, 636 parts of diethylene glycol, 350 parts of toluene and 31 parts of paratoluenesulfonic acid were added, and the mixture was heated to 110 to 125 ° C. in an air stream, and water produced was removed by azeotropic dehydration. Reaction start 1
After 5 hours, it was confirmed that 126 parts of produced water had been distilled off, and then cooled, and the content was washed with 800 ml of saturated sodium hydrogen carbonate.
Once, and twice with 800 ml of deionized water. Then, the organic phase is heated to 90 ° C., and the internal pressure is reduced to 50 hpa while stirring while bubbling a small amount of air. For 5 hours,
Acid value 5, number average molecular weight 1420, weight average molecular weight 2
560 polyester methacrylates were synthesized. Let the obtained polyester methacrylate be (a-4).

(Examples 13 to 15) Resin synthesis examples 2, 7 to
Using the unsaturated polyester and polyester methacrylate obtained in 9 above, a resin composition was prepared by mixing with a polymerizable monomer, a radical polymerization initiator and a polymerization accelerator, and the resin viscosity, room temperature pot life, and touch drying The properties and the tensile strength of the cast plate were measured. Table 4 shows the results.

[0081]

[Table 4]

From the results in Table 4, it can be seen that increasing the molecular weight of the polyester methacrylate (b) increases the viscosity of the resin composition. However, at least in the range described in the examples, the working viscosity is sufficiently high. The air-drying property and the tensile strength of the cured product are within the range where there is no problem.

<Resin Synthesis Example 10> 72 parts of acrylic acid and 3.8 parts of triethylbenzylammonium chloride were added to a four-necked flask equipped with a stir bar, a thermometer, a gas inlet tube, a dropping funnel and a cooling tube, and air was added. Heated to 100 ° C. under air flow. Then, propylene oxide (58 parts) was added dropwise from the dropping funnel at the same temperature over 1 hour, and then 98 parts of maleic anhydride was added while paying attention to heat generation, followed by stirring for 1 hour. Further, the operation of adding and reacting 58 parts of propylene oxide and 98 parts of maleic anhydride was repeated three times each,
Finally, propylene oxide (70 parts) was added dropwise at the same temperature over 1 hour, and the mixture was further reacted for 3 hours. After the completion of the reaction, the internal temperature of the flask was lowered to 80 ° C., and while stirring, the internal pressure was reduced to 50 hpa while bubbling a small amount of air, and devolatilized for 1 hour in that state. A polyester acrylate having a weight average molecular weight of 750 and 800 was synthesized. Let the obtained polyester acrylate be (a-5).

Resin Synthesis Example 11 130 parts of hydroxyethyl methacrylate, 294 parts of maleic anhydride, and 2.7 parts of triethylbenzylammonium chloride were added to an autoclave equipped with a stir bar, a gas inlet tube, and a thermometer, and sealed. To 100 ° C. Next, 145 parts of ethylene oxide were injected at the same temperature over 2 hours, and reacted for 3 hours. After completion of the reaction, the internal temperature is 80 ° C.
The internal pressure was reduced to 50 hpa while bubbling a small amount of air under stirring, and devolatilized for 1 hour in that state.
Polyester methacrylate having an acid value of 3, a number average molecular weight by GPC of 540, and a weight average molecular weight of 620 was synthesized. The obtained polyester methacrylate was (a)
−6).

<Resin Synthesis Example 12> In an autoclave equipped with a stir bar, a gas inlet tube and a thermometer, 228 parts of a maleic acid reaction product of hydroxyethyl methacrylate, 196 parts of maleic anhydride, 444 parts of phthalic anhydride and 443 parts of triethylbenzyl were added. 5.6 parts of ammonium chloride were added, and the mixture was heated to 100 ° C. in a sealed state. Next, 290 parts of ethylene oxide were injected at the same temperature over 2 hours, and 3 more parts were added.
Allowed to react for hours. After completion of the reaction, the internal temperature was lowered to 80 ° C., and while stirring, the internal pressure was reduced to 50 hp while bubbling a small amount of air.
a, and devolatilized for 1 hour in that state.
A polyester methacrylate having a number average molecular weight of 1,120 and a weight average molecular weight of 1,350 by PC was synthesized.
Let the obtained polyester methacrylate be (a-7).

<Resin Synthesis Example 13> 130 parts of hydroxyethyl methacrylate, 98 parts of maleic anhydride and 296 parts of phthalic anhydride were placed in a four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a dropping funnel and a cooling tube. And 4.8 parts of triethylbenzylammonium chloride, and the mixture was heated to 100 ° C. in an air stream. Next, 447 parts of glycidyl methacrylate was added dropwise at the same temperature over 2 hours,
The reaction was further performed for 3 hours. After the completion of the reaction, the internal temperature of the flask was lowered to 80 ° C., and while stirring, the internal pressure was reduced to 50 hpa while bubbling a small amount of air, and devolatilized for 1 hour in that state. 950,
A polyester methacrylate having a weight average molecular weight of 1080 was synthesized. Let the obtained polyester methacrylate be (a-8).

<Comparative resin production example 3> In a four-necked flask equipped with a stir bar, a thermometer, a gas inlet tube and a cooling tube, 215 parts of methacrylic acid, 1135 parts of a bisphenol A type epoxy resin (epoxy equivalent 454) and After charging 6.8 parts of triethylamine, the temperature was raised to 110 ° C. in an air stream, and the reaction was carried out at the same temperature for 8 hours to synthesize an epoxy acrylate resin having an acid value of 7, a number average molecular weight of 11,10, and a weight average molecular weight of 2,080. . Let the obtained epoxy methacrylate be (e-1).

<Comparative resin production example 4> A four-necked flask equipped with a stir bar, a thermometer, a gas inlet tube, a dropping funnel and a cooling tube was charged with 85 parts of diethylene glycol and bisphenol A.
Of ethylene oxide adduct (hydroxyl equivalent: 162) and 0.3 part of dibutyltin dilaurate were heated to 60 ° C. under a nitrogen stream, and 348 parts of 2,4-tolylene diisocyanate was added dropwise at the same temperature in one hour. did. Then, 288 parts of 2-hydroxypropyl methacrylate was added dropwise at 1 hour in the air at the same temperature, and the reaction was carried out at the same temperature for 5 hours. A methacrylate was synthesized. The obtained urethane methacrylate was converted to (u-1)
And

(Examples 16 to 19 and Comparative Examples 7 and 8) Unsaturated polyesters and polyesters (meth) obtained by Resin Production Examples 2 and 10 to 13 and Comparative Resin Production Examples 3 and 4
Using acrylate, epoxy methacrylate and urethane methacrylate, a resin composition was prepared by mixing with a polymerizable monomer, a radical polymerization initiator and a polymerization accelerator, and the resin viscosity, room temperature pot life, dryness to the touch and injection The template tensile strength was measured. Table 5 shows the results.

[0090]

[Table 5]

From the results shown in Table 5, one or more compounds selected from the group consisting of (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group and (meth) acrylate having a carboxylic acid group were used as starting materials. The polyester (meth) acrylate (b-1) produced from an alkylene oxide and an unsaturated polybasic acid anhydride and / or a saturated polybasic acid has a narrow molecular weight distribution, and therefore can give a resin composition having a particularly low viscosity. I understand.
Further, the viscosity of the resin composition is high in any composition obtained by dissolving unsaturated polyester and general epoxy methacrylate or urethane methacrylate in a polymerizable monomer,
It is also inferior in air drying properties.

<Resin Synthesis Example 14> 86 parts of methacrylic acid and 3.6 parts of triethylbenzylammonium chloride were added to a four-necked flask equipped with a stir bar, a thermometer, a gas inlet tube, a dropping funnel, and a cooling tube. 100 ° C under air flow
Until heated. Next, 58 parts of propylene oxide 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, propylene oxide 5
8 parts, phthalic anhydride 148 parts, propylene oxide 58
And 98 parts of maleic anhydride in that order, and finally 70 parts of propylene oxide were added dropwise at the same temperature over 1 hour, and the mixture was further reacted for 3 hours. After the reaction is completed, the internal temperature of the flask is set to 80.
C., while stirring and bubbling a small amount of air, the internal pressure was reduced to 50 hpa, and devolatilized for 1 hour in that state. The acid value was 1, the number average molecular weight by GPC was 710, the weight average molecular weight was 760, A polyester methacrylate having a transfer rate of maleic acid to fumaric acid of 5% was synthesized. Let the obtained polyester methacrylate be (a-9).

The NMR was obtained from Barian 400M.
The measurement was performed using Hz-proton NMR and deuterated chloroform as a solvent. The rate of transfer from maleic acid to fumaric acid was calculated from the area ratio between the peak at which the chemical shift (δ) value was 6.1 (derived from the maleic ester structure) and the peak at 6.9 ppm (derived from the fumaric acid ester structure). did. The following NMR measurement was also performed under the same conditions.

<Resin Synthesis Example 15> 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. 100 ° C under air flow
Until heated. Next, 58 parts of propylene oxide 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, propylene oxide 5
8 parts, 148 parts of phthalic anhydride, 58 propylene oxide
And 98 parts of maleic anhydride in that order, and finally 70 parts of propylene oxide were added dropwise at the same temperature over 1 hour, and the mixture was further reacted for 3 hours. After the reaction is completed, the internal temperature of the flask is set to 80.
C., while stirring, while bubbling a small amount of air, reducing the internal pressure to 50 hpa, devolatilizing for 1 hour in that state, adding 7.1 parts of morpholine at the same temperature after completion of devolatilization, and further reacting for 1 hour. Polyester methacrylate having an acid value of 1, a number-average molecular weight by GPC of 710, a weight-average molecular weight of 780, and a transfer rate of maleic acid to fumaric acid of 94% by NMR was synthesized. Let the obtained polyester methacrylate be (a-10).

Examples 20 and 21 and Comparative Example 9 Using the unsaturated polyester and polyester methacrylate obtained in Resin Production Examples 2 and 14.15, a polymerizable monomer, a radical polymerization initiator and a polymerization accelerator were used. A resin composition mixed with the agent was prepared, and the resin viscosity, room temperature pot life, dryness to the touch, and cast plate tensile strength were measured. Table 6 shows the results. The method for measuring the water resistance of the cast plate is described below.

(Water Resistance of Casting Plate) Each resin composition was cast into a glass casting container (thickness: 3 mm), cured at room temperature, allowed to stand for 24 hours, and then subjected to after-curing at 110 ° C. for 2 hours. The casting plate was cut into a test piece of 75 mm × 25 mm, immersed in boiling deionized water, and the time until cracks occurred in the test piece was measured.

[0097]

[Table 6]

From the results shown in Table 6, one or more compounds selected from the group consisting of (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group and (meth) acrylate having a carboxylic acid group were used as starting materials. The polyester (meth) acrylate (b-1) produced from the alkylene oxide and the unsaturated polybasic anhydride and / or the saturated polybasic anhydride has improved water resistance as compared with the unsaturated polyester alone of Comparative Example. However, it has been clarified that particularly when the fumaric acid content is large, the water resistance is significantly improved.

Using the resin compositions before casting in Examples 1 to 4, lamination molding was performed on a 450-ply glass ply 2-ply. After curing, an FRP molded article having a good appearance was obtained.

[0100]

The curable resin composition of the present invention provides a curable resin composition which has a low viscosity and low odor, has excellent surface drying properties upon curing, and can provide a cured product having excellent water resistance and strength. be able to. The curable resin composition of the present invention is used for various FRP
Base materials, adhesives, paints, linings, coatings such as coatings, floor coverings, casting, resin concrete, putty,
It can be suitably used for various applications such as bolt fixing materials, printing inks, solder resists, photoresists, stereolithography resins, etc. In particular, applications that can effectively exhibit the above features include FRP ships, bathtubs, and septic tanks. It is suitable for civil engineering and construction materials such as waterproof lining materials, painted floor materials, exterior wall paints, etc., mainly for open mold molding or indoor and outdoor site construction.

The polyester (meth) acrylate (b) of the present invention is a compound selected from the group consisting of (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group and (meth) acrylate having a carboxylic acid group. Polyester (meth) prepared from alkylene oxide and unsaturated polybasic anhydride and / or saturated polybasic anhydride using one or more compounds as starting materials
It is preferably acrylate (b-1). This reaction mode is a sequential ring-opening addition reaction using a weak acid or a weak base, in which by-products generated by a side reaction such as a transesterification reaction are reduced, and a polyester (meth) acrylate having a uniform molecular weight and a low viscosity is obtained. Therefore, the present invention is one of the preferred embodiments.

Continued on the front page F term (reference) 4J027 AB06 AB07 AB08 AB13 AB15 AB16 AB17 AB18 AB19 AB23 AB24 AB25 AB26 AB29 AB33 AJ08 BA04 BA05 BA07 BA17 BA18 BA19 BA20 BA21 BA25 BA26 BA27 BA28 BA29 CB04 CB09 CB10 CC02 CD08

Claims (3)

[Claims] 1. An unsaturated polyester having a norbornene skeleton (a), a polyester (meth) acrylate (b)
And a curable resin composition containing a polymerizable monomer (c). 2. The unsaturated polyester (a) having a norbornene skeleton, wherein the introduction rate of the norbornene skeleton is 5 to 100 mol% based on all polybasic acid components constituting the unsaturated polyester (a). The curable resin composition according to claim 1. 3. The polyester (meth) acrylate (b) is one of compounds selected from the group consisting of (meth) acrylic acid, (meth) acrylate having an alcoholic hydroxyl group and (meth) acrylate having a carboxylic acid group. A polyester (meth) acrylate (b-1) produced from an alkylene oxide and an unsaturated polybasic anhydride and / or a saturated polybasic anhydride using at least one compound as a starting material, The curable resin composition according to claim 1.