JP3467884B2 - Oligomer excellent in curability, method for producing the oligomer, curable resin composition using the oligomer, and cured product obtained by curing the composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel oligomer and a curable resin composition. More specifically, an oligomer that provides a cured product having improved curability and excellent toughness, a method for producing the oligomer, a curable resin composition using the oligomer, and a cured product obtained by curing the composition. Regarding

[0002]

2. Description of the Related Art Diallyl phthalate (hereinafter referred to as "DAP")
Abbreviated. The DAP resin using (1) as a monomer has excellent electrical characteristics, thermal characteristics, chemical characteristics, etc., and is used for molding materials, decorative boards, laminated boards and the like. However, since the pre-polymerization of the monomer is used and the solid pre-polymer is isolated before use, the pre-polymer must be melted once and inevitably subjected to high temperature molding. It has a drawback that cannot be achieved. Also,
Efficient production of prepolymer is an important issue, and at present, it cannot be said that the production method is satisfactory.

When diallyl terephthalate having excellent symmetry is used as a monomer, the heat resistance is improved, but the secondary cured product is very brittle and not practical. Moreover, when diallyl isophthalate is used, it has excellent heat resistance, but since it is expensive in monomer, it is used only for limited purposes. Further, an allyl ester oligomer having an allyl ester group at the terminal and having the following structure derived from a polyvalent saturated carboxylic acid and a polyvalent saturated alcohol inside is also known.

[0004]

[Chemical 3]

Here, X represents an organic residue derived from a polyvalent saturated carboxylic acid, and Y represents an organic residue derived from a polyvalent saturated alcohol.

In this case, when terephthalic acid having excellent symmetry is used as the polyvalent saturated carboxylic acid, a cured product having very excellent physical properties is obtained. However, in order to improve the physical properties, it is necessary to make the molecular weight higher than a certain level, but the higher the molecular weight, the lower the double bond concentration and the polymerization rate becomes extremely slow. Further, in any of the methods, the curing rate of the allyl group in curing is slow, and thus a molding method under high temperature is required, and it is difficult to give a cured product sufficient performance under mild conditions. Further, in JP-A-4-146919, as an allyl oligomer having excellent curability, an organic residue consisting of a derivative of a fatty acid having an unsaturated group such as maleic acid and fumaric acid in the skeleton of an allyl ester oligomer is appropriately prepared. Introduced groups are described. According to this method, maleic acid or fumaric acid accelerates the curing of the allyl group, and thus the curability is excellent.

Further, by using a reactive monomer such as styrene as a diluent, curing can be further accelerated. However, the allyl oligomer having maleic acid has a problem that the curing is slow even if a reactive monomer such as styrene is used in combination unless the temperature is substantially high. Further, when an allyl oligomer having fumaric acid is cured, the copolymerization of the allyl group and fumaric acid is excellent, and therefore curing can be performed under relatively mild conditions. However, the allyl oligomer usually undergoes a synthetic reaction at a high temperature, but at that time, thermal polymerization is likely to occur between the allyl group and fumaric acid, and particularly in the production of a high molecular weight oligomer,
Control of thermal polymerization was difficult. Further, the cured product of the allyl oligomer having fumaric acid was not sufficiently satisfactory in terms of toughness.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a novel oligomer having an allyl ester group which gives a cured product having excellent curability and toughness, a method for producing the oligomer, and a curable resin composition using the oligomer. And a cured product obtained by curing the composition.

[0009]

In the production of unsaturated polyester which is a thermosetting resin, maleic anhydride, fumaric acid and the like are used as the unsaturated dibasic acid as a raw material.
However, itaconic acid is known to be used as the unsaturated dibasic acid when imparting toughness to the cured product. The present inventors have paid attention to this fact, and as a result of earnest research, when itaconic acid was contained in the skeleton of an oligomer having an allyl ester group at the molecular end, the toughness of the cured product was excellent and It was found that the curability of the oligomer is also excellent and that it can be cured without problems under relatively mild conditions.
The present invention has been accomplished.

That is, the present invention (I) is represented by the following general formula (1)
Is an oligomer having at least one of the groups represented by as a terminal group and having the group represented by the following general formula (2) as a repeating unit. General formula (1)

[0011]

[Chemical 4]

(In the general formula (1), R is a kind selected from the group consisting of an aliphatic dicarboxylic acid which is an independent organic residue and has an unsaturated group, a saturated aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. Moreover, in general formula (1), X represents a C1-C3 alkyl group or an allyl group. However, at least one of Xs present in one molecule is an allyl group.
Further, when the terminal structure is on the right side of the group represented by the general formula (2), the terminal structure is X instead of the general formula (1). ) General formula (2)

[0013]

[Chemical 5]

(In the general formula (2), R is a kind selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, each of which is an independent organic residue and has an unsaturated group. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. In the general formula (2), B each independently represents one or more polyvalent organic residues derived from a polyhydric alcohol. However, B may have a branched structure having an end group of the general formula (1) and a repeating unit of the general formula (2) by an ester bond. The total number of repeating groups represented by the general formula (2) contained in one molecule is in the range of 1 to 20. )

The present invention (II) is a process for producing the oligomer of the present invention (I), which comprises the following steps. In the presence of a catalyst, a step of transesterifying a dicarboxylic acid diester mixture containing itaconic acid diester as an essential component with a polyhydric alcohol to obtain an oligomer

The present invention (III) comprises the oligomer of the present invention (I) in an amount of 30% by weight based on the total amount of the curable resin composition.
It is a curable resin composition characterized by being contained in the range of 80 wt%.

The present invention (IV) contains 0.1 to 5 parts by weight of at least one radical polymerization initiator based on 100 parts by weight of the curable resin composition described in the present invention (III). It is a curable resin composition characterized by the above.

The present invention (V) is a cured product obtained by curing the curable resin composition according to the present invention (III) or the present invention (IV).

The term "total amount of curable resin composition" described in the present specification means the total amount of radically curable compounds containing the oligomer of the invention (I) contained in the composition as an essential component. To do.

Further, the present invention comprises the following items, for example.

[1] An oligomer having at least one or more of the groups represented by the following general formula (1) as a terminal group and having the group represented by the following general formula (2) as a repeating unit. General formula (1)

[0022]

[Chemical 6]

(In the general formula (1), R is a group selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, each of which is an independent organic residue and has an unsaturated group. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. Moreover, in general formula (1), X represents a C1-C3 alkyl group or an allyl group. However, at least one of Xs present in one molecule is an allyl group.
Further, when the terminal structure is on the right side of the group represented by the general formula (2), the terminal structure is X instead of the general formula (1). ) General formula (2)

[0024]

[Chemical 7]

(In the general formula (2), R is a kind selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, each of which is an independent organic residue and has an unsaturated group. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. In the general formula (2), B each independently represents one or more polyvalent organic residues derived from a polyhydric alcohol. However, B may have a branched structure having an end group of the general formula (1) and a repeating unit of the general formula (2) by an ester bond. The total number of repeating groups represented by the general formula (2) contained in one molecule is in the range of 1 to 20. )

[2] The total number of organic residues derived from itaconic acid with respect to the total number of Rs contained in one molecule is 10
It is characterized by being mol% to 80 mol% [1]
The oligomer according to 1.

[3] The method for producing an oligomer according to [1] or [2], which comprises the following steps. In the presence of a catalyst, a step of transesterifying a dicarboxylic acid diester mixture containing itaconic acid diester as an essential component with a polyhydric alcohol to obtain an oligomer

[4] The method for producing an oligomer according to [3], wherein the catalyst used in the step described in [3] is at least one catalyst containing dibutyltin oxide.

[5] The oligomer according to any one of [1] and [2] is used in an amount of 3 relative to the total amount of the curable resin composition.
A curable resin composition, which is contained in the range of 0% by weight to 80% by weight.

[6] The oligomer according to either [1] or [2] is used in an amount of 3 relative to the total amount of the curable resin composition.
0% to 80% by weight, the balance being at least one selected from the group consisting of other unsaturated polyesters, vinyl ester resins and reactive diluents, a curable resin composition.

[7] The reactive diluent is unsaturated fatty acid ester, aromatic vinyl compound, unsaturated fatty acid and its derivative, unsaturated dibasic acid and its derivative, and saturated fatty acid or aromatic carboxylic acid vinyl or allyl. The curable resin composition according to [6], which is at least one selected from the group consisting of esters and derivatives thereof.

[8] The reactive diluent is methyl (meth)
Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (iso) bornyl (meth) acrylate, phenyl (meth) acrylate, Benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, biphenyl (meth) acrylate, bromobenzyl At least one unsaturated fatty acid selected from the group consisting of (meth) acrylate, glycidyl (meth) acrylate, and alkylamino (meth) acrylate. Curable resin composition having the constitution [6] that.

[0033]

[9] The reactive diluent comprises styrene, divinylbenzene, ethylvinylbenzene, α-methylstyrene, α-ethylstyrene, α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene and methoxystyrene. The curable resin composition according to [6], which is at least one aromatic vinyl compound selected from the group.

[10] The reactive diluent is at least one selected from the group consisting of (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and (meth) acrylic acid. The curable resin composition according to [6], which is the above unsaturated fatty acid and its derivative.

[11] The reactive diluent is N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N- Carboxyphenyl maleimide, maleic acid, maleic anhydride, dimethyl maleate,
Characterized in that it is at least one or more unsaturated dibasic acid selected from the group consisting of diethylmalate, fumaric acid, dimethylfumarate, diethylfumarate, itaconic acid, dimethylitaconate and diethylitaconate and derivatives thereof. The curable resin composition according to [6].

[12] The reactive diluent is vinyl acetate,
A vinyl or allyl ester of at least one saturated fatty acid or aromatic carboxylic acid selected from the group consisting of vinyl propionate, vinyl benzoate, vinyl n-butyrate, allyl acetate, allyl propionate, allyl benzoate and derivatives thereof. Curable resin composition as described in [6] characterized by the above.

[13] 0.1 part by weight to 5 parts by weight of at least one radical polymerization initiator based on 100 parts by weight of the curable resin composition described in any one of [5] to [12]. A curable resin composition comprising:

[14] A cured product obtained by curing the curable resin composition according to any one of [5] to [13].

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. First, the oligomer of the present invention (I) will be described. The present invention (I) is an oligomer having at least one group represented by the following general formula (1) as a terminal group and a group represented by the following general formula (2) as a repeating unit. General formula (1)

[0040]

[Chemical 8]

(In the general formula (1), R is a group selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, each of which is an organic residue and has an unsaturated group. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. Moreover, in general formula (1), X represents a C1-C3 alkyl group or an allyl group. However, at least one of Xs present in one molecule is an allyl group.
Further, when the terminal structure is on the right side of the group represented by the general formula (2), the terminal structure is X instead of the general formula (1). ) General formula (2)

[0042]

[Chemical 9]

(In the general formula (2), R is a group selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, each of which is an independent organic residue and has an unsaturated group. An organic residue derived from the above dicarboxylic acids, provided that R present in one molecule
At least one of the is an organic residue derived from itaconic acid. In the general formula (2), B each independently represents one or more polyvalent organic residues derived from a polyhydric alcohol. However, B may have a branched structure having an end group of the general formula (1) and a repeating unit of the general formula (2) by an ester bond. The total number of repeating groups represented by the general formula (2) contained in one molecule is in the range of 1 to 20. )

In the general formula (1), X represents an alkyl group having 1 to 3 carbon atoms or an allyl group. However, at least one of Xs present in one molecule is an allyl group.

When the group represented by the general formula (2) has a terminal structure on the right side, the terminal structure is X instead of the general formula (1).

The alkyl group mentioned here represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group or the like. In the oligomer of the present invention (I), even if all of the part represented by X in the terminal group represented by the general formula (1) is an allyl group, a part is an allyl group and the other part is an alkyl group. Means that it can be. However, at least one of Xs present in one molecule must be an allyl group.

Further, "when the group represented by the general formula (2) has a terminal structure on the right side, the terminal structure is X, not the general formula (1)." The terminal means that an allyl group or an alkyl group must be bonded to R by an ester bond.

In the general formulas (1) and (2), R is
Each is an independent organic residue and is an organic residue derived from one or more dicarboxylic acids selected from the group consisting of an aliphatic dicarboxylic acid having an unsaturated group, a saturated aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. .

However, at least one of Rs present in one molecule must be an organic residue derived from itaconic acid.

Specific examples of the divalent carboxylic acid which induces R include maleic acid, fumaric acid, itaconic acid, citraconic acid, and saturated aliphatic dicarboxylic acids such as succinic acid, adipic acid, suberic acid, terephthalic acid and isophthalic acid. , 1,
3- or 1,4-cyclohexanedicarboxylic acid, 1,
4- or 1,5- or 2,7-naphthalene dicarboxylic acid, diphenyl-m, m'-dicarboxylic acid, diphenyl-p, p'-dicarboxylic acid, benzophenone-4,4 '
-Dicarboxylic acid, p-phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid, tetrachlorophthalic acid, endic acid anhydride, chlorendic acid anhydride and the like.

This component is not necessarily an organic residue derived from one kind of carboxylic acid, and the total number of organic residues derived from itaconic acid to the total number of R contained in one molecule is 10 mol%. Is 80 mol% and the balance is an organic residue derived from at least one dicarboxylic acid selected from the group consisting of an aliphatic dicarboxylic acid having an unsaturated group, a saturated aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. preferable.

When the R component contains an organic residue derived from itaconic acid, the curing of the terminal allyl group is promoted.
Further, the cured product after curing has excellent toughness. On the other hand, when the content of the organic residue derived from the R component, itaconic acid, exceeds 80 mol%, the surface hardness increases, but
The heat resistance tends to decrease. If it is less than 10 mol%, curing tends to be delayed.

In the general formula (2), each B independently represents one or more polyvalent organic residues derived from polyhydric alcohol. However, B may have a branched structure having an end group of the general formula (1) and a repeating unit of the general formula (2) by an ester bond.

As used herein, "B is independent of each other" means
In the following structural formula (1), which is an example of the repeating unit represented by the general formula (2), it means that each of n B's contained in the repeating structure is an independent organic residue. . Structural formula (1)

[0055]

[Chemical 10]

(In the structural formula (1), each independently represents one or more polyvalent organic residues derived from diol, n represents an integer of 1 to 20. n represents an integer of 1 to 20. R is an independent organic residue and is derived from at least one dicarboxylic acid selected from the group consisting of an aliphatic dicarboxylic acid having an unsaturated group, a saturated aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. (However, at least one of Rs present in one molecule is an organic residue derived from itaconic acid.)

For example, n B in the structural formula (1)
Are all organic residues derived from different diols (ie, organic residues derived from n kinds of diols are 1
Each of them), or all of the organic residues derived from the same diol (that is, n organic residues derived from one type of diel), or n of B, Any mixed structure may be used, some of which are organic residues derived from the same diol and some of which are organic residues derived from another type of diol. Furthermore, the mixed structure may be completely random or may be partially repeated.

Specific examples of the polyol for deriving B include ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol and 1,4-. Or 1,3-cyclohexanediol, 1,4- or 1,3-cyclohexanedimethanol, 1,3-butanediol, neopentyl glycol, p-xylene glycol, styrene glycol, bisphenol A / propylene oxide adduct, bisphenol A -Ethylene oxide adduct and the like can be mentioned.

Examples of other polyols which induce B include trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and sorbitol.

The component B does not necessarily have to be an organic residue derived from one kind of polyol, but a polyol having a valence of 3 or more improves the heat resistance, but significantly increases the viscosity of the allyl ester oligomer produced. It is preferable to keep the amount to a small amount.

The total number of repeating groups represented by the general formula (2) contained in one molecule is in the range of 1 to 20. In the case of n> 20, the viscosity of the reaction solution becomes too high during the synthesis of the oligomer, and the risk of thermal polymerization increases, which is not preferable. Although low molecular weight raw material monomers such as a diallyl ester monomer may remain in the synthesized oligomer, these residual monomers can be used as they are without separation.

Next, the present invention (II) will be described in detail. The present invention (II) is a method for producing the oligomer of the present invention (I), which comprises the following steps. In the presence of a catalyst, a step of transesterifying a dicarboxylic acid diester mixture containing itaconic acid diester as an essential component with a polyhydric alcohol to obtain an oligomer

The method of synthesizing the oligomer used in the present invention is not particularly limited.
It can be synthesized by the method described in Japanese Patent No. 146919.

On the other hand, the catalyst used in the step is not particularly limited as long as it is a catalyst which can be generally used in a transesterification reaction. However, it is preferable to contain dibutyltin dioxide.

The molecular weight of the obtained oligomer is the gel permeation chromatography method (hereinafter,
Abbreviated as "GPC". It is preferable that the polystyrene-converted average molecular weight (Mn) and the weight-average molecular weight (Mw) measured in the above are in the ranges of 500 to 30,000 and 1,000 to 100,000, respectively. In addition, as described above, after the synthesis of the oligomer, a low-molecular-weight raw material monomer such as a diallyl ester monomer may remain in the oligomer, but it can be used as it is without separation.

When synthesizing the oligomer of the present invention, a dibasic acid having an alkyl group having about 1 to 3 carbon atoms can be used as one of the raw material monomers for providing the dicarboxylic acid structure. In this case, even if the oligomer whose terminal is the alkyl group remains, it can be used as it is without separation.

Next, the present invention (III) and the present invention (I
V) will be described in detail. The present invention (III) is
A curable resin composition comprising the oligomer of the invention (I) in an amount of 30% by weight to 80% by weight based on the total amount of the curable resin composition.

The present invention (IV) also includes the present invention (II
With respect to 100 parts by weight of the curable resin composition described in I),
A curable composition comprising 0.1 to 5 parts by weight of at least one radical polymerization initiator.

The curable resin composition of the present invention (III) contains the oligomer of the present invention (I) in the range of 30% by weight to 80% by weight based on the total amount. The component other than the oligomer of the present invention (I) contained in the curable resin composition is not particularly limited, but the present invention (I) is used for the purpose of improving various physical properties such as polymerizability and surface hardness. It is desirable that at least one selected from the group consisting of unsaturated polyesters other than the oligomers, vinyl ester resins, and reactive diluents.

The unsaturated polyester is a known unsaturated polyester, for example, maleic anhydride (anhydrous),
Polybasic unsaturated acids such as fumaric acid and itaconic acid (anhydride), (anhydrous) phthalic acid, isophthalic acid, terephthalic acid, tetrahydro (anhydrous) phthalic acid, methyltetrahydro (anhydrous) phthalic acid, endomethylene tetrahydro (anhydrous) ) At least one organic polybasic acid selected from phthalic acid, adipic acid, sebacic acid, chlorendic acid, tetrabromo (anhydrous) phthalic acid, and ethylene glycol,
Propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-
It is selected from butanediol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol-A, bisphenol A / propylene oxide adduct, dibromoneopentyl glycol, pentaerythritol diallyl ether, allyl glycidyl ether and the like. Included are those produced by a conventional method using at least one polyhydric alcohol, having an acid value of about 5 to 100 and being viscous at room temperature or solid at a softening point of 200 ° C. or lower.

As an example of the vinyl ester resin,
Those obtained by reacting (meth) acrylic acid with an epoxy resin such as glycidyl ether of bisphenol A, novolac type epoxy resin and polybasic acid glycidyl ester, and 2-hydroxyethyl methacrylate, 2
-Unsaturated alcohols having a (meth) acryloyl group such as hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate, and maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and chlorendic acid. , Adducts with polybasic acid anhydrides such as tetrabromophthalic anhydride, and functional groups such as hydroxyl groups, amines and carboxylic acids such as glycidyl methacrylate and polyphenols, novolacs, aromatic amine polycarboxylic acids or their anhydrides The thing obtained by making it react with the compound which has a group is mentioned.

As the reactive diluent, for example, unsaturated fatty acid ester, aromatic vinyl compound, unsaturated fatty acid and its derivative, unsaturated dibasic acid and its derivative, saturated fatty acid or aromatic carboxylic acid vinyl or allyl are used. Examples thereof include esters and their derivatives.

As the unsaturated fatty acid ester, for example,
Alkyl such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (iso) bornyl (meth) acrylate (Meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth ) Acrylate, biphenyl (meth) acrylate,
Acrylic acid aromatic esters such as bromobenzyl (meth) acrylate, (meth) acrylic acid esters such as glycidyl (meth) acrylate, alkylamino (meth) acrylate and the like can be mentioned.

As the aromatic vinyl compound, for example, styrene, divinylbenzene, ethylvinylbenzene or α-methylstyrene, α-ethylstyrene, α
Α-substituted styrenes such as chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene, nuclear substituted styrenes such as methoxystyrene.

Examples of the unsaturated fatty acid and its derivative include (meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and (meth) acrylic acid. Etc. can be mentioned.

Further, as the unsaturated dibasic acid and its derivative, for example, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenyl maleimide,
N-substituted maleimides such as N-carboxyphenyl maleimide, maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, itaconic acid, dimethyl itaconate, diethyl itaconate, etc. Can be mentioned.

Examples of vinyl or allyl esters of saturated fatty acids or aromatic carboxylic acids and their derivatives include, for example, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl n-butyrate, allyl acetate, allyl propionate, benzoic acid. Allyl etc. can be mentioned.

Among these reactive diluents, it is preferable to use an aromatic vinyl compound. Particularly, styrene and divinylbenzene have high polymerizability with itaconic acid,
It imparts excellent curability. In addition, the surface height of the cured resin can be improved. The amount of styrene or divinylbenzene used is 2% by weight to 20% by weight, preferably 2% by weight to 10% by weight of the resin composition. Use of more than 20% by weight may result in deterioration of the mechanical properties of the cured resin.

Further, a crosslinkable polyfunctional monomer may be used in order to increase the surface hardness, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate and triethylene glycol di (meth). Bifunctional cross-linkable monomers such as acrylate, diallyl terephthalate, diallyl isophthalate and diallyl carbonate, diallyl malate,
Trifunctional cross-linking monomers such as diallyl fumarate, diallyl itaconate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triallyl trimellitate, and tetraerythritol tetra (meth) acrylate. Examples thereof include functional crosslinking monomers.

The compounding ratio of the unsaturated polyester, the vinyl ester resin and the reactive diluent is 0% to 70% by weight, preferably 20% by weight of the thermosetting resin composition of the present invention.
~ 50% by weight. When the blending ratio of the unsaturated polyester, the vinyl ester resin and the reactive diluent is increased, the curing rate may be unduly delayed or the toughness of the cured product may be decreased.

It is possible and desirable to use a radical polymerization initiator in the curable resin composition of the present invention (III) for the purpose of promoting curing.

The radical polymerization initiator used for curing the curable resin composition of the present invention is, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, bis (4-t). -Butylcyclohexyl) peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and the like. These are preferably added in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the curable resin composition of the present invention.

The curable resin composition of the present invention may be, for example, a filler, a polymerization inhibitor, a polymerization accelerator, an internal release agent, a coupling agent, if desired, as in the conventional curable resin composition.
By using a pigment, a flame retardant, and other additives in an amount that does not impair the characteristics of the composition, the molding processability or the physical properties of the molded article can be improved.

The molding method of the resin composition of the present invention is as follows:
A known molding method similar to that of the conventional curable resin can be applied as it is. That is, a casting method in which the composition of the present invention is injected into a mold and cured, a compression molding method in which the composition is heated and pressed in the mold to cure, dissolved in a suitable organic solvent and impregnated into a fibrous sheet, After drying, if necessary, under pressure conditions, it is impregnated into a laminated plate molding method, printing paper, etc. that is cured in a fibrous sheet,
After the drying, there is a decorative board molding method in which the substrate is heated and pressed to be cured. The present invention will be described in detail below with reference to examples.

[0085]

[Examples] In the following examples, a method for measuring the analytical value of the synthesized allyl ester oligomer will be shown. <Iodine number> Oligomer is precisely weighed in the range of 0.25 to 0.35 g, put in a 200 ml iodine flask, and 30 m
Add 1 l of chloroform to dissolve completely. to this,
Wijs reagent (7.9 g iodine trichloride and iodine 8.
2 g of each was dissolved in 200 ml to 300 ml of glacial acetic acid, and both solutions were mixed to make 1 liter), 20 ml was accurately added using a whole pipette, and then 10 ml of 2.5% mercuric glacial acetic acid glacial acetic acid was added. Leave for a minute in the dark to complete the reaction. To this, 5 ml of the prepared 20% KI solution was added, and a 1% starch solution was used as an indicator.
a2 CO3 standard solution is added dropwise. Perform a blank test at the same time,
The iodine value is calculated from the following formula.

Iodine value = {(AB) × f × 1.27}
/ SA: m of 0.1 N-Na ₂ CO ₃ standard solution required for blank test
1 B: m of 0.1 N-Na ₂ CO ₃ standard solution required for this test
lf: Normality of Na ₂ CO ₃ standard solution S: g of sample

<Measurement of Mn and Mw by GPC method> Mn and Mw in terms of polystyrene are measured by GPC.
SHODEX column AC-80P, 802, 804, 8
Each one of 06 was connected in series in this order and used, using chloroform as a solvent at a temperature of 25 ° C. and a flow rate of 1.0 ml / mi.
Measure with n. 1) First, at least 10 kinds of commercially available standard polystyrenes having known average molecular weights were used, and the relationship between the respective storage times together with the DATP monomer was approximated by a cubic curve or a broken line to prepare a calibration curve.

2) 20 mg of sample is replaced with 20 ml of chloroform
And inject 0.5 ml through a line filter into the column using a loop injector. The obtained elution curve data is automatically calculated in a data processor such as Shimadzu CR-3A based on the calibration curve prepared in 1) to determine Mn and Mw. Here, the peak is 1
It is divided at 0 second intervals, and the molecular weight of each division point is Mi,
The height of the peak was defined as Hi, and calculation was performed using the following formula.

Mn = ΣHi / {Σ (Hi / Mi)} Mw = ΣMiHi / ΣHi

Example 1 In a 2 liter three-necked flask equipped with a distillation apparatus, 985 g of diallyl terephthalate and 420 g of diallyl itaconate were added.
g, 380 g of propylene glycol, and 0.8 g of dibutyltin oxide were charged and heated at 180 ° C. under a nitrogen stream to distill off the produced alcohol. When the amount of the distillate reached about 70% by weight of the theoretical amount, the pressure in the reaction system was gradually reduced to 50 mmHg to accelerate the rate of distilling alcohol. When almost no distillate was produced, the inside of the reaction system was adjusted to 2 mmHg, and the reaction was further continued for 1 hour to cool the reaction product. Table 1 shows the physical properties of the obtained oligomer.

(Examples 2 to 6) As shown in Table 1, synthesis was performed in substantially the same manner as in Example 1 except that the aromatic diallyl ester and the polyol were changed. The physical property values of the resulting oligomer are also shown in Table 1.

Comparative Examples 1 and 2 Table 1 shows the physical properties of the oligomers obtained by the same synthesis as in Example 1 except that diallyl malate and diallyl fumarate were used as the unsaturated dibasic acid. .

[0093]

[Table 1]

(Examples 7 to 17 and Comparative Examples 3 to 6) The allyl ester oligomers synthesized in Examples 1 to 6 and Comparative Examples 1 and 2 were mixed with styrene, divinylbenzene and commercially available at the compounding ratios shown in Table 2. The mixture was mixed with the unsaturated polyester and vinyl ester, and cast-cured. 2 phr of perloyl TCP (manufactured by NOF CORPORATION) was used as an initiator.
The curing temperature and time are 50 ° C for 1 hour and 80 ° C.
It took 1 hour. Barcol hardness of the obtained cast cured product,
The tensile strength and the Charpy impact value are also shown in Table 2. The tensile strength was measured according to JIS K-7113, and the Charpy impact value was measured according to JIS K-7111 at a temperature of 23 ° C.

[0095]

[Table 2]

As can be seen from Table 2, the oligomer of the present invention and the curable resin composition containing the oligomer as an essential component have higher tensile strength and Charpy than those of the comparative examples containing maleic acid and fumaric acid. It can be seen that the impact value is clearly high and the toughness is excellent. Further, when cured under relatively mild conditions as in this example, the terminal allyl oligomer containing maleic acid in the skeleton of Comparative Example 3 had a low Barcol hardness and was insufficiently cured. On the other hand, Example 8 of the same composition except that maleic acid was changed to itaconic acid has a high Barcol hardness, so that the curable resin composition of the present invention is also improved in curability. I can say.

[0097]

When an organic residue derived from itaconic acid is introduced into the skeleton of an oligomer having an allyl group at the terminal,
It is clear that a thermosetting resin having high tensile strength and Charpy impact value and excellent toughness can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Uchida No.2 Nakasu, Oita City, Oita Prefecture Showa Denko Co., Ltd. Oita Laboratory (56) Reference JP-A-1-217024 (JP, A) (58) ) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (14)

(57) [Claims] 1. An oligomer having at least one group represented by the following general formula (1) as a terminal group and having a group represented by the following general formula (2) as a repeating unit. General formula (1) (In the general formula (1), R is an independent organic residue and has an unsaturated group. One or more dicarboxylic acids selected from the group consisting of aliphatic dicarboxylic acids, saturated aliphatic dicarboxylic acids, and aromatic dicarboxylic acids. An organic residue derived from an acid, provided that at least one of Rs present in one molecule is an organic residue derived from itaconic acid, and in the general formula (1), X is a carbon atom. Represents an alkyl group having 1 to 3 carbon atoms or an allyl group, provided that at least one of Xs present in one molecule is an allyl group, and the terminal to the right of the group represented by the general formula (2). When it has a structure, its terminal structure is X instead of general formula (1).) General formula (2) (In the general formula (2), R is an independent organic residue and has one or more dicarboxylic acids selected from the group consisting of an aliphatic dicarboxylic acid having an unsaturated group, a saturated aliphatic dicarboxylic acid and an aromatic dicarboxylic acid. An organic residue derived from an acid, provided that at least one of Rs present in one molecule is an organic residue derived from itaconic acid. Represents one or more polyvalent organic residues derived from polyhydric alcohols, provided that
B may have a branched structure with an ester bond and further having the general formula (1) as a terminal group and the general formula (2) as a repeating unit. The total number of repeating groups represented by the general formula (2) contained in one molecule is 1 to 2
It is an integer range of 0. ) 2. The total number of organic residues derived from itaconic acid relative to the total number of R contained in one molecule is 10 mol.
% To 80 mol%, The oligomer according to claim 1, wherein 3. The method for producing an oligomer according to claim 1, comprising the following steps. In the presence of a catalyst, a step of transesterifying a dicarboxylic acid diester mixture containing itaconic acid diester as an essential component with a polyhydric alcohol to obtain an oligomer 4. The catalyst used in the step of claim 3,
The method for producing an oligomer according to claim 3, wherein the catalyst is at least one catalyst containing dibutyltin oxide. 5. The oligomer according to claim 1 or 2 with respect to the total amount of the curable resin composition.
A curable resin composition, which is contained in the range of 80% by weight to 80% by weight. 6. The oligomer according to claim 1 or 2 in an amount of 30 relative to the total amount of the curable resin composition.
% To 80% by weight, and the balance being at least one selected from the group consisting of other unsaturated polyesters, vinyl ester resins and reactive diluents. 7. The reactive diluent is unsaturated fatty acid ester, aromatic vinyl compound, unsaturated fatty acid and its derivative, unsaturated dibasic acid and its derivative, and saturated fatty acid or aromatic carboxylic acid vinyl or allyl ester. And at least one selected from the group consisting of derivatives thereof and the curable resin composition according to claim 6. 8. The reactive diluent is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth).
Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (iso) bornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthyl (meth). Acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, biphenyl (meth) acrylate,
The curable resin composition according to claim 6, which is at least one or more unsaturated fatty acids selected from the group consisting of bromobenzyl (meth) acrylate, glycidyl (meth) acrylate, and alkylamino (meth) acrylate. object. 9. The reactive diluent is styrene, divinylbenzene, ethylvinylbenzene, α-methylstyrene,
7. At least one or more aromatic vinyl compounds selected from the group consisting of α-ethylstyrene, α-chlorostyrene, fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene and methoxystyrene. The curable resin composition described. 10. The reactive diluent is (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N,
The curable resin composition according to claim 6, which is at least one unsaturated fatty acid selected from the group consisting of N-diethyl (meth) acrylamide and (meth) acrylic acid and a derivative thereof. 11. The reactive diluent is N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide or N-methylmaleimide.
-Cyclohexylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, N-carboxyphenylmaleimide, maleic acid, maleic anhydride, dimethylmalate, diethylmalate, fumaric acid, dimethylfumarate, diethylfumarate 7. The curable resin composition according to claim 6, which is at least one unsaturated dibasic acid selected from the group consisting of rate, itaconic acid, dimethyl itaconate and diethyl itaconate, and derivatives thereof. 12. The reactive diluent is at least one saturated fatty acid selected from the group consisting of vinyl acetate, vinyl propionate, vinyl benzoate, vinyl n-butyrate, allyl acetate, allyl propionate and allyl benzoate, or The curable resin composition according to claim 6, which is a vinyl or allyl ester of an aromatic carboxylic acid and a derivative thereof. 13. 0.1 to 5 parts by weight of at least one or more radical polymerization initiators relative to 100 parts by weight of the curable resin composition according to any one of claims 5 to 12. A curable resin composition characterized by the above. 14. A cured product obtained by curing the curable resin composition according to any one of claims 5 to 13.