JPS6132329B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition. More specifically, general formulas (), (),
() (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and are hydrogen or an alkyl group. X and Y may be the same or different and are hydrogen, halogen, hydroxyl group, acyl group, acyloxy group, alkoxy group, nitrile group, allyl group, substituted allyl group, propargyl group, substituted propargyl group, allyloxy group,
It is a propargyloxy group. x, y, x', y' are 0
or a positive integer, z, z′ are positive integers, x+
y+z≦5 and x′+y′+z′≦5. ) or a mixture of two or more thereof, one or two or more selected from maleic anhydride, maleic acid, fumaric acid, maleic hydrazide, fumaric hydrazide, maleimide, and bismaleimide. This invention relates to a curable resin composition containing a compound. Furthermore, one or more dienes such as a phenol resin, an unsaturated polyester, a liquid rubber, an epoxy resin, a vinyl monomer, a diene monomer, and an oligomer are added to the resin composition. The present invention relates to a curable resin composition.

Many compounds having a vinyl group and an epoxy group in one molecule, such as compounds of general formulas (), (), and (), are known, and their polymerization and curing methods are also already known. However, little is known about compounds having an epoxy group and an anhydride carboxyl group in one molecule, such as those obtained by reacting compounds represented by the general formulas (), (), and () with maleic anhydride. Not yet. Such compounds include polyalcohols,
It can be polymerized and cured using reactive curing agents such as phenols, amines, polycarboxylic acids, epoxy resins, and phenolic resins. It can also be cured by simply heating. In particular, the combination of compounds represented by formulas () and () with maleic anhydride can polymerize vinyl monomers, and even mixtures of epoxy resins and vinyl monomers can be easily polymerized and cured. It is very convenient because it can be chemically bonded to the cured product.

The compound represented by the general formula () is obtained by glycidyl etherification of isopropenylphenol monomer, and the compound represented by the general formula () and () is a linear form of isopropenylphenol monomer. It can be obtained by glycidyl etherification of a dimer or linear dimerization of a compound represented by the general formula ().

Examples of the alkenylphenol as a precursor of the glycidyl ether represented by the general formula () include isopropenylphenol (ortho, meta, para), isopropenyl cresol, isopropenyl chlorophenol,
These include isopropenylcatechol, isopropenylresorcin, isopropenylhydroquinone, and isopropenyldichlorophenol.

Further, as the alkenylphenol linear dimer as a precursor of the glycidyl ether represented by the general formula () or (), for example, 4-
Methyl-2,4-bis(2-, or 3-, or 4
-hydroxyphenyl)-penta-1- or 2-
ene, 4-methyl-2,4-bis(dihydroxyphenyl)-pent-1- or 2-ene, 4-methyl-2,4-bis(3,5-dichloro-4-hydroxyphenyl)-penta -1 or 2-ene,
Examples include 4-methyl-2,4-bis(3-chloro-4-hydroxyphenyl)-pent-1- or 2-ene.

The compounds represented by the general formulas (), () and () and maleic anhydride form a stable 1:1 adduct. In addition to maleic anhydride,
maleic acid, fumaric acid, maleic hydrazide,
It also forms adducts with maleimide, bismaleimide, etc.

The curable resin composition of the present invention has the general formula (),
One or more compounds shown in () and () are selected and mixed, and maleic anhydride, maleic acid, fumaric acid, maleic hydrazide, fumaric hydrazide are added to 1 mol of these alone or as a mixture. One or more compounds selected from , maleimide, and bismaleimide can be used in varying amounts in the range of 0.05 to 20 mol, preferably 0.1 to 2 mol.

The curing reaction is carried out at a temperature ranging from 0 to 300°C, preferably from 50 to 200°C. The curing reaction time varies depending on the reaction temperature, purpose of use, etc., but is from 5 minutes to 24 hours. In addition, during the curing reaction,
The pressure may be increased or reduced.

In addition, during the curing reaction, organic solvents such as
It does not matter if it contains benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, methylene chloride, chloroform, etc., and even polyalcohols (such as glycerin, glucose, polyvinyl alcohol, cellulose, starch, chitin cellulose, pepperin). ), phenols (e.g., resorcinol, catechol, bisphenol, cresol, phenol, etc.), amines (e.g., ethylenediamine, paraphenylenediamine, polyethyleneimine, etc.), polycarboxylic acids (e.g., terephthalic acid, isophthalic acid, pyromellitic acid), , polyacrylic acid, polymethacrylic acid, copolymers with acrylic acid or methacrylic acid, etc.), phenolic resins (e.g. resol resins, novolac resins, zyrock resins or xyloc resins, polyhydroxystyrene, polyhydroxy α-methyl Copolymers with styrene, vinylphenol or isopropenylphenol, etc.), epoxy resins (e.g. manufactured by Ciel, trade names Epicote 828 and Epicote 1001, polymethacrylic acid glycidyl ether, etc.), unsaturated polyesters, liquid rubbers, etc. One or more of these may be added and blended. The amount used varies depending on the purpose, but the general formula (),
When the total amount of the compounds represented by () and () is 1 mol, it can be varied within the range of 0 to 50 mol, preferably 0 to 10 mol.

Among the above-mentioned additives, phenolic resins, unsaturated polyesters, liquid rubbers and epoxy resins are particularly useful.

In the compounds represented by the general formulas (), (), and (), a charge transfer complex is generated in the process of forming an adduct with maleic anhydride, and this complex has an activity for polymerizing vinyl monomers. That is, the combination of the compounds represented by the general formulas (), (), and () with maleic anhydride can act as a curing agent as well as a polymerization initiator for vinyl monomers. A composition containing a body is
A curable resin composition is formed.

Vinyl monomers that can be used in the present invention include, for example, styrene and its substituted derivatives, acrylic acid and its ester derivatives, methacrylic acid and its ester derivatives, acrylonitrile, acrylamide, bismaleimide, maleimide, butadiene, cyclopentadiene, etc. be. The amount of these monomers used is in the range of 0.01 to 100 mol per mol of whichever is smaller between the total amount of compounds represented by general formulas (), (), and () and the total amount of maleic anhydride. It can be used by changing it. The reaction temperature is 0 to 300°C, preferably
The temperature is 50 to 200°C, and the reaction may be carried out under increased pressure or reduced pressure as necessary.

Further, in the above reaction, organic solvents such as benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, chloroform, methylene chloride, dioxane, etc. may be included, and epoxy resins, unsaturated polyesters and liquid polybutadiene may be used. Dienes such as 0.01 to 1 mole of vinyl monomer
It may be added and blended in a range of 100 moles.
Note that a polymerization initiator such as a vinyl monomer or a diene monomer may be used in combination.

The curable resin composition of the present invention is useful, for example, as a molding, laminating, adhesive, casting, or covering material.

The present invention will be explained in more detail with reference to Examples below.

Example 1 19.0 g of p-isopropenyl phenyl glycidyl ether and 10.0 g of maleic anhydride were mixed at room temperature, and this mixture was heated and melted at 100°C.
It hardened in 10 minutes and became insoluble and infusible.

Example 2 20.0 g of 4-methyl-2,4-bis(4-glycidyloxyphenyl)-pent-1ene and 5.0 g of maleic anhydride were mixed at room temperature and melted by heating to 100°C. It hardened and became insoluble and infusible.

Example 3 p-isopropenyl phenyl glycidyl ether 10.0 g, 4-methyl-2,4-bis(4-glycidyloxyphenyl)-pent-1-ene 10
g, 4-methyl-2,4-bis(4-glycidyloxyphenyl)-pent-2-ene 5g, epoxy resin (manufactured by Ciel, trade name Epicote 828)
Mix 50g and 10g of maleic anhydride at room temperature,
It was heated and melted at 120°C. The mixture cured in 20 minutes.

Example 4 10 g of p-isopropenyl glycidyl ether,
5.0 g of maleic anhydride and 50 g of unsaturated polyester (manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name: Ester) were mixed well at room temperature, and when heated to 130° C., it hardened in 18 minutes.

Example 5 10 g of p-isopropenyl phenyl glycidyl ether and 3 g of maleic acid hydrazide were mixed well at room temperature, and when heated to 80° C., the mixture was cured in 30 minutes.

Example 6 4-methyl-2,4-bis(4-glycidyloxyphenyl)-pent-1-ene 40 g of resol resin with a gelation time of 8 minutes at 150°C
g and 10 g of maleic anhydride were added and blended, and when heated to 120°C, it hardened in 13.5 minutes.

Example 7 Resin M (manufactured by Maruzen Oil Co., Ltd., poly-p-hydroxystyrene) 12 g, epoxy resin (manufactured by Ciel Co., Ltd., trade name Epicote 828) 20 g, p-isopropenyl phenyl glycidyl ether 10 g, maleic anhydride 4 g, maleic acid When 2 g of hydrazide was mixed well at room temperature and heated to 130°C, it hardened in 25 minutes.

Example 8 5 g of p-isopropenyl phenyl glycidyl ether, 10 g of bisphenol A diglycidyl ether (Epicote 828 liquid epoxy resin) and 25 g of 4,4'-bismaleimido diphenylmethane were mixed and mixed well at room temperature.

When 1 g of this mixture was taken out and heated on a hot plate kept at a temperature of 160°C, it was cured in 50 minutes.

Claims (1)

[Claims] 1 General formulas (), () and () (In the formula, R ₁ , R ₂ and R ₃ may be the same or different and are hydrogen or an alkyl group. X and Y may be the same or different and are hydrogen, halogen, hydroxyl group, acyl group, acyloxy group, alkoxy group, nitrile group, allyl group, substituted allyl group, propargyl group, substituted propargyl group, allyloxy group,
It is a propargyloxy group. x, y, x', y' are 0
or a positive integer, z, z' is 1 or 2, x+y
maleic anhydride, maleic acid, fumaric acid, maleic hydrazide, fumaric hydrazide, maleimide to 1 mol of the compound represented by , bismaleimide, and bismaleimide in an amount of 0.05 to 20 moles. 2. A curable resin composition obtained by adding and blending one or more resins selected from phenolic resin, unsaturated polyester, liquid rubber, and epoxy resin to the resin composition according to claim 1. . 3. A curable resin composition obtained by adding and blending a vinyl monomer and/or a diene to the resin composition according to claim 1 or 2.