JPS6164725A - Polymerizable resin composition - Google Patents

Abstract

PURPOSE:A polymerizable resin composition freed of curing volume shrinkage, excellent in dimensional accuracy in molding and suitable as, e.g., a molding material or a paint, obtained by mixing a compound having a spiro- orthocarbonate group, a cation-polymerizable compound and a curing agent. CONSTITUTION:A compound having at least one spiro-orthocarbonate group in the molecule, represented by the formula (wherein R<1> and R<2> are each a bivalent organic group), e.g., 1,4,6,9,-tetraoxaspiro[4.4]nonane or 1,5,7,11- tetraoxaspiro[5.5]undecane, is mixed with other cation-polymerizable compounds (e.g., phenyl glycidyl ether or bisphenol A epoxy resin) and a curing agent for these compounds (e.g., succinic anhydride or phenolic resin) to obtain the purpose polymerizable resin composition.

Description

Detailed Description of the Invention (() Object of the Invention [Field of Industrial Application] The present invention relates to a resin composition for polymerization, particularly a resin composition suitable for thermosetting, such as casting, filling, painting, etc.
It can be used in a wide range of fields such as adhesion and molding.

[Conventional technology]

Epoxy resins, unsaturated polyester resins, diallyl fusylate resins, phenol resins, etc. have been used as thermosetting resins, but they suffer from volumetric shrinkage during curing.

[Problem that the invention seeks to solve]

The present invention provides a resin composition that exhibits minimal volumetric shrinkage during curing, improves dimensional accuracy during molding, reduces internal stress and crevices during casting, and improves adhesion when used as a paint. This is an attempt to make improvements.

(b) Structure of the invention [Means for solving the problems] The present invention comprises a spiro-orthocarbonate compound represented by the above formula [1], a cationically polymerizable compound other than the spiro-orthocarbonate compound, and a curing agent thereof. By structuring the resin composition, a composition that exhibits almost no volumetric shrinkage or, on the contrary, volumetric expansion upon curing, is provided.

[Spiro orthocarbonate]

1 in the above formula representing spiroorthocarbonate (1 and R2 are the same or the same divalent organic group, more specifically, the moiety constituting the ring of formula [1] in R1 and Hz is preferably It is a divalent organic group with a skeleton of 2 to 4 carbon atoms, and the carbon atoms constituting these rings include various atoms including hydrogen atoms, alkyl groups, aryl groups, alkylene groups, and halogen atoms. Organic groups may be bonded, and of course, these groups may have a ring structure themselves, contain atoms such as oxygen, nitrogen, or sulfur, or may be a residue of polyester, polyether, polyurethane, etc. There may be some.

Specific examples of spiroorthocarbonates used in the present invention include the following compounds. 1, 4, 6.
9-tetraoxaspiro(4,4)nonane; 1,5,7
．． 11-tetraoxaspiro(5,5]undecane; 1
,6゜8.13-tetraoxaspiro[6,6]tridecane; 1,4,6.10-tetraoxaspiro(4,5
1 decane; 2,7-dimethyl-1°4, 6. 9-tetraoxaspiro(4,4)nonane; 2. 5. 7.
8-tetramethyl-1,4°6.9-tetraoxaspiro(4,4)nonane; 8-ethyl-8-hydroxymethyl-1,4°6.10-tetraoxaspiro[4,5
] Decane; s, q-diethyl-6,9-dihydroxymethyl-1,5,7,11-tetraoxaspiro(5,5
) Undecane; 3. 3. 9. 9-tetramethyl-
1,5,7,11-tetraoxasubiO+:S,S]undecane;8,8-dihydroxymethyl-1,4,6,
10-tetraoxaspiro[4,5]decane; 6-methylene-1゜5.7.11-tetraoxaspiro[4,5]decane;
) Kundecane; 3-methylene-1,5,7,12-tetraoxaspiro[5,6]dodecane; 3゜9-dimethylene-1,5,7,11-tetraoxaspiro(5,5)
Kundecane; 8,10°19.20-tetraoxatetraspiro [5°2, -2.5.2.21 Heneicosane; 1,4°6.10,12,15,16,19-octaoxatetraspiro( 4,2,2-4,2,2) Nonadecane: 3,9-diethyl-3,9-di,hydroxymethyl-1,5,7,11-tetraoxaspiro(5,5)undecane and hexamethylene Ure of the following formula synthesized from diisocyanate (where X' represents an integer of 1 or more)
.

[Unexamined Japanese Patent Publication No. 1983-. 10582, patent application No. 57-15884
4. Overseas polymer research, Sl.

187 (1983)].

These are examples of spiro-orthocarbonates and are not intended to limit the scope thereof.1゜[Cationically polymerizable compounds] Cationically polymerizable compounds other than the above-mentioned compounds that constitute the composition together with the spiro-orthocarbonate compound in the present invention There are various types of epoxy compounds such as phenylglycidyl ether, bisphenol, A type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, polyglycidyl ether of polyhydric alcohol, and JP-A-Sho. Spiroorthoester compound known as 57-67628 etc., JP-A-58-L
Examples include bicycloorthoester compounds known as 54115 and the like, lactones such as ε-caprolactone, and cyclic ethers such as oxetane and nato-2hydrofuran, and the types thereof are not particularly limited. The blending ratio of these cationically polymerizable compounds to the spiro-orthocarbonate compound can be uniquely selected in order to adjust the volume change and other physical properties to the purpose of use.

[Curing agent]

The curing agent preferably used in the present invention is selected from phenolic resins, organic polybasic acids, organic polybasic acid anhydrides, cationic polymerization initiators, etc., and is as described in more detail below. be.

The organic polybasic acid or its acid anhydride includes any one commonly used as a curing agent for epoxy compounds, such as the following.

Succinic anhydride, methylsuccinic anhydride, dodecenylsuccinic anhydride, dichlorosuccinic anhydride, azelaic anhydride, sebacic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrahydroheptalic anhydride, methyltetrahydro anhydride Phthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydroheptalic anhydride, tricarballylic anhydride, trimellitic anhydride, pyromellitic anhydride, and In addition to polybasic acids derived from these or mixtures of two or more of these, mixtures of these with basic acid anhydrides, or silic acid adducts of maleic anhydride,
These derivatives have a carboxylic acid or its acid anhydride structure at the end or side chain of the molecule obtained from the acid anhydride, such as compounds with a structure in which these acid anhydrides are added to the hydroxyl group of a phenolic resin, etc. can also be used.

Also tartaric acid, malic acid, tartronic acid, alkyl tartronic acid, α-methylmalic acid, β-methylmalic acid, α
-oxyglutaric acid, β-oxyglutaric acid, dicrotaric acid, α-oxysheric acid, α-oxysebacic acid,
Oxypolycarboxylic acids such as citric acid, ink citric acid, etc. can be used.

As a carboxylic acid type polyester, for example, a trivalent or higher polybasic acid anhydride or an acid anhydride consisting of this and a dibasic acid anhydride is reacted with a hexavalent or higher polyol or a polyol consisting of this and a diol. More specifically, for example, polyols with a valence of 6 or more or polyols consisting of this and diols,
A carboxylic acid type obtained by reacting a polybasic acid anhydride or an acid anhydride consisting of a dibasic acid anhydride with a polybasic acid anhydride at a ratio of α7 to 13 equivalents of acid anhydride per 1 equivalent of hydroxyl group in the polyol. There is polyester.

The phenolic resin is a resin having a phenolic hydroxyl group, such as polyvinylphenol, non-logenated polyvinylphenol, and ordinary phenolic resins such as phenol, ortho (or para)-cresol, para-ethylphenol, para-tert. -Butylphenol, para-5ec -Butyl7'L! - Novolac type resins, resol type resins and their Modified products such as butylated products can also be used.

Examples of the cationic polymerization initiator include aromatic onium salts of Group VIa elements of the periodic table, such as φ-N-N-PF salts: (1) H3 H3.

In addition, other cationic polymerization initiators include, for example, B
F5. FeC1,,5nC1,,5bC1,,SbF,
, Lewis acids such as TiCl4: BF30Et, ,B
Lewis acids such as F, -aniline complex etc. and 0
Coordination compounds with compounds having , S, N, etc. oxonium salts, diazonium salts, carbonium salts of Niluiz acid: halogen compounds, mixed halogen compounds, perhalogen acid derivatives, etc.

The optimum proportion of the curing agent may be determined as appropriate depending on the chemical properties of the resin used and the properties required for the prepared curable composition and the cured product provided by it.
The desirable blending ratio is as follows.

Per total equivalent of cationic polymerizable groups such as spiro-orthocarbonate groups in the composition, acid anhydride groups, carboxylic acid groups, or phenolic hydroxyl groups (combined with organic polybasic acids, acid anhydrides, or phenolic resins) (if the total amount) is Q, 2 to 10 equivalents, preferably 0.3 to 10 equivalents
5 equivalents, and the amount of the cationic polymerization initiator blended is preferably in the range of 0.001 to 10 wt% in the composition.

Other additives include quartz powder, alumina, fillers such as β-eucryptite, dyes, and flame retardants.

Although there are no particular limitations on the curing temperature of the resin composition of the present invention, curing is usually carried out at room temperature to 250°C, but it is more advantageous to cure under heating.

[Examples and comparative examples]

Example 1 20 parts (parts by weight, same below) of 2.8-dimethyl-1,5,7,11-tetraoxaspiro[5,5)undecane
BP and 2 parts of monoethylamine complex were dissolved in a mixture of 80 parts of Ebiko) 828 (bisphenol A type epoxy resin trade name manufactured by Yuka Shell, Epoxy ■) and degassed.
It was heat-cured at 150°C for 2 hours. The volumetric shrinkage after curing determined from specific gravity measurements was only 0.6 inches.

Comparative example 1 BF for 100 parts of the Epikote 828.

Two parts of the monoethylamine complex were dissolved and cured in the same manner as in Example 1.

The volume shrinkage after curing determined from specific gravity measurement was 6.5 inches.

Example 2 11 parts of 5.3,9.9-tetramethyl-1,5,7゜11-tetraoxaspiro(5,5)undecane and Evototo YDCN-701 (Tobu Kasei's resol novolac type epoxy resin product) name) 45 copies, Rikajid PAZ
-90 (Brand name of organic polybasic acid anhydride manufactured by Shin Nippon Rika) 4
4 parts and further 1 part of 2-ethyl-4-methylimidazole were taken and mixed to form a finely powdered composition.

This composition was hot pressed at 140° C. for 2 hours to obtain a cured product. The volumetric shrinkage determined from specific gravity measurements was zero.

Comparative Example 2 156 parts of Evotote YDCN-70, Rikajid P
44 parts of AZ-90 and further 1 part of 2-ethel-4-methylimidazole are taken and mixed to form a fine powder composition,
It was cured in the same manner as in Example 2. Volumetric shrinkage determined from specific gravity measurement was 0.5%.

Example 6 2, 2. 4. 8. 8. 10-hexamethyl-
1°5.7.13 parts of 11-tetraoxaspiro(5,5)undecane, 41 parts of the above Epicote 828, 46 parts of methylhexahydrophthalic anhydride, and further 2-ethyl-
After dissolving 1 part of 4-methylimidazole and degassing, 120
It was heated and cured at 150°C for 1 hour and then at 150°C for 1 hour. The volume change after curing determined from specific gravity measurement was zero.

Comparative Example 6 M Epikote 82B St part, 47 parts of methylhexahydrophthalic anhydride, and further 1 part of 2-ethyl-4-methylimidazole were dissolved and cured in the same manner as in Example 5. The volumetric shrinkage determined from specific gravity measurement was 4.0.

(3) Effects of the invention According to the resin composition of the present invention, there is almost no volumetric shrinkage during curing, dimensional accuracy during molding is good, internal stress and crevices are less generated during casting, and it can be used as a paint. The composition of the present invention is useful in various fields because it can sometimes form a cured product with advantages such as good adhesion.

Name of patent originator Toagosei Chemical Industry Co., Ltd.

Claims (1)

[Claims] 1. A compound for polymerization comprising a compound having one or more spiro-orthocarbonate groups in the molecule represented by the following formula [1], a cationically polymerizable compound other than the spiro-orthocarbonate compound, and a curing agent for these compounds. Resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the above formula, R^1 and R^2 are the same or different divalent organic groups.)