JPS6164726A - Curable resin composition for production for electronic or electric parts - Google Patents

Abstract

PURPOSE:A curable resin composition substantially free of curing volume shrinkage and suitable for the production of, e.g., electronic parts, containing a specified compound having a spiro-orthocarbonate group in the molecule and a curing agent as components. CONSTITUTION:A compound having at least one spiro-orthocarbonate group in the molecule, represented by the formula (wherein R1 and R2 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 a curing agent therefor (e.g., succinic anhydride or phenolic resin) and, optionally, a cation-polymerizable compound (e.g., phenyl glycidyl ether or bisphenol A epoxy resin) to obtain the titled curable resin composition.

Description

[Detailed description of the invention] (b) Purpose of the invention [Industrial application field] The present invention can be used, for example, for coating small electronic parts.

The present invention provides a curable resin composition for manufacturing electronic or electrical components, which is useful as an impregnating or sealing material, or as a base or laminated material for large electrical components.

[Conventional technology]

Currently, epoxy resin-based curable resin compositions are often used for coating, impregnating, or sealing small electronic parts, casting Oya electrical parts, and manufacturing laminated products. Since volumetric shrinkage occurs during curing, problems arise when used in the above-mentioned applications, such as distortion and warpage, and large internal stress that may cause failure.

[Problem that the invention seeks to solve]

The present invention aims to improve the above-mentioned problems, that is, the occurrence of distortion, warpage, internal stress, etc., by using a curable resin composition that exhibits almost no volumetric contraction or, on the contrary, volumetric expansion during polymerization.

(B) Structure of the invention [Means for solving the problem] In the present invention, the spiroorthocarbonate compound represented by the above formula [1] and its curing agent are blended as constituent components of a curable resin composition. This results in a curable resin composition that exhibits almost no volumetric shrinkage upon curing and is suitable for coating, impregnating, or sealing small electronic components, casting large electrical components, and manufacturing laminates.

[Spiroorthocarbonate compound]

W and R2 in the above formula [1] representing a spiroorthocarbonate compound are the same or different divalent organic groups; more specifically, W and t in the formula [1]
The moiety constituting the ring is preferably a divalent organic group having a skeleton of 2 to 4 carbon atoms, and the carbon atoms constituting these rings include hydrogen atoms, alkyl groups, aryl groups, and alkylene groups. , various atoms or organic groups including halogen atoms may be bonded, and of course, these groups may have a ring structure themselves, contain atoms such as carbon atoms, nitrogen, sulfur, etc. It may also be a residue of ether, polyurethane, etc.

Specific examples of spiroorthocarbonates that can be used in the present invention include the following compounds. 1.4,6
．． 9-tetraoxaspiro(4,4)nonane; 1,5,
7.11-tetraoxaspiro(S,S)undecane;
1,6,8.13-tetraoxaspiro[6,6]tridecane; 1.4,6.10-tetraoxaspiro("4
．． 5) Decane; 2゜7-dimethyl-1.4,6.9-tetraoxaspiro(4,4)nonane; 2,3,7,8-
Tetramethyl-1,4,6,9-tetraoxaspiro (
4,4) Nonane; 8-ethyl-8-hydroxymethyl-
1,4,6,10-tetraoxaspiro(4,5)decane; 3゜9-diethyl-3,9-dihydroxymethyl-
1,5,7,11-tetraoxaspiro(s,s)undecane; 3. ! 1,9.9-terene-1.5,7.11
-tetraoxanepyro(5,5)undecane; 3-methylene-1,5,7,12-tetraoxanepyro[5°6
] Dodecane; 3,9-dimethylene-1,5,7,11-
Tetraoxaspiro(S,S)undecane; 8,10,
19,20-tetraoxatetraspiro[5,2,2,
5,2゜2] Heneikosan; 1,4,6,10゜12
．． 15,16.19-octaoxatrispiro l', I
1.2. ．． 2.4.2.2) Nonadecane; 3,9-diethyl-3,9-dihydroxymethyl-1,5,7,11
- A urethane of the following formula synthesized from tetraoxaspiro(5,5)undecane and hexamethylene diisocyanate.

(Here, 7 represents an integer greater than or equal to 1).

[Unexamined Japanese Patent Publication No. 58-10582, Patent Application No. 57-158844
, Foreign Polymer Research, 29° 187 (19135)] These are examples of spiroorthocarbonates, and are not intended to limit the scope thereof.-1° [Curing agent] Spiroorthocarbonates used in the present invention Examples of the curing agent for the compound include curing agents selected from polybasic acids or their anhydrides, phenolic resins, cationic polymerization catalysts, and the like.

As an organic polybasic acid or its acid anhydride.

Any curing agent commonly used as a curing agent for epoxy compounds is included, and examples thereof include the following.

Succinic anhydride, methylsuccinic anhydride, dodecenylsuccinic anhydride, dichlorocono-phosphoric anhydride, azelaic anhydride,
Sebacic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydro anhydride 7-talic acid, methylendomethylenetetrahydrophthalic anhydride, tricarballylic anhydride, trimellitic anhydride.

In addition to pyromellitic anhydride, polybasic acids derived from it, or mixtures of two or more of these,
A mixture of these and a basic acid anhydride, or a silicic acid adduct of maleic anhydride, a compound having a structure in which these acid anhydrides are added to the hydroxyl group of a phenolic resin, etc. can be obtained from the above acid anhydrides. Derivatives thereof having a carboxylic acid or its acid anhydride structure at the terminal or side chain of the molecule 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, isocitric acid, etc. can also 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 trivalent or higher polyol or a polyol consisting of this and a diol. More specifically, for example, polyols having a valence of 3 or more or polyols consisting of this and a diol,
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 and halogenated polyvinylphenol, as well as ordinary phenolic resins such as phenol, ortho (or para)-cresol, para-ethylphenol, para-tert- Butylphenol, para-5ec-butylphenol, para-
Novolac type resins, resolya resins and modified products thereof, such as butylated products, manufactured using n-butylphenol, ortho (or para)-phenylphenol, para-cyclohexylphenol, para-octylphenol, para-benzylphenol, bisphenol A, etc. etc. can also be used.

Examples include aromatic onium salts of group VIa elements of the periodic table.

In addition, other cationic polymerization initiators include, for example, B
F,,FeC1,,5nC1,,5bC1,,SbF3
, TiC1, etc.: BF, OEt, , BF
Lewis acids such as s-aniline complex etc. and 0,
Coordination compounds with compounds having S, N, etc. oxonium salts, diazonium salts, carbonium salts of Lewis acid: halogen compounds, mixed halogen compounds, perhalogen acid derivatives, and the like.

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.

The amount of acid anhydride group, carboxylic acid group, or phenolic hydroxyl group per equivalent of spiroorthocarbonate group in the composition (or the total amount when organic polybasic acid, acid anhydride, or phenolic resin is used together) is 02-10
equivalent, preferably 0.3 to 5 equivalents, and the amount of the cationic polymerization initiator is usually Q, 001 to 10wt in the composition.
A range of % is preferred.

[Other ingredients]

It is desirable to further include a cationically polymerizable compound other than the spiroorthocarbonate compound in the composition of the present invention, and there are no particular restrictions on the type thereof. Examples of suitable compounds include:

Epoxy compounds such as phenylglycidyl ether, bisphenol A type epoxy resin, cresol novolak disk epoxy resin, alicyclic epoxy resin, polyglycidyl ether of polyhydric alcohol, spiro-orthoester compound known from JP-A-57-67628, etc. , Japanese Patent Publication No. 1983
Examples thereof include a bicycloorthoester compound known as -1341154, lactones such as ξ-caprolactone, and cyclic ethers such as oxetane and tetrahuman ct7 run. The specific gravity of these cationically polymerizable compounds relative to the spiro-orthocarbonate compound should be selected in accordance with the volume change and other physical properties depending on the purpose of use (it may be selected at any ratio).

Other additives for the composition of the present invention include quartz powder,
Examples include fillers such as alumina and β-eucryptite, dyes, and flame retardants.

Although there are no particular limitations regarding the curing temperature of the resin composition of the present invention, curing is usually carried out at room temperature to 250°C.

[For production]

When electronic or electrical parts are manufactured using the resin composition of the present invention, the volume resistivity of the cured resin product is almost the same as that of the cured product of epoxy resin, and the volume change before and after curing is almost zero.

[Examples and comparative examples]

Example 1 20 parts of 2.8-dimethyl-1,5,7,11-tetraoxaspiro C5,5'J undeforcen (parts by weight, the same applies hereinafter) and Bisphenol A manufactured by Ebicor) 82B (Yuka Shell Epoxy ■) BF and 2 parts of monoethylamine complex were dissolved in a mixture of 80 parts of epoxy resin (trade name) and applied to a resistor, followed by heating and curing at 150° C. for 2 hours.

The volumetric shrinkage after curing was determined from a separate specific gravity measurement of only 0.
It was 5%.

Comparative example 1 BF to 100 parts of the Epicote 828.

Two parts of the monoethylamine complex were dissolved and cured in the same manner as in Example 1. Volumetric shrinkage after curing determined from specific gravity measurement is 5
．． It was Section 5.

Example 2 3.5,9.9-tetramethyl-1,5,7°11-tetraoxaspiro(5,5) 7f force 11 parts Toebototo YDCN-701 (Resol Novo 2 manufactured by Tobu Kasei)
Tsuku type epoxy resin product name) 45 parts, Rikajid PAZ
-90 (Brand name of organic polybasic acid anhydride manufactured by Shin Nippon Rika) 4
4 parts of Kira and 1 part of 2-ethyl-4-methylimidazole were mixed to form a fine powder composition. This composition was sprayed onto a preheated unpainted polyethylene tere-7 tallate film capacitor.

After repeating this operation three times, the capacitor was heat-treated at 140'C for 2 hours to obtain a resin-coated polyethylene terephthalate film capacitor. The volume shrinkage after curing, which was determined separately from specific gravity measurements, was zero, and the volume resistivity was 3.
It was 10”Ω.

Comparative Example 2 A mixed fine powder composition of 156 parts of the above Evoto YDCN-70, 44 parts of the above Rikazid PAZ-9, and 1 part of 2-ethyl-4-methylimidazole was cured in the same manner as in Example 2.

The volume shrinkage after curing determined from the specific gravity is 0.5%,
Further, the volume resistivity was 2×10”Ωa.

Example 3 2.2,4,8,8,10-hexamethyl-1,5°7
．． 11-tetraoxaspiro[:5.5]unde 1
After dissolving 3 parts, 41 parts of the above-mentioned dipico-)828, 46 parts of methylhexahydrophthalic anhydride, and 1 part of 2-ethyl-4-methylimidazole and degassing, the solution was heated at 120°C for 1 hour, and further heated at 150°C for 1 hour. The IC was sealed with a resin by heating and curing for a period of time. The volume change after curing, which was determined separately from specific gravity measurements, was zero.

Comparative Example 6 53 parts of Epicor 828, 47 parts of methylhexahydrophthalic anhydride, and 1 part of 2-ethyl-4-methylimidazole were dissolved and cured in the same manner as in Example 3.

The volumetric shrinkage determined from specific gravity measurement was 4.0 inches.

Example 4 The curable resin composition of Example 3 was dissolved in methylene chloride to prepare a 50% by weight resin solution. This is impregnated into linter paper that has been treated with phenol resin in advance and dried.
A resin-impregnated paper with a resin content of 58 cm was obtained. Stack 10 of these and heat press (temperature 150°C, pressure 100 kg/cr)
IL) for 2 hours to obtain a laminate with a thickness of 1.6 mm.

(c) Effects of the invention The curable resin composition according to the invention has a volume resistivity of the cured product equivalent to that of an epoxy resin, and has almost no volumetric shrinkage during curing, so it is suitable for manufacturing electronic or electrical parts. It is suitable as a resin composition.

Claims (1)

[Scope of Claims] 1. A compound for manufacturing electronic or electrical parts comprising a compound having one or more spiroorthocarbonate groups in the molecule represented by the following formula [1] (hereinafter referred to as a spiroorthocarbonate compound) and a curing agent thereof curable resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (R^1 and R^2 in the above formula are divalent organic groups that are the same or different from each other.)