JPS6060126A - Epoxy composition - Google Patents

Abstract

PURPOSE:The titled composition excellent in cracking resistance and thermal shock resistance and stable to heat, oxidative degradation and photodegradation, prepared by mixing a specified polyepoxyurethane compound with a dicarboxylic acid anhydride and a dihydrazide compound. CONSTITUTION:A polyepoxyurethane compound (A) is obtained by reacting 0.2- 4 equivalent of the alcoholic hydroxyl groups of an alcoholic hydroxyl group- containing polyepoxy compound such as a diglycidyl ether of average MW >=400, obtained by reacting disphenol A with epichlorohydrin with 1 equivalent of the isocyanato groups of a 4,4'-alkylidenedicyclohexyl diisocyanate compound of the formula (wherein R is H or CH3). Component a is mixed with (B) such an amount of a curing agent comprising 100pts.wt. dicarboxylic acid anhydride (e.g., phthalic anhydride) and 0.5-50pts.wt. dihydrazide compound (e.g., succinic acid dihydrazide) that the total number of acid anhydride groups and dihydrazide groups per epoxy group is 0.3-1.5.

Description

Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a new epoxy resin composition, which has excellent performance in particular in terms of stability against light and heat, and is suitable for casting and sealing of electronic and electrical components. This invention relates to transparent epoxy resin compositions suitable for stopping, combining, coating, etc.

[Technical Prohibition of Invention No. 1; Point 1] Recently, it has become important to use epoxy resins for coating and restraining parts, especially in the electrical and electronics fields. It was a song.

Such transparent epoxy resins should not undergo any discoloration that impairs light permeability during curing, and should not undergo any deterioration caused by heat or oxidation after curing, and the discoloration and malfunction associated with such deterioration. It is necessary to cure excellent stability against deterioration of optical properties.

Furthermore, in addition to stability against thermal and oxidative deterioration912 and optical deterioration, it also suppresses shear strain during heat curing (2), which increases the surface cracking properties of meconium compounds and heat resistance1Φ
At the same time, there is a strong demand for improvement in the physical properties of aluminum.

Conventionally, as a transparent epoxy resin, bisphenol A
Anhydride-curable epoxy resin compacts based on type epoxy compounds, alicyclic compounds, epoxy compounds, etc. are used, but in particular, the resin cured products have a high resistance to copper cracking, cracking, and heat resistance. No results were obtained for sufficient titration.

[Purpose of the invention]

As a result of extensive research, the present inventor has discovered that the disadvantages of the prior art are as follows: Transparent, with excellent crack resistance and thermal shock resistance, and excellent stability against thermal and oxidative deterioration, as well as optical deterioration. "We have discovered an epoxy resin composition.

[Departure IsujO) Approximately the following day]

That is, the present invention ['', (a) alcoholic water! alcoholic hydroxyl group of a polyepoxy compound having a group and 4,4-alkylidene dicyclohexyl represented by the general formula [1] Provided is an epoxy resin composition comprising a polyepoxyurethane compound obtained by reacting incyanate groups of a diisocyanate, and (b) a dicarboxylic acid anhydride and a dihydrazide compound as a curing agent. It is.

In the present invention (2), a polyepoxy compound having an alcoholic hydroxyl group refers to a compound having both an alcoholic hydroxyl group and two or more epoxy groups in the molecule, and a compound having an alcoholic hydroxyl group and two or more epoxy groups in the molecule. It is a mixture of a compound that has both alcoholic hydroxyl groups and a compound that has two or more epoxy groups without an alcoholic hydroxyl group in the molecule. The compound is, for example, a diglycidyl ether obtained from the reaction of bisphenol A or bisphenol F or hydrogenated bisphenol A with epichlorohydrin and has an alcoholic hydroxyl group;
Alternatively, there are embodiments of the above epoxy compounds. On the other hand, compounds having an epoxy group without an alcoholic hydroxyl group in the molecule include, for example, polybricidyl ether of phenol novolak or cresol novolak, or bisphenol A1, bisphenol F, or compounds obtained from the reaction of hydrogenated bisphenol A and epichlorohydrin. There are diglycidyl ethers that do not have an alcoholic hydroxyl group, and those that are the embodiments of the above-mentioned s4xy compounds. Among these polyepoxy compounds having an acid content of O) alcohol, diglycidyl ethers derived from bisphenol A and epichlorohydrin, and those having an average molecular weight of 400 or more are excellent. When the average molecular weight is less than 400 (2), the content of alcoholic water groups decreases, the function of the isocyanate group as a masking agent decreases, and the storage stability at room temperature decreases.

Furthermore, the formula 4. shown in the above formula [1] used in the present invention
4-7, n, in the compound of kylidene dicyclohexyl resinocyanate, [1] Formula C2 R force 1.11
When R is CH, it is dicyclohexylmethane-4,4-diisocyanate, and when R is CH, it is 11° dichlorohexyl-4,4-cyanate. When these 4,4-alkylidene dicyclohexyl diisocyanates are used, compounds with good optical stability, heat resistance, and properties can be obtained.

Furthermore, 4,4-alkylidene dicyclohexyl diincyanate represented by the formula [1] and the former Re alcoholic water i! The combination ν) with a polyincyanate compound having 12 groups can be selected as appropriate, but preferably 05 to 5 epoxy groups and alcoholic water (02 groups) per equivalent of incyanate group. ~4 equivalents.If the epoxy group is 0.5 equivalents or less than 1 equivalent of incyanate (compared to 7), many urethane bonds will remain in the final cured product,
Free isocyanate groups tend to remain, resulting in decreased heat resistance and moisture resistance. Moreover, when the epoxy group is on the upper side, the thermal property decreases.

On the other hand, if the alcoholic hydroxyl group is less than 0.2 times per isocyanate group (2), a large number of free isocyanates remain in the polyepoxyurethane compound, and the storage stability decreases. Moreover, if the amount of alcoholic hydroxyl groups is more than 4 equivalents, the final cured product (many dihydroxyl groups will remain) and moisture resistance etc. will decrease.

Furthermore, the dicarboxylic acid anhydride used in the present invention is
For example, phthalic anhydride, maleic anhydride.

Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, dicycloconophosphoric anhydride, and the like are used.

Examples of the dihydrazide compound used in the present invention include succinic acid dihydrazide, adipic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, gimaric acid dihydrazide, and terephthalic acid dihydrazide, among which adipic acid dihydrazide and inphthalic acid dihydrazide are preferred. .

The amount of the dihydrazide compound to be used is 0.5 to 50 parts by weight per 100 parts by weight of the dicarboxylic acid anhydride, and the stability of the cured epoxy resin against thermal and oxidative deterioration, as well as optical deterioration. A cured product can be obtained which has extremely good properties and can significantly improve crack resistance and thermal shock resistance. If the dihydrazide compound is used in an amount of 50 parts by weight or more, the resulting reaction product improves the thermal shock resistance of the cured epoxy resin, but deteriorates the resin properties of the epoxy resin; If less than 1 part is used, the reaction product obtained cannot improve the thermal shock resistance of the cured epoxy resin, which is not preferable.

In addition, the blending ratio of the polyepoxy urethane compound obtained by reacting the alcoholic hydroxyl group of the polyepoxy compound having an alcoholic hydroxyl group with the incyanate group of the polyisocyanate compound, the dicarboxylic acid anhydride, and the dihydrazide compound may be adjusted depending on the purpose. Although it can be selected, the amount is preferably such that the total number of acid anhydride groups and hydrazide groups per epoxy group is 0.3 to 1.5.

In the present invention, the addition of a catalyst is useful because the reaction proceeds more rapidly. Catalysts used in the present invention include those used as ordinary urethane group-forming catalysts, or those used as catalysts for the reaction of epoxy compounds with dicarboxylic acid anhydrides and dihydrazide compounds. Examples include tertiary amines, boron trifluoride-amine complex salts, quaternary ammonium salts, metal halides, metal alkoxides, organometallic compounds, imidazole compounds, tertiary phosphines, quaternary phosphonium salts, and the like.

0.01 to 1 or more of the above catalysts
It is useful to include 0 parts by weight.

In addition, this resin composition (2) is an extender, 1) is a filler, a colorant, a plasticizer, a flow control agent, a ticuntrobe agent,
Various additives or modifiers such as a recording polarizing agent and a mold release agent can be added thereto.

[ Parts] are all parts by weight.

[Embodiments of the invention]

Example 1 Dicyclohexylmethane-4,4-diisocyanate (
(hereinafter abbreviated as C, HMDI) 100 parts, bisphenol A
Diglycidyl ether obtained from the reaction of and epichlorohydrin (average molecular weight approximately 1 ooo, engineering Si xy equivalent approximately 480, alcoholic hydroxyl group = RFJ500)
) in a nitrogen stream at 100° C. for 3 hours to obtain a polyepoxy-urethane compound.

600 parts of this polyepoxy urethane compound, 100 parts of hexahydrophthalic anhydride, and 15 parts of isolatal acid dihydrazide were added to form Evazixy resin 8Vi! 1 Adjusted.

This resin composition was poured into an aluminum mold (height: 10 mm).
Pour and heat air oats into a circular mold with a diameter of 100mm.

One stool was immersed at 160°C x 30 minutes + 175°C x 4 hours in a chamber. The resulting sample was subjected to high pressure heating at 100°C for 1000 hours, and the color stability was measured. Color stability picture I11. Evaluation was made from ft r2. The results are shown in Table 1.

This resin composition was coated with an outer diameter of 33 am and an inner diameter of 11.5 mm.
, 10 aluminum containers with a diameter of 40 mm each containing 1 set of screw washers (made of stainless steel with a thickness of 3 mm)
Add gr at a time, curing conditions 160'0 x 30 minutes + 175
Cured at 4 hours at °OX. The obtained cured product was then returned to room temperature, and the number of cracks and thermal softening temperature were measured.

The results are shown in Table 1.

Next, two types of experiments (A) and (B) shown in Table 1 were conducted as comparative examples. Comparative Example (A) uses diphenylmethane-4,4-instead of CHMDI used in the above-mentioned examples of the present invention.
The procedure was carried out in exactly the same manner as in the examples of the present invention, except that the equivalent number of moles of diisocyanate was used.

Comparative Example (B) was carried out in exactly the same manner as the example of the present invention except that a corresponding number of moles of hexahydrophthalic anhydride was used in place of the inphthalic dihydrazide used in the example of Akira Motokura.

[Note] In the above table *Cure at 1160°C for 30 minutes, 175°C for 4 hours*
2 Visual evaluation; 0 - best score 5 = worst score Example 2 100 parts of isopropylidene dicyclohexyl-4,4 diincyanate (hereinafter abbreviated as IPCI) obtained from the reaction of bisphenol A and epichlorohydrin Diglycidyl ether (average molecular weight approximately 700, epoxy equivalent approximately 340, alcoholic hydroxyl equivalent approximately 700) 600
part, polyglycidyl ether of cresol novolac (
A polyepoxy-urethane compound was obtained by reacting with 100 parts of (average molecular weight: about 1400, epoxy equivalent: about 230, no alcoholic hydroxyl group) at 100°C for 3 hours in a nitrogen stream.

An epoxy resin composition was prepared by adding 800 parts of this polyepoxy urethane compound, 200 parts of methyltetrahydrophthalic anhydride, and 40 parts of adipic acid dihydrazide.

Color stability, number of cracks, and thermal softening temperature were measured in the same manner as in Example 1.

The results are shown in Table 2.

Next, two types of experiments (A) and (B) shown in Table 2 were conducted as comparative examples. Comparative example (A) was carried out in exactly the same manner as the example of the present invention, except that the equivalent number of moles of 2,4-tolylene diisocyanate was used instead of IPCI used in the example of the present invention. . Comparative Example (B) was carried out in exactly the same manner as the Example of the present invention, except that a corresponding number of moles of methyltetrahydrophthalic anhydride was used in place of the adipic acid dihydrazide used in the Example of the present invention.

Table 2 [Note] In the above table *1160°0 (Second 30 minutes, cured at 175℃ for 4 hours *2 Visual evaluation; 0 = Best evaluation score 5 - Worst evaluation score [Effect of the invention] According to the present invention, a transparent resin composition having excellent crack resistance, thermal shock resistance, and stability can be obtained.

Claims (1)

[Claims] (a) The alcoholic hydroxyl group of a polyepoxy compound having an alcoholic hydroxyl group and the general formula [1] ■ 几 (In the formula [1], each R is I (or Cl-13) A polyepoxyurethane compound obtained by reacting the incyanate group of the 4,4-alkylidene dicyclohexyl diincyanate compound shown, and (b) a dicarboxylic acid anhydride and a dihydrazide compound as a li!lT-forming agent, An epoxy 111% composition characterized by blending.