JPH04154860A - Curable epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a curable epoxy resin composition containing an epoxy resin having an aromatic amide structure, polyethersulfone and a specific curing agent and having excellent mechanical characteristics, especially of toughness, adhesivity, etc. CONSTITUTION:The objective composition consisting of (A) 100 pts.wt. epoxy resin expressed by formula I (R1 is formula II or formula III; R2 is H or methyl; (n) is >=0), e.g. obtained by reaction of a phenol compound obtained by reacting terephthalic acid dichloride with p-aminophenol in an amide based solvent with epihalohydrin, preferably epoxy resin expressed by formula IV, (B) 5-70 pts.wt. polyethersulfone expressed by formula V ((m) is 5-500) and (C) 10-40 pts.wt. one or more kinds of curing agents selected from an aliphatic amine, aromatic amine, acid anhydride and a compound (e.g. diamine or diaminodiphenylmethane) expressed by formula IV (A is O, CH2 or SO2).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention particularly relates to a curable epoxy resin composition having excellent mechanical properties such as toughness and adhesive strength.

[Conventional technology and its issues]

Epoxy resins are commonly used as encapsulants and heat-resistant adhesives for IC boards, but they have problems such as residual strain due to volumetric shrinkage during polymerization, generation of internal stress, and toughness.

Conventionally, as an improvement method, an epoxy resin composition containing a filler such as an elastomer has been developed.

For example, a composition is known in which liquid nitrile rubber (CTBN, ATBN) having carboxyl groups or amino groups at both ends is blended with bisphenol A type epoxy resin.
The composition has a sea-island structure with spherical domains of rubber dispersed in an epoxy resin medium. However, this epoxy resin composition has not yet been commercialized. This is because in the case of a mixed system of epoxy resin/nitrile rubber, the phase separation rate is too fast, so that no significant structural control is possible.

As a result of intensive research, the present inventors found that in a mixed system of a new epoxy resin having an aromatic amide structure, polyether sulfone, and a specific curing agent, the microphase structure can be controlled in the range of 0.1 to 10 μm. The inventors have discovered that this is possible, and have completed the present invention.

[Failure to solve the problem]

The curable epoxy resin composition of the present invention comprises (A) an epoxy resin represented by the following general formula (1), Rz
Rz Rzl
1
1 group, R2 is a hydrogen atom or a methyl group,
n represents a number of 0 or more. ) (B) Polyether sulfone represented by the following general formula (2), (in the formula, m is a number from 50 to 500) (C) Aliphatic or aromatic amine, acid anhydride, and the following general formula (3) It is characterized by containing one or more types of curing agent selected from the group consisting of compounds represented by (in the formula, any one of o, CI+2 group, and SO2 group is represented).

The epoxy resin (A
) is a phenol compound represented by the general formula (4) (in which R1 is the same as in formula (1) above) and general formula (5) (in the formula, 1? is a hydrogen atom or (Methyl group, X represents a halogen atom) It is obtained by reacting epihalohydrin represented by:

The phenol compound represented by formula (4) above can be obtained by reacting terephthalic acid dichloride or isophthalic acid dichloride with para-aminophenol or meta-aminophenol in an amide solvent. Furthermore, the phenol compound represented by the general formula (4) of the present invention can be obtained by treating the reaction product of para-acetoxybenzoyl chloride or meta-acetoxybenzoyl chloride with para-aminophenol or meta-aminophenol in an aqueous alcohol solution with alkali carbonate. It can also be obtained by

Furthermore, as the epihalohydrin represented by the general formula (5) of the present invention, a boat fishing epihalohydrin can be used,
Examples include epichlorohydrin, β-methylepichlorohydrin, shrimp bromohydrin, and β-methylepibromohydrin. Preferably epichlorohydrin is used.

A phenol compound represented by general formula (4) of the present invention,
The reaction with epihahydrin represented by general formula (5) of the present invention is preferably carried out in an amide solvent in the presence of an alkali hydroxide. In this case, the epihalohydrin is
2 to 100 times the mole of the phenol compound, preferably 10
It is preferable to use up to 50 times the molar amount.

Examples of the alkali hydroxide that can be used here include sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc., but sodium hydroxide is preferably used.

The alkali hydroxide is used in an aqueous solution in a slightly excess amount relative to the hydroxyl group of the phenol compound represented by formula (4).

The reaction temperature of this reaction is 40 to 150°C, preferably 6
The temperature is preferably 0 to 120°C. Also, the reaction time is 0.5
~10 hours, preferably 1 to 5 hours.

As the solvent used in the reaction, amide solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone are preferably used.

It is preferable to use the minimum amount of solvent that can dissolve the phenol compound represented by formula (4) above.

A preferred example of the epoxy resin (A) represented by the general formula (1) of the present invention is an aromatic amide type epoxy resin represented by the following formula (6).

The polyether sulfone (B) represented by the general formula (2) of the present invention has a repeating unit number m of 50 to 500, preferably 50 to 300.

- The blending ratio of the epoxy resin (A) represented by the formula (1) and the polyether sulfone (B) represented by the formula (2) is 100 parts by weight of the epoxy resin (A) to the polyether sulfone (B) is 5 to 70 parts by weight, preferably 2
It is 0 to 40 parts by weight.

In the present invention, the epoxy resin curing agent (C) is an aliphatic amine or aromatic amine, an acid anhydride, and a formula (3).
) is used. - Examples of the compound represented by formula (3) include diaminodiphenyl ether, diaminodiphenylmethane, and diaminodiphenyl sulfone.

The curing agent (C) is used in an amount of 10 to 40 parts by weight per 100 parts by weight of the epoxy resin (^) represented by the general formula (1) of the present invention.
It is preferable to blend it in an amount of 20 to 30 parts by weight, preferably 20 to 30 parts by weight.

In curing the curable epoxy resin composition of the present invention, each component is mixed and dissolved in a solvent such as dimethylacetamide or dimethyl sulfoxide to prepare a 5-30% solution. After casting the obtained solution, 150-27
Cure at 0''C, preferably 180-250C, for 1-5 hours, preferably 2-3 hours.

When used, the cured epoxy resin composition of the present invention includes:
Various commonly used additives, fillers, etc. can be added.

〔Example〕

Examples of the present invention are listed below.

In the following examples, the gelation time is TBA (tors
ional braid analysis).

This gelation time corresponds to the time until the structure is fixed by curing of the epoxy resin. Further, the state of phase separation due to curing of the curable epoxy resin composition of the present invention and the final structural period were measured by observing changes in the profile over time using a light scattering method. The appearance of a maximum in the light scattering profile indicates the existence of a regular structure with a certain period, and the period Δm is calculated from the light scattering wavelength λ and the scattering angle θm giving the maximum using the following formula. Ru.

In addition, structural observation was performed using an optical microscope and a scanning electron microscope to confirm the microstructure.

Production Example 1 The epoxy resin represented by the above formula (6) was prepared in accordance with Japanese Patent Application No. 110
Prepared according to Example 2 of No. 2374.

Example 1 Epoxy resin 1 represented by formula (6) produced in Production Example 1
00 parts by weight, polyether sulfone (vICTl?EX 4100P manufactured by Sumitomo Chemical Co., Ltd., degree of polymerization approximately 200
) 3 oiqs, 29.7 parts by weight of diaminodiphenylsulfone, and 1 of N,N-dimethylacetamide.
It was made into a 0% solution.

A glass blade was immersed in this solution, dried at room temperature, and then used as a T BA sample. Is it the same again? 8 liquid onto a cover glass = l-1. 1, then remove the solvent for 24 hours at room temperature.
The sample was cured for 3 hours at C for 3 hours and used as a sample for light scattering measurement and optical microscopic observation.

The results of TBA measurement are shown in FIG.

Light scattering measurements revealed a maximum in the profile. The change over time of the structural period Am determined from the maximum position is calculated as the second
As shown in the figure. The structure grows over time and is fixed at a certain time, but the fixation time roughly matches the gelation time obtained from TBA. The structural period of the final cured product is shown in FIG. 3 as a function of the curing temperature. The higher the curing temperature, the larger the periodic structure.

FIG. 4 shows the results of optical microscopic observation under each curing condition. A periodic structure was observed that corresponded well to the light scattering results (Figure 3).

Example 2 100 parts by weight of the epoxy resin represented by formula (6) produced in Production Example 1, polyether sulfone (VICTl?EX 4100P1 manufactured by Sumitomo Chemical Co., Ltd. Polymerization degree of about 20)
0) 30 parts by weight, diaminodiphenylmethane 21.6
10 parts by weight of N,N-dimethylacetamide
% solution.

A glass blade was immersed in this solution, dried at room temperature, and then used as a sample for TBA. The results of TBA measurement are shown in FIG. This gelation time was so fast that it could not be measured by the final method. Although measurements cannot be made during the initial 2 minutes using the final method, gelation appears to have progressed during that time.

Furthermore, a thin film cured in the same manner as in Example 1 was used as a sample for light scattering and microscopic observation.

In light scattering and optical microscopy, no clear structure as seen in Example 1 was observed. Therefore, the sample was subjected to ultrasonic cleaning with methylene chloride to remove the polyether sulfone phase, and then observed with a scanning electron microscope. As a result, a structure of about 0.2 μm was observed (FIG. 5). This is because the curing speed of diaminodiphenylmethane is faster than that of diaminodiphenyl sulfone, so the three-dimensional network structure is also disrupted, and as a result, the structure is fixed at the early stage of phase separation, making it easier to It can be said that a cured product with a large phase structure was obtained.

Example 3 100 parts by weight of the epoxy resin represented by formula (6) produced in Production Example 1, polyether sulfone (VICTIInχ4100P manufactured by Sumitomo Chemical Co., Ltd., with a degree of polymerization of about 2
00) 30 parts by weight, diaminodiphenyl ether 21.
8 parts by weight of N,N-dimethylacetamide.
It was made into a 0% solution.

The results of TBA measurement and microscopic observation of the cured product cured in the same manner as in Example 1 were almost the same as in Example 2, and a cured product with micro phase separation was obtained.

Comparative Example 1 Instead of the epoxy resin of formula (6) in Example 1, 100 parts by weight of 1-bisphenol A type epoxy resin (Epicoat 828 US manufactured by Mitsubishi Yuka Co., Ltd.), 30 parts by weight of polyether sulfone, 26 parts by weight of diaminodiphenylmethane
Parts by weight of the composition were prepared according to Example 1. That TD
The results of the A measurement are shown in FIG.

〔Effect of the invention〕

The curable epoxy resin composition of the present invention can control the microstructure period in the range of 0.1 to 1.0 μm by selecting the curing agent and adjusting the curing temperature, thereby improving mechanical properties such as toughness and adhesiveness. An epoxy resin composition with excellent properties can be obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the results of TBA measurements of samples obtained in Examples 1 to 3 and Comparative Example 1. FIG. 2 is a graph showing changes over time in the structural period of the sample obtained in Example 1. FIG. 3 is a graph showing the relationship between the structural period and curing temperature of the sample obtained in Example 1. FIGS. 4(a) to 4(C) are optical micrographs showing the particle structure (phase structure) of the sample obtained in Example 1. FIGS. 5(a) to 5(b) are electron micrographs showing the particle structure (phase structure) of the sample obtained in Example 2. Applicant's agent: Yoshihide Furuya (3 others) Procedural amendment (voluntary) November 9, 1990 Patent application 2 filed on October 19, 1990, title of invention: Curable epoxy resin composition 3, amendment Patent application: Person (038) Asahi Denka Kogyo Co., Ltd. 4, Agent: Nihonbashi TM, 1-8-11 Nihonbashi Horidome-cho, Chuo-ku, Tokyo
Bill (63B9) Patent Attorney Kaoru Furuya (03
) 663-7808 (Main) 5, Claims and Detailed Description of the Invention column 6 of the specification to be amended, Contents of the amendment (1) Amend the statement of the claims as attached (1) Specification The general formula (2) in the 6th line from the bottom of page 4 of the book is 0.
” and amended (1) “The situation is broken” in line 5 of page 13 is corrected to “formation is fast” 2, Claim 1. (A) An epoxy resin represented by the following general formula (1), (B) Polyether sulfone represented by the following general formula (2), R2 is a hydrogen atom or a methyl group, and n is a number of 0 or more.・One or more curing agents selected from the group consisting of a phenol compound represented by (C) an aliphatic or aromatic amine, an acid anhydride, and a compound represented by the following general formula (3) (in the formula 1. A curable epoxy resin composition, characterized in that A represents any one of 0, CH, group, and SO2 group. Procedural amendment (voluntary) February 13, 1991 1, Case indication Patent application No. 2-281102 2, Name of the invention Curable epoxy resin composition 3, Person making the amendment Relationship to the case Patent application Asahi Denka Kogyo Co., Ltd. 4, Agent 5, Claims column 6 of the specification subject to amendment, Contents of amendment 2, Claims 1, (^) Expressed by the following general formula (1) epoxy resin,
R2 represents a hydrogen atom or a methyl group, and n represents a number of 0 or more. ) (B) Polyether sulfone represented by the following general formula (2), (in the formula, m is a number from 50 to 500) (C) Aliphatic or aromatic amine, acid anhydride, and the following general formula (3) ) A curable epoxy resin characterized by containing one or more curing agents selected from the group consisting of compounds represented by (wherein A represents any one of 0, CH2 group, and SO2 group) Composition.

Claims (1)

[Claims] 1. (A) an epoxy resin represented by the following general formula (1);
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1 is a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_2 is a hydrogen atom or Methyl group, n represents a number greater than or equal to 0.) (B) Polyether sulfone represented by the following general formula (2), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (In the formula, m is 50 - 500), (C) one or more curing agents selected from the group consisting of aliphatic or aromatic amines, acid anhydrides, and compounds represented by the following general formula (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) (In the formula, A represents any one of O, CH_2 group, SO_2 group) A curable epoxy resin composition characterized by containing the following.