JPH06136056A - Thermosetting resin composition and its use - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition giving a cured product having excellent moisture-resistance, adhesiveness and heat-resistance by using an imide compound, a cure accelerator, an epoxy resin and an epoxy hardener as essential components. CONSTITUTION:The composition is produced by compounding (A) a compound of formula (R<1> and R<2> are halogen, OH, phenyl, etc.; R<3> is H, phenyl or 1-6C alkyl; K is 0-3; L is 0-4; M is 1-5; the average number of recurring units n is 0-10; D is 2-24C bivalent organic group having polymerizable unsaturated double bond) with (B) a cure accelerator (preferably triphenyl phosphine, etc.), (C) an epoxy resin (preferably o-cresol novolak epoxy resin, etc.) and (D) an epoxy hardener (preferably phenolic novolak resin). The amount of the component B is arbitrary and the ratio of A/(A+B+D) is 90-10%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition which is particularly useful as a sealing material for electronic parts and a material for laminated boards, and electronic parts and copper clad laminated boards molded from the composition. Regarding

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used for molding and sealing electronic parts such as semiconductors or molding laminated plates. This epoxy resin has been widely put into practical use because it is economically advantageous as compared with the hermetic sealing method using glass, metal, or ceramic. However, in recent years, the usage conditions of electronic parts have tended to become severe. For example, as the mounting method shifts from conventional insertion mounting to surface mounting, the sealing material itself is exposed to the solder bath temperature. As a result, the heat resistance of the sealing material has become an important characteristic. Recently, thermosetting polyimide resin encapsulation has been proposed for the purpose of obtaining high heat resistance. Further, there is a strong demand for heat resistance in laminated boards as well, and thermosetting polyimide resins have been used in fields where heat resistance is highly required.

[0003]

However, although the electronic encapsulation component molded and encapsulated using a polyimide resin has excellent heat resistance, it has a major drawback in terms of moisture resistance, which is a characteristic of a thermosetting polyimide resin. have. Also,
For laminated boards using thermosetting polyimide resin,
It had a defect in terms of moisture resistance or adhesiveness with copper foil. An object of the present invention is to provide a thermosetting resin composition excellent in moisture resistance, adhesiveness and heat resistance of a cured product, an electronic component using the same and a copper clad laminate.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventor has found that a thermosetting resin composition containing a specific imide compound is suitable for the above purpose, and completed the present invention. That is, the present invention is as follows. (1) (A) General formula (1)

[0005]

[Chemical 2]

(Wherein R ¹ and R ² are halogen atoms,
When a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group, a substituted phenoxy group having 10 or less carbon atoms or an alkyl group or an alkenyl group having 6 or less carbon atoms, and each of R ¹ and R ² is plural They may be the same or different from each other. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms and may be the same or different. K is 0
Is an integer of 3 to 3, L is an integer of 0 to 4, M is an integer of 1 to 5, and the average repeating unit number n is a number of 0 to 10. D represents a divalent organic group having a polymerizable unsaturated double bond and having 2 to 24 carbon atoms. The thermosetting resin composition which has an imide compound and the (B) hardening accelerator which are represented by these as an essential component.

(2) Thermosetting with (A) the imide compound represented by the general formula (1), (B) a curing accelerator, (C) an epoxy resin and (D) an epoxy curing agent as essential components Resin composition.

(3) An electronic component molded and encapsulated with the thermosetting resin composition as described in (1) or (2) above.

(4) A base material is impregnated with a resin varnish obtained by dissolving the thermosetting resin composition described in (1) or (2) above in an organic solvent, and a heat-treated prepreg and a copper foil are laminated and laminated. Thermosetting resin copper clad laminate formed by heat molding.

The present invention will be described in detail below. In the general formula (1) representing the imide compound of the component (A) used in the present invention, specific examples of R ¹ and R ² are:
Halogen atom such as fluorine, chlorine, bromine and iodine; hydroxyl group; phenyl group; alkoxy group having 4 or less carbon atoms such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group; phenoxy group; p -, M- or o-methylphenoxy group, p-, m- or o-ethylphenoxy group, p-, m- or on-propylphenoxy group, p-, m- or on-butylphenoxy group A substituted phenoxy group having 10 or less carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-
Examples thereof include alkyl groups and alkenyl groups having 6 or less carbon atoms such as butyl group, isobutyl group, n-amyl group, isoamyl group, n-hexyl group, vinyl group, allyl group and crotyl group. Further, specific examples of R ³ include a hydrogen atom; a phenyl group, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include alkyl groups having 6 or less carbon atoms such as isopropyl group, n-butyl group, isobutyl group, n-amyl group, isoamyl group and n-hexyl group. As a specific example of D, −
CH = CH -, - C ( = CH 2) -CH 2 -, - C (C
_{H 3) = CH -, -} CCl = CCl-, formula (a)

[0011]

[Chemical 3] And the like. In general, 0 to 10 representing the average number of repeating units is suitable, and 0 is preferable.
-5, more preferably 0-2. If n is too large, the viscosity of the imide compound becomes too high, which is not preferable.

The imide compound represented by the general formula (1) is
It can be obtained by reacting a polyamine described below with an unsaturated dicarboxylic acid anhydride by a known method to imidize. For example, a method of imidizing using a dehydrating agent such as acetic anhydride or a method described in Japanese Patent Publication No. 2-58267 can be applied. The polyamine used here has the general formula (2)

[Chemical 4] (In the formula, the meanings of R ¹ , R ² , R ³ , K, L, M and n are the same as those in formula (1).).

The above polyamine is obtained by a condensation reaction between anilines and a carbonyl compound. Specific examples of anilines include aniline, toluidine, ethylaniline, propylaniline, butylaniline, xylidine,
Diethylaniline, ethylmethylaniline, ethylpropylaniline, ethylbutylaniline, methylpropylaniline, dipropylaniline, trimethylaniline,
Cyclohexylaniline, phenylaniline, chloroaniline, dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, chlorotoluidine, chloroxylidine, aminophenol, aminocresol,
Examples include various isomers such as methoxyaniline, dimethoxyaniline, methoxymethylaniline, hydroxymethoxyaniline, phenoxyaniline, methylphenoxyaniline, vinylaniline and allylaniline. These anilines can be used not only alone but also as a mixture of two or more kinds.

The carbonyl compound is represented by the general formula (2)
A compound in which one carbonyl group is directly bonded to a benzene nucleus having at least one substituent R ² which is the same as
Specifically, tolualdehyde, ethylbenzaldehyde,
Propylbenzaldehyde, butylbenzaldehyde,
Various kinds of cyclohexylbenzaldehyde, hydroxybenzaldehyde, methoxybenzaldehyde, phenylbenzaldehyde, phenoxybenzaldehyde, methylphenoxybenzaldehyde, vinylbenzaldehyde, allylbenzaldehyde, methylacetophenone, benzophenone, chlorobenzaldehyde, dichlorobenzaldehyde, bromobenzaldehyde, dibromobenzaldehyde, fluorobenzaldehyde, difluorobenzaldehyde, etc. Examples include isomers and derivatives.

These carbonyl compounds can be used not only alone but also as a mixture of two or more kinds.
Other carbonyl compounds may be mixed with the carbonyl compound of the present invention to the extent that the effects of the present invention are not impaired. Other carbonyl compounds include formaldehyde, acetaldehyde, acetone, benzaldehyde,
Examples include various isomers and derivatives such as acetophenone, aminobenzaldehyde, acrolein, crotonaldehyde, cinnamic aldehyde, glyoxal, and 2,3-naphthalenedialdehyde.

Condensation reaction of these anilines and carbonyl compounds is carried out by using inorganic acids such as HCl and H ₂ SO ₄ , acetic acid, p
-Toluenesulfonic acid, organic acids such as thioglycolic acid,
In the presence of an acidic catalyst such as Lewis acid, or an ion exchange resin,
It can be obtained by a well-known method of post-treatment such as condensation at a temperature of 40 to 150 ° C., neutralization, washing with water, distillation of unreacted aniline and the like. When the target substance precipitates as crystals, the crystals may be filtered off, washed and dried.

N in the general formula (2) representing polyamine
Can be adjusted according to the synthesis conditions such as the charged molar ratio of aniline and carbonyl compound and the amount of catalyst.

The unsaturated dicarboxylic acid anhydride, which is another raw material for synthesizing the imide compound, includes maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, pyrocinconic anhydride, and tetrahydrophthalic anhydride. , And Diels-Alder reaction products of these unsaturated dicarboxylic acid anhydrides and dienes, for example, cyclized adducts which are Diels-Alder reaction products of maleic anhydride with cyclopentadiene, furan and terpinene. . These are used alone or in combination of two or more.

The reaction between the polyamine and the unsaturated dicarboxylic acid anhydride is carried out, for example, by using 1 to 1.3 mol of the unsaturated dicarboxylic acid anhydride per 1 equivalent of the amino group in the polyamine compound, using an aromatic hydrocarbon solvent or halogen. The addition reaction in a mixed solvent of a hydrocarbon compound and an aprotic polar solvent,
In the presence of an acidic catalyst, in the temperature range of 80 to 200 ° C, 0.5 to
A dehydration ring closure reaction is performed for 10 hours.

The aromatic hydrocarbon solvent used here is, for example, benzene, toluene, xylene or the like, and the halogenated hydrocarbon solvent is, for example, chloroform, 1,2-dichloroethane or chlorobenzene. As the aprotic polar solvent, N, N-dimethylformamide, N, N-dimethylacetamide,
Dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like can be used. In the mixed solvent, the mixing ratio of the aromatic hydrocarbon solvent or halogenated hydrocarbon solvent and the aprotic polar solvent is about 50:50 to 99: 1. This mixed solvent is usually used in an amount of 1 to 10 times the weight of the raw materials.

After the reaction between the polyamine and the unsaturated dicarboxylic acid anhydride is completed, the reaction solution is dropped into a poor solvent to precipitate a product, which is then filtered, washed and dried to obtain an imide compound as a product.

As the curing accelerator of the component (B) used in the present invention, known curing accelerators can be used. Examples thereof include organic phosphine compounds such as triphenylphosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tributylphosphine, trioctylphosphine and tri-2-cyanoethylphosphine, tributylamine, triethylamine, 1 , 8-diazabicyclo (5,4,0) undecene-7, tertiary amines such as triamylamine, quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium hydroxide, triethylammonium tetraphenylborate, imidazoles, Boron trifluoride complex, transition metal acetylacetonate, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide Methyl ethyl ketone peroxide, cyclohexanone peroxide, t- butyl hydroperoxide, although radical initiator such as azobisisobutyronitrile and the like, but is not limited thereto. Among these, organic phosphine compounds, 1,
8-Diazabicyclo (5,4,0) undecene-7 and triethylammonium tetraphenylborate are particularly preferable from the viewpoint of moisture resistance and curability.

It is also possible to use a known polymerization inhibitor together in order to adjust the curing speed. Examples thereof are 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-methylenebis (2,6-).
Di-t-butylphenol), 4,4'-thiobis (3
-Methyl-6-t-butylphenol), phenols such as hydroquinone monomethyl ether, hydroquinone, catechol, pt-butylcatechol, 2,6-
Polyphenols such as di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone and pyrogallol, phenothiazine, benzophenothiazine,
There are phenothiazine compounds such as acetamidophenothiazine and N-nitrosamine compounds such as N-nitrosodiphenylamine and N-nitrosodimethylamine.

As the epoxy resin as the component (C) used in the present invention, known epoxy resins can be used. Specific examples of these include novolac-based epoxy resins derived from novolac resins, which are reaction products of phenol, phenol such as o-cresol, and formaldehyde, phloroglysin, tris- (4-hydroxyphenyl) -methane, 1,1,2,2-tetrakis (4
-Hydroxyphenyl) ethane and other glycidyl ether compounds derived from trihydric or higher phenols, bisphenol A, bisphenol F, hydroquinone, resorcin, 1,1'-bis (3-t-butyl-6-methyl-4-) Glycidyl ether compounds derived from dihydric phenols such as (hydroxyphenyl) butane and tetramethylbiphenol, or tetrabromobisphenol A
Diglycidyl ether compounds derived from halogenated bisphenols such as

Glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds, p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4 '-Diaminodiphenylmethane,
3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene,
1,3-bis (3-aminophenoxy) benzene, 2,
2-bis (4-aminophenoxyphenyl) propane,
p-phenylenediamine, m-phenylenediamine,
2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine),
Amine-based epoxy resin derived from 1,3-cyclohexanebis (methylamine), p-oxybenzoic acid,
Glycidyl ester compounds derived from aromatic carboxylic acids such as m-oxybenzoic acid, terephthalic acid and isophthalic acid,

Hydantoin-based epoxy compounds derived from 5,5-dimethylhydantoin, etc., 2,2-bis (3,4-epoxycyclohexyl) propane, 2,2
-Bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide,
There are alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, N, N-diglycidylaniline, and the like, and one or more kinds of these epoxy resins are used.
Of these, o-cresol novolac epoxy resins and glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols with aromatic carbonyl compounds are preferable from the viewpoint of curability and heat resistance.

As the epoxy curing agent which is the component (D) used in the present invention, known epoxy curing agents can be used. Examples of these are bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ethane, 1,3,3-trimethyl-1-m-hydroxy. Reaction products of phenol with phenols such as phenylindan-5 or 7-ol, 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol and phenol, o-cresol Phenols such as polyphenol compounds such as novolac, polycarboxylic acids such as maleic acid, phthalic acid, nadic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and their anhydrides, diaminodiphenylmethane, diaminodiphenyl Sulfone, diaminodiphenyl ether,
Polyamine compounds such as phenylenediamine, diaminodicyclohexylmethane, xylylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (each containing isomers), ethylenediamine, hexamethylenediamine, and further dicyandiamide, tetramethylguanidine, etc.,
Examples thereof include active hydrogen-containing compounds capable of reacting with an epoxy group. Of these, phenol novolac resins are preferably used from the viewpoint of curability and moisture resistance.

In the thermosetting resin composition of the present invention,
The proportion of the curing accelerator used as the component (B) varies depending on the degree of curing speed required. This degree depends on the application. For example, in the case of a sealing material such as a semiconductor, usually the resin 10
The amount of the curing accelerator is 1 to 3 parts by weight with respect to 0 parts by weight. In the thermosetting resin composition of the present invention, (A), (C),
The proportion of each component (D) used can be appropriately selected depending on the intended use, desired heat resistance and the like. Generally, it is preferable to select the content rate of the imide compound {(A) / [(A) + (C) + (D)]} to be 90% to 10%. More preferably,
It is 70 to 30%. If the blending ratio of the imide compound deviates from the above range, the moisture resistance and the heat resistance decrease, which is not preferable. Further, (C) component epoxy resin and (D)
With respect to the mixing ratio with the curing agent which is a component, it is preferable to use an equal amount. If the blending amount of the component (C) and the component (D) deviates from the equimolar blending amount, moisture resistance, curability and the like are deteriorated, which is not preferable.

A filler may be added to the thermosetting resin composition of the present invention if necessary. As the filler used, fused silica, crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica,
Red iron oxide, glass fiber and the like can be mentioned, and among them, fused silica, crystalline silica and alumina are preferably used. The blending ratio of the filler can be appropriately determined according to the purpose, but when used for semiconductor encapsulation, it is preferably 30 to 90% by weight, more preferably 60 to 85% by weight based on the total amount of the resin composition. %. If the amount of the filler is less than 30% by weight, the moisture resistance is inferior, and if it exceeds 90% by weight, there is a problem in moldability.

In the thermosetting resin composition of the present invention, if necessary, a natural wax, a synthetic wax, a higher fatty acid and a metal salt thereof, a releasing agent such as paraffin or a coloring agent such as carbon black, and You may add surface treatment agents, such as a silane coupling agent. Further, a flame retardant such as antimony trioxide, a phosphorus compound and a brominated epoxy resin may be added. A brominated epoxy resin is particularly preferable for producing a flame retardant effect.

In order to reduce the stress, for example, various elastomers may be added or reacted in advance and used. Specific examples thereof include addition-type or reaction-type elastomers such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber, and silicone oil. The thermosetting resin composition thus obtained can be compounded by melt-mixing with a general kneader such as a roll or a co-kneader.

In order to seal an electronic component such as a semiconductor using the thermosetting resin composition according to the present invention, it may be cured and molded by a conventionally known molding method such as transfer molding, compression molding or injection molding.

The copper-clad laminate using the thermosetting resin composition of the present invention can be prepared by a known method. That is, by impregnating a base material with a resin varnish obtained by dissolving the thermosetting resin composition in an organic solvent, and then heat-treating the prepreg and a copper foil to form a copper-clad laminate by heating and laminating a prepreg and a copper foil. is there. The organic solvent used is methyl cellosolve, N, N-dimethylformamide,
Dissolvable substances such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, dioxane, and tetrahydrofuran can be preferably used, and among these, a single solvent or a mixed solvent of two or more types can be used. To be selected.

The base material impregnated with the resin varnish is an inorganic fiber such as glass fiber, polyester fiber or polyamide fiber,
Woven cloth made of organic fibers, or non-woven cloth or mat,
It is paper or the like, and these may be used alone or in combination. The heat treatment conditions for the prepreg are appropriately selected depending on the solvent used, the catalyst added, and the types and amounts of various additives used, but are usually at a temperature of 80 ° C. to 220 ° C. for 3 minutes to 30 minutes. Heat molding conditions are exemplified 20 to 300 minutes of thermal press molding at a molding pressure of 10kg / cm ² ~100kg / cm ² at a temperature of 0.99 ° C. to 300 ° C..

[0035]

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention is excellent in processability, heat resistance of the cured product, particularly strength and humidity resistance when heated, and is more adhesive than the conventionally known heat resistant resin composition. And is extremely useful as a sealing material and a resin composition for copper-clad laminates. The electronic component such as a semiconductor and the copper-clad laminate according to the present invention have excellent heat resistance and moisture resistance.

[0036]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The evaluation of the kneaded product and the cured molded product is as follows. -Gel time: 0.5 g of the kneaded product obtained in each of the examples and comparative examples was placed in a recess of a hot plate at 180 ° C, and the time until gelation was measured.・ Glass transition temperature: Thermomechanical analyzer (SHIMADZ
It was measured using UDT-30). Barcol hardness: 93 according to ASTM D-648
It was measured with a type 5 under the condition of 175 ° C./3 minutes. Bending strength, flexural modulus: Instron universal material testing machine (SHIMADZU) according to JIS K-6911
IS-10T). Moisture absorption rate: Using a thermo-hygrostat (TABAI PR-2), the weight change was measured under the conditions of 85 ° C / 85% RH.・ Spiral flow: 17 according to EMMI-1-66
It was carried out under the conditions of 5 ° C./70 kg / cm ² . -Adhesive strength (aluminum peel): A molded product was transfer-molded on an aluminum foil, and the peel strength was evaluated.

Solder cracking property: Simulated IC (52-pin QFP package: package thickness 2.05 mm) 85
The number of individual ICs with cracks, which were obtained by absorbing moisture under the condition of ° C / 85% RH / 72 hours and immediately after soaking in a solder bath at 240 ° C for 30 seconds. 10 test individuals.・ Copper foil peeling strength, solder heat resistance, boiling water absorption: JIS
The measurement was performed according to C-6481.

Reference Example 1 Synthesis of Polyamine 595.2 g (6.40 mol) of aniline was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer and a condenser.
3-Phenoxybenzaldehyde 158.4 g (0.8
0 mol) and 32.4 g (0.32 mol) of concentrated hydrochloric acid were charged, the internal temperature was raised to 110 ° C., and the temperature was kept for 7 hours. After completion of the reaction, 48% sodium hydroxide aqueous solution at an internal temperature of 60 ° C. 3
2.0 g (0.38 mol) was added while paying attention to the heat of neutralization, and the mixture was stirred for 1.5 hours to precipitate crystals. After cooling to room temperature and separating the crystals by filtration, the crystals are washed twice with 300 g of water and twice with 500 g of toluene, and dried under reduced pressure at 70 ° C. to obtain white crystals (hereinafter referred to as ANPA) 2.
32 g was obtained. The average number of repeating units n (see general formula (2)) of this product was 0 according to GPC analysis. FD-
The MS spectrum detected a fragment of 198 (corresponding to the molecular weight of the desired product). In the general formula (2), L = 0, R ² : a phenoxy group (3 position),
It is a compound in which M = 1, R ³ : H, and n = 0.

Reference Example 2 Synthesis of Imide Compound Maleic anhydride 10.8 g was placed in a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser.
(0.11 mol) and 67.9 g of acetone were charged and dissolved by stirring. 18.4 g of ANPA (0.05
(Mol) was separately charged over 2 hours at an internal temperature of 5 ° C., and the mixture was further stirred for 1 hour and left overnight. Nickel acetate tetrahydrate 0.107 g (0.00043 mol) and triethylamine 3.04 g (0.03 mol) were charged, followed by an internal temperature of 4
At 0 ° C, 13.3 g (0.13 mol) of acetic anhydride was added dropwise over 30 minutes, and the mixture was kept at 40 ° C for 10 hours. After completion of the reaction, a water-methanol mixed solvent (= 1 /
1) It was crystallized by dropping it into 390 g and stirring for 1 hour. The crystals were separated by filtration, washed twice with 320 g of methanol and then 6
By drying under reduced pressure at 0 ° C, the target yellow crystals (ANPA-M
And ) 21.0 g were obtained. The melting point of this product is 132
It was ℃.

Reference Example 3 Synthesis of Polyamine 390.6 g (4.20 mol) of aniline was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer and a condenser.
4-isobutylbenzaldehyde 113.4 g (0.7
(0 mol) and 21.7 g (0.26 mol) of concentrated hydrochloric acid were charged, the internal temperature was raised to 110 ° C., and the temperature was kept for 4 hours. After completion of the reaction, 48% sodium hydroxide aqueous solution at an internal temperature of 60 ° C. 3
3.6 g (0.27 mol) was charged and neutralized. Chloroform (537 g) was charged, and the mixture was washed 3 times with ion-exchanged water (300 g) and liquid separation was repeated, and the organic layer was concentrated to obtain 203.4 g of a target resinous material (referred to as ANIB). The average number of repeating units n of this product by GPC analysis was 0.17. By FD-MS spectrum, 330, 567,
804 fragments were detected. In the general formula (2), L = 0, R ² : isobutyl group (4
Position), M = 1, R ³ : H, n = 0.17 (average value).

Reference Example 4 Synthesis of imide compound Maleic anhydride 1 was placed in a 500 ml four-necked flask.
0.8 g (0.11 mol) and 108 g of toluene were charged and dissolved. A solution prepared by previously dissolving 16.5 g (0.01 equivalent) of ANIB in 16.5 g of NMP and 16.5 g of toluene was added dropwise to the solution at an internal temperature of 25 ° C. over 1 hour, and the mixture was stirred for 4 hours after the addition. p-toluenesulfonic acid
2.85 g (0.015 mol) of monohydrate was charged, the internal temperature was raised to the toluene reflux temperature, and an azeotropic dehydration cyclization reaction was carried out at 120 ° C. for 4 hours. During this period, toluene was returned to the reaction system by the azeotropic dehydration tube, and the produced water was continuously distilled out of the reaction system. After cooling, washing with 400 g of ion-exchanged water and liquid separation were repeated 4 times. After washing with water, the organic layer was concentrated under reduced pressure at 80 ° C. to obtain a solid. After crushing this solid material, an additional 80
It was dried under reduced pressure at ℃. In this way, the target yellow powder (AN
IB-M) was obtained. The softening point of this product is 120 ° C.
Met.

Examples 1-6 ANPA-M, AN obtained in Reference Examples 2 and 4 above
IB-M; glycidyl ether of o-cresol novolac as an epoxy resin (trade name: Sumiepoxy ESCN
-195XL, Sumitomo Chemical Co., Ltd., epoxy equivalent 2
01 g / equivalent, hydrolyzable chlorine 330 ppm) and glycidyl ether of polyphenol obtained by condensation of phenols with hydroxybenzaldehyde (epoxy equivalent 213 g / equivalent, hydrolyzable chlorine content 200 pp
m) (hereinafter referred to as PHG), phenol novolac as an epoxy curing agent (manufactured by Arakawa Chemical Industry Co., Ltd., trade name Tamanol 759, OH equivalent = 106 g / eq), triphenylphosphine and triethylammonium as a curing accelerator. Tetraphenyl borate, crushed fused silica as a filler (trade name FS-891, Denki Kagaku Kogyo Co., Ltd.)
Manufactured), spherical fused silica (trade name FB-74, manufactured by Denki Kagaku Kogyo KK), carnauba wax as a release agent, coupling agent (trade name SH-6040, manufactured by Toray Dow Corning Silicone Co., Ltd.) and Trade name KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd. was blended in an amount (g) shown in Table 1, heated and kneaded with a roll, and transfer molding was performed. Post-cure for 5 hours at 200 ℃
A cured molded product was obtained. Table 1 shows the compounding formulation, the physical properties of the obtained resin composition and the physical properties of the cured moldings thereof.

Comparative Examples 1-2 N, N '-(4,4'-diaminodiphenylmethane) bismamaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-180) as an imide compound, and Sumiepoxy ESCN as an epoxy resin -195XL,
Tamanol 759 was used as an epoxy curing agent (Comparative Example 1), no imide compound was used, and triphenylphosphine and a coupling agent (trade name SH-604) were used.
A cured molded article was obtained in the same manner as in Example except that the amount of 0) was changed (Comparative Example 2). For post cure, Comparative Example 1 was at 200 ° C. for 5 hours, and for Comparative Example 2 was 1
It carried out at 80 degreeC for 5 hours. Table 1 shows the compounding formulation, the physical properties of the obtained resin composition and the physical properties of the cured moldings thereof.

Examples 7 to 10 Imide compounds obtained in Reference Examples 2 and 4 (ANPA-
M, ANIB-M), as epoxy resin, trade name Sumiepoxy ESB-500 (Sumitomo Chemical Co., Ltd., epoxy equivalent 472 g / eq) and trade name Sumiepoxy ES
B-400 (Sumitomo Chemical Co., Ltd., epoxy equivalent 39)
8 g / eq), dicyandiamide as an epoxy curing agent and phenol novolac (manufactured by Arakawa Chemical Industry Co., Ltd.,
According to the formulation shown in Table 2, Tamanole 758 (trade name), OH equivalent of 106 g / eq) and triphenylphosphine as a curing accelerator were dissolved in N, N-dimethylformamide to obtain a uniform resin varnish. A glass cloth (trade name: KS-1600, E-glass, manufactured by Kanebo Co., Ltd.) was impregnated with the varnish, and heat-treated in a hot air dryer at 180 ° C. for 10 to 20 minutes to obtain a prepreg. Six pieces of this prepreg and copper foil (manufactured by Furukawa Electric Co., Ltd., TTAI treatment, 35 μ thickness) were layered, press-molded at 200 ° C. and a pressure of 50 kg / cm ² for 2 hours, and further cured at 200 ° C. for 3 hours to thicken 1m
m copper-clad laminate was obtained. The results of measuring the physical properties of this laminate are shown in Table 2.

Comparative Example 3 N, N '-(4,4'-diaminodiphenylmethane) bismaleimide (trade name Bestlex BH-180, manufactured by Sumitomo Chemical Co., Ltd.) and 4,4'-diaminodiphenylmethane (trade name) Sumicure M and Sumitomo Chemical Co., Ltd.) were dissolved in N, N-dimethylformamide, and the obtained resin varnish was formed into a copper-clad laminate by the same method as in Examples 7-10. The physical properties of this laminate were measured by the same methods as in Examples 7-10. The results are shown in Table 2.

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[Table 1]

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[Table 2]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location H01L 23/31 (72) Inventor Kazuo Takebe 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd. (72 ) Inventor Shinichiro Kitayama 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. (A) General formula (1): (In the formula, R ¹ and R ² are a halogen atom, a hydroxyl group, a phenyl group, an alkoxy group having 4 or less carbon atoms, a phenoxy group,
When a substituted phenoxy group having 10 or less carbon atoms or an alkyl group or an alkenyl group having 6 or less carbon atoms is present, and a plurality of R ¹ and R ² are present, they may be the same or different. R ³ represents a hydrogen atom, a phenyl group or an alkyl group having 6 or less carbon atoms and may be the same or different. K represents an integer of 0 to 3, L represents an integer of 0 to 4, M represents an integer of 1 to 5, and the average number of repeating units n represents a number of 0 to 10. D represents a divalent organic group having a polymerizable unsaturated double bond and having 2 to 24 carbon atoms. The thermosetting resin composition which has an imide compound and the (B) hardening accelerator which are represented by these as an essential component. 2. A heat containing (A) an imide compound represented by the general formula (1) according to claim 1, (B) a curing accelerator, (C) an epoxy resin and (D) an epoxy curing agent as essential components. Curable resin composition. 3. An electronic component molded and encapsulated with the thermosetting resin composition according to claim 1. 4. A base material is impregnated with a resin varnish obtained by dissolving the thermosetting resin composition according to claim 1 or 2 in an organic solvent, and a heat-treated prepreg is laminated on a copper foil and laminated and heat-molded. A thermosetting resin copper clad laminate.