JPH06157680A - Thermosetting resin composition and its use - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition which can give a cured product excellent in humidity resistance, adhesion and heat resistance, is useful as especially a sealing material for an electronic component, and essentially consists of a specified unsaturated imide compound and a cure accelerator. CONSTITUTION:This resin composition essentially consists of an unsaturated imide compound of formula I [wherein Q is a 10-15C bivalent organic group containing an alicyclic structure; A1, A2 and A3 are each a group of formula I, II or III (wherein R1 to R6 are each H, halogen, a 1-6C hydrocarbon group or a 1-6C halohydrocarbon group; and D is a 2-24 C bivalent unsaturated organic group), provided that at least two of them contain imido; (x) and (y) are each the average number of repeating units and is 0-10; (p), (q), (r) and (s) are each the average number of repeating units and is 1-20; and (t) is 0 or 1, provided that a hydrogen atom is bonded to one of the three valencies of group A3 when t=0] and a cure accelerator. This composition is excellent in humidity resistance, adhesion and heat resistance and is useful as especially a sealing material for an electronic component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention particularly relates to a thermosetting resin composition containing a specific unsaturated imide compound which is useful as a sealing material for electronic parts, and an electronic material obtained by molding and sealing the composition with the composition. Regarding parts.

[0002]

2. Description of the Related Art Conventionally, electrical and electronic parts such as semiconductors, which are molded and sealed with epoxy resin, have been widely used. 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.

[0003]

However, although the electronic sealing parts molded and sealed using a polyimide resin have excellent heat resistance, they have a major drawback in terms of moisture resistance which is a characteristic of the polyimide resin. There is. The purpose of the present invention is to
It is intended to provide a thermosetting resin composition that gives a cured product having excellent moisture resistance, adhesiveness, and heat resistance, and an electronic component molded and sealed using the thermosetting resin composition.

[0004]

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

[0005]

[Chemical 5] [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. A ₁ , A ₂ and A ₃ are each represented by the general formula (1) -1, the same (1) -2 and the same (1) -3.

[0006]

[Chemical 6] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. Represents a hydrogen group, and D represents a divalent unsaturated organic group having 2 to 24 carbon atoms). At least two of the groups including A ₁ , A ₂ and A ₃ each contain an imide group. x and y each independently represent an average repetition number of 0 to 10, and p, q, r and s each independently represent 1 to 20.
Represents the average number of repetitions of. t is 0 or 1. t =
When it is 0, a hydrogen atom is bonded to one of the three bonds from A ₃ . ] An unsaturated imide compound represented by
(B) A thermosetting resin composition containing a curing accelerator as an essential component.

(2) (a) Thermosetting property containing the unsaturated imide compound described in (1) above, (b) curing accelerator, (c) epoxy resin and (d) epoxy resin curing agent as essential components Resin composition.

(3) An electronic component molded and sealed with the thermosetting resin composition according to (1) or (2) above.

These inventions will be described below. In the unsaturated imide compound represented by the general formula (1) used in the present invention, a typical example of the divalent organic group having 10 to 15 carbon atoms and containing an alicyclic structure of Q is represented by the formula (a). , (B), (c), (d) and (e)

[0010]

[Chemical 7] And the like.

R _{1 to} R ₆ in A _{1 to} A ₃ represented by the general formulas (1) -1, (1) -2 and (1) -3.
Specific examples of hydrogen atom; halogen atom such as fluorine, chlorine, bromine, iodine; linear or branched alkyl group such as methyl, ethyl, propyl, butyl, amyl and hexyl; cyclohexyl group; phenyl group 1 to 6 carbon atoms
A hydrocarbon group; a group in which one or more hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom.

The unsaturated imide compound used in the present invention has the general formula (2):

[0013]

[Chemical 8] [Wherein B ₁ , B ₂ and B ₃ are each represented by the general formula (2)
-1, the same (2) -2 and the same (2) -3

[0014]

[Chemical 9] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ have the same meanings as those in formula (1) -1). At least two of the groups including B ₁ , B ₂ and B ₃ each include an amino group. When t = 0, a hydrogen atom is bonded to one of the three bonds out of B ₃ . Q,
x, y, p, q, r, s and t have the same meanings as those in the general formula (1). ] And an aromatic amino compound represented by the general formula (3)

[0015]

[Chemical 10] (In the formula, the meaning of D is the same as that of the general formula (1).) It can be produced by reacting with an unsaturated dicarboxylic acid anhydride represented by the formula. The aromatic amino compounds represented by the general formula (2) are represented by the general formula (4)

[0016]

[Chemical 11] [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. C ₁ , C ₂ and C ₃ are each represented by the general formula (4) -1, the same (4) -2 and the same (4) -3.

[0017]

[Chemical 12] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. It represents a hydrogen group). At least two of the combined groups of C ₁ , C ₂ and C ₃ contain a nitro group. x and y
Each independently represents an average repeat number of 0 to 10,
p, q, r and s each independently represent an average repeat number of 1 to 20. t is 0 or 1. When t = 0, a hydrogen atom is bonded to one of the three bonds out of A ₃ . ] It can manufacture by reducing the aromatic nitro compound represented by these.

The reduction can be carried out by applying a known method. For example, Industrial Organic Chemistry (Tokyo Kagaku Dojin)
Examples include the catalytic reduction method described and the method of treatment with hydrazine in the presence of ferric chloride hexahydrate described in Chem. Lett., 259 (1975).

Typical examples of the aromatic nitro compounds represented by the above general formula (4) are as follows. In the formula, x = t = 0, q = 1, Q is a group derived from dipentene, and a nitro group is at the 4-position in C ₁ .
And R _{1 to} R ₄ are both hydrogen,
1,8-bis [4- (4-nitrophenoxy) phenyl] menthane, 1,8-bis [2- (4-nitrophenoxy) phenyl] mentane, 1- [2- (4-nitrophenoxy) phenyl]- Examples include 8- [4- (4-nitrophenoxy) phenyl] menthane and the like.

In the equation, x = t = 0 and q = 1,
Q is a group derived from dipentene, and R _{1 to} R
_As a group in which at least one of ₄ is a group other than a hydrogen atom, 1,8-bis [4- (4-nitrophenoxy)
-3-Methylphenyl] menthane, 1,8-bis [4-
(4-nitrophenoxy) -3,5-dimethylphenyl] menthane, 1,8-bis [4- (4-nitrophenoxy) -3-butyl-6-methylphenyl] mentane,
1,8-Bis [4- (4-nitro-5-methylphenoxy) -3-methylphenyl] menthane, 1,8-bis [4- (4-nitro-5-methylphenoxy) -3,5
-Dimethylphenyl] menthane, 1,8-bis [4-
(4-Nitro-5-methylphenoxy) -3-butyl-
6-methylphenyl] menthane, 1,8-bis [2-
(4-Nitrophenoxy) -3-methylphenyl] menthane, 1- [2- (4-nitrophenoxy) -3-methylphenyl] -8- [4- (4-nitrophenoxy)-
3-methylphenyl] menthane, 1,8-bis [4-
(3-Nitrophenoxy) -3-methylphenyl] menthane, 1,8-bis [4- (3-nitrophenoxy)-
3,5-Dimethylphenyl] menthane, 1,8-bis [4- (3-nitrophenoxy) -3-butyl-6-methylphenyl] mentane, 1,8-bis [4- (3-nitro-6- Methylphenoxy) -3-methylphenyl]
Menthane, 1,8-bis [4- (3-nitro-6-methylphenoxy) -3,5-dimethylphenyl] menthane, 1,8-bis [4- (3-nitro-6-methylphenoxy) -3 -Butyl-6-methylphenyl] menthane, 1,8-bis [2- (3-nitrophenoxy) -3
-Methylphenyl] menthane, 1- [2- (3-nitrophenoxy) -3-methylphenyl] -8- [4- (3
-Nitrophenoxy) -3-methylphenyl] menthane and the like are exemplified.

Further, in the above equation, x = t = 0, q = 1
And Q is a group derived from dicyclopentadiene, a nitro group in C ₁ is at the 4-position, and R _{1 to} R _1
As a group in which both ₄ are hydrogen atoms, bis [4-
(4-Nitrophenoxy) phenyl] dicyclopentane, bis [2- (4-nitrophenoxy) phenyl] dicyclopentane, [2- (4-nitrophenoxy) phenyl]-[4- (4-nitrophenoxy) phenyl ] Dicyclopentane etc. can be illustrated.

In the equation, x = t = 0 and q = 1,
As a group in which Q is a group derived from dicyclopentadiene, and at least one of R _{1 to} R ₄ is a group other than a hydrogen atom, bis [4- (4-nitrophenoxy) -3-methylphenyl ] Dicyclopentane, bis [4- (4-nitrophenoxy) -3,5-dimethylphenyl] dicyclopentane, bis [4- (4-nitrophenoxy) -3-butyl-6-methylphenyl] dicyclopentane , Bis [4- (4-nitro-5-methylphenoxy) -3-methylphenyl] dicyclopentane, bis [4- (4-nitro-5-methylphenoxy) -3,
5-dimethylphenyl] dicyclopentane, bis [4-
(4-Nitro-5-methylphenoxy) -3-butyl-
6-methylphenyl] dicyclopentane, bis [2-
(4-Nitrophenoxy) -3-methylphenyl] dicyclopentane, [2- (4-nitrophenoxy) -3-
Methylphenyl]-[4- (4-nitrophenoxy)-
3-methylphenyl] dicyclopentane, bis [4-
(3-Nitrophenoxy) -3-methylphenyl] dicyclopentane, bis [4- (3-nitrophenoxy)-
3,5-Dimethylphenyl] dicyclopentane, bis [4- (3-nitro-6-methylphenoxy) -3,5
-Dimethylphenyl] dicyclopentane, bis [4-
(3-Nitro-6-methylphenoxy) -3-butyl-
6-methylphenyl] dicyclopentane, bis [4-
(3-nitro-6-methylphenoxy) -3-methylphenyl] dicyclopentane, bis [2- (3-nitrophenoxy) -3-methylphenyl] dicyclopentane,
Examples include [2- (3-nitrophenoxy) -3-methylphenyl]-[4- (3-nitrophenoxy) -3-methylphenyl] dicyclopentane.

The aromatic nitro compounds represented by the general formula (4) are represented by the general formula (5)

[Chemical 13] [Wherein, E ₁ , E ₂ and E ₃ are each represented by the general formula (5)
-1, the same (5) -2 and the same (5) -3

[0024]

[Chemical 14] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are represented by the general formula (1)-
It has the same meaning as that of 1. ) Is a group represented by. t
When = 0, a hydrogen atom is bonded to one of the three bonds out of E ₃ . Q, x, y, p, q, r, s and t
Has the same meaning as that of the general formula (1). ] And the general formula (6)

[0025]

[Chemical 15] (In the formula, X represents a halogen atom or a nitro group, and R ₅
And R ₆ have the same meanings as in general formula (1) -1. It can be produced by reacting with nitrobenzene represented by the formula (1) in the presence of a basic compound.

The method for producing aromatic nitro compounds by reacting polyphenols with nitrobenzene is as follows:
It can be carried out by a known method of reacting a phenol and a nitrobenzene derivative in the presence of a basic compound. Org.Synth., 445,
(Vol. II), US Pat. No. 4,538,006, J.Org.Che.
m., 50 (20) , 3717 (1985), J.Org.Chem., 50 (17) , 3091
(1985), JP-A-61-194055, JP-A-62-70347, Macromolecules, 25 , 64 (1992) and the like.

Here, the polyphenols represented by the general formula (5) are alicyclic hydrocarbons having a divalent reaction site and phenols as catalysts such as boron trifluoride and boron trifluoride ether complex. Friedel-Cra in the presence of
It can be obtained by a known method which is a kind of fts reaction (for example, Chemich Berichte, 57 , 854 (1924), British Patent No. 1043159 (1963), Dutch Patent No. 6513).
720 (1967), JP-A-4-139142, etc.).

The alicyclic hydrocarbons having a divalent reaction site used herein include dipentene which gives polyphenols in which p, q, r or s is 1 in the general formula (5). , Limonene, terpinolene, terpenes such as α-, β- or γ-terpinene,
Examples thereof include dicyclopentadiene, and among these, dipentene and dicyclopentadiene are preferable.

In the general formula (5), the alicyclic hydrocarbon as a raw material which gives the polyphenols in which p, q, r or s is 2 to 20 is 2 of the above-exemplified alicyclic hydrocarbons.
.About.20 mer. These oligomers are obtained by reacting the above-mentioned alicyclic hydrocarbon monomers under acidic conditions. In addition, when the alicyclic hydrocarbons and phenols described below are reacted with each other, both reactions are performed, and both reactions are simultaneously performed by selecting conditions under which the alicyclic hydrocarbons react with each other to form an oligomer. You can also

The phenols used for synthesizing polyphenols by reacting with alicyclic hydrocarbons include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol and amylphenol. ,
Hexylphenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, cyclohexylphenol, phenylphenol, chlorophenol, chlorocresol, chloroxylenol, bromophenol, bromocresol, bromoxylenol, etc. However, cresol, xylenol, and methylbutylphenol are preferable.

When the alicyclic hydrocarbons and phenols are reacted to synthesize the polyphenols represented by the general formula (5), a compound of t = x = 0 in the general formula (5) is prepared. Is to react in the presence of an excess amount of raw material phenols with respect to the alicyclic hydrocarbons. It is a general method that phenols more than stoichiometrically required are charged in a kettle in advance, and then alicyclic hydrocarbons are dropped little by little.

At this time, in the general formula (5), t =
In order to prepare a compound of 0, x = 1 to 10, two ortho positions and one para position of the phenol molecule, a total of three reaction active points, one activity such as o-cresol, p-cresol, etc. A point is blocked by a substituent, and two active points are alive (hereinafter referred to as having two active points). It is sufficient to react a phenol with an alicyclic hydrocarbon. Since the raw material phenol has two active sites, the polyphenols produced have a chain structure without branching.

At this time, in the general formula (5), t =
1, x = 1 to 10 and y = 0 are prepared by first reacting a phenol having two active sites such as o-chlorophenol and p-bromophenol with an alicyclic hydrocarbon, and then One active point such as 2,6-xylenol, 2,4-xylenol, etc. is reacted with this (hereinafter referred to as having one active point) phenols are reacted to block the reaction active point at the end of the molecule. By synthesizing halogenated polyphenols of, and then removing the halogen atom which is a protective group by reduction, polyphenols with a chain structure having no branching and one reaction active point for each phenol in the main chain Is generated. In this case, the protecting group is not limited to a halogen atom,
Similar results can be obtained by using other protecting groups depending on the reaction conditions. Then add to it 2,6-xylenol, 2,
The desired product is obtained by reacting a phenol having one active site such as 4-xylenol with a 1: 1 adduct composed of alicyclic hydrocarbons.

At this time, in the general formula (5), t =
1, x = 1 to 10 and y = 1 to 10 are produced by a method in which three active points are alive (hereinafter referred to as having three active points) and an equivalent ratio of alicyclic hydrocarbons. May be brought into close contact with each other within a range where gelation does not occur and reacted. By adjusting the charging ratio and reaction conditions in the reaction, polyphenols having a desired structure and number of nuclides can be obtained. Usually, phenols are 1 for alicyclic hydrocarbons.
It is preferably a molar ratio or more.

The nitrobenzenes represented by the general formula (6) include p-fluoronitrobenzene, p-chloronitrobenzene, p-bromochloronitrobenzene and p-
Examples thereof include iodonitrobenzene, m-dinitrobenzene, o-chloronitrobenzene and the like, but p-chloronitrobenzene and m-dinitrobenzene are preferable. Nitrobenzenes are usually used in an amount of 1.4 times or less mol, preferably 1.1 times or less mol, per 1 mol of hydroxyl groups of polyphenols. If the amount used exceeds 1.4 times, unreacted nitrobenzenes tend to remain in the product, which is not preferable. Further, an unreacted hydroxyl group may remain in the molecule of the aromatic nitro compound represented by the general formula (4) (see the explanation of C ₁ , C ₂ or C _{3 in} the same formula). If the proportion is too high, the hygroscopicity of the product becomes high, which is not preferable. Therefore, in order to avoid this, the proportion of nitrobenzenes used in the synthesis reaction is preferably 0.5 times or more moles with respect to 1 mole of hydroxyl groups of polyphenols.

Examples of the unsaturated dicarboxylic acid anhydride represented by the general formula (3) include maleic anhydride, itaconic anhydride, citraconic anhydride, dichloromaleic anhydride, pyrocinconic anhydride, and tetrahydrophthalic anhydride. Etc., or Diels-Alder reaction products of these unsaturated carboxylic acid anhydrides and dienes, such as cyclopentadiene,
At least one of cycloaddition reaction products of furan, terpinene and maleic anhydride can be used.

The aromatic amino compounds represented by the general formula (2) and the unsaturated dicarboxylic acid anhydride represented by the general formula (3) are used as starting materials and are represented by the general formula (1) of the present invention. The method for synthesizing the unsaturated imide compound is not limited to this, but the amic acid is prepared in the first step, and then the ring closure reaction is performed in the second step to obtain the unsaturated imide compound. There is a method.

The method for preparing the amic acid in the first step is generally a method in which an unsaturated dicarboxylic acid anhydride and an aromatic amino compound are contacted in an organic solvent. Commonly used solvents are ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, methylene chloride,
Halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic esters such as ethyl acetate, butyl acetate and butyl lactone, dimethylformamide, 1-methyl An aprotic solvent such as 2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, sulfolane, 1,3-dimethyl-2-imidazolidinone is used. These may be used alone or in combination of two or more.

The amount of the solvent used is 1 to 30 times by weight based on the total weight of the unsaturated dicarboxylic acid anhydride and the aromatic polyamine compound. Reaction temperature is -20 to 10
It is carried out in the range of 0 ° C, preferably in the range of room temperature to 60 ° C. If the temperature is too low, the reaction progresses slowly, and if it is too high, the purity of the target product is lowered due to by-products such as polymers. As an example of the reaction method, to an organic solvent solution of unsaturated dicarboxylic acid anhydride, aromatic polyamino compounds directly, or 0.5 ~ while stirring the organic solvent solution under a nitrogen stream.
Add slowly over 6 hours, keep warm until reaction is complete,
Continue stirring. Usually, the reaction is completed in about 2 hours after the addition is completed. After completion of the reaction, the produced amic acid may be used in the next step without isolation, or the amic acid may be isolated and purified.

The method for ring-closing the amic acid in the second step is carried out by advancing the dehydration reaction of the amic acid produced in the first step in an organic solvent in the presence of a catalyst. As the reaction conditions, known methods described in the specifications such as US Pat. No. 2444536, US Pat. No. 3018292, US Pat. No. 3018292, and US Pat. No. 3127414 can be applied. The dehydrating agent used is usually an acid anhydride. Among them, acetic anhydride is preferable because it is easy to handle, post-process, and industrially easily available. The amount used is 1. for 1 mol of amic acid.
Use 05-1.5 moles. As the catalyst, 0.05 to 0.8 mol of a tertiary amine such as triethylamine is used with respect to 1 mol of amic acid, and 0.005 to 0.5 mol of a metal acetate such as nickel acetate is used with respect to 1 mol of amic acid. The reaction time is usually about 3 to 12 hours.

Examples of commonly used organic solvents include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, methylene chloride, chloroform and carbon tetrachloride. , Halogenated hydrocarbons such as chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, chain or cyclic esters such as ethyl acetate, butyl acetate and butyl lactone, dimethylformamide, 1-methyl-
Aprotic solvents such as 2-pyrrolidone, dimethylsulfoxide, dimethylacetamide, sulfolane, and 1,3-dimethyl-2-imidazolidinone can be mentioned. These may be used alone or in combination of two or more.

As an example of the reaction method, triethylamine is added to the acetone solution of the amic acid prepared in the first step, stirred at room temperature, and then nickel acetate is added. Next, under a nitrogen stream, acetic anhydride is added dropwise in the temperature range of room temperature to 60 ° C. The time required for dropping is usually about 0.5 to 3 hours.
Insulation and stirring are continued in the temperature range of room temperature to 60 ° C. After the reaction is completed, the precipitated target substance is collected by filtration. In order to efficiently obtain the desired product, the reaction solvent may be distilled off under normal pressure or reduced pressure, or the reaction solution may be concentrated or concentrated as long as the fluidity is not impaired. good. The solvent is preferably distilled off at a temperature which does not exceed the reaction temperature for the purpose of suppressing side reactions derived from the dehydrating agent. The solvent may be distilled off while the reaction is proceeding.

After the completion of the reaction, the target substance may be dissolved in the solvent due to the difference in the type and amount of the solvent, so that it may not be precipitated in the reaction solution. In this case, the reaction solvent is distilled off under normal pressure or reduced pressure, or after the reaction mixture is concentrated to such an extent that fluidity is not impaired, it is discharged into a poor solvent such as water or methanol, or a poor solvent is used. Can be added dropwise to the reaction mixture to obtain the desired product as a solid. The amount of the poor solvent used is 0.5 to 20 times the amount of the solvent used in the reaction.

The target product obtained by the above operation is washed with a small amount of a volatile organic solvent such as acetone, and then washed with water.
After washing with water, water may be replaced with a poor solvent such as methanol.
Subsequently, the target product is dried under normal pressure or reduced pressure. The unsaturated imide compound obtained by such a method has a sufficient purity as an industrial raw material, but may be further purified by a method such as recrystallization from a solvent such as an alcohol solvent, if necessary.

As the curing accelerator of the component (B) used in the present invention, known compounds 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, benzoylper Examples of radical initiators include oxides, di-t-butyl peroxide, dicumyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butyl hydroperoxide, and azobisbutyronitrile. However, the present invention is not limited to these. 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.

In order to adjust the curing rate of the composition of the present invention, it is possible to use a known polymerization inhibitor together with the above curing accelerator. For example, 2,6-
Di-t-butyl-4-methylphenol, 2,2'-methylenebis (4-ethyl-6-t-butylphenol),
Phenols such as 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-thiobis (3-methyl-6-t-butylphenol), hydroquinone monomethyl ether, hydroquinone, catechol, p- t
-Polyphenols such as butylcatechol, 2,5-di-t-butylhydroquinone, methylhydroquinone, t-butylhydroquinone and pyrogallol, phenothiazine compounds such as phenothiazine, benzophenothiazine and acetamidophenothiazine, N-nitrosodiphenylamine, N- There are N-nitrosamine-based compounds such as nitrosodimethylamine.

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

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 ( Amine-based epoxy resin derived from methylamine), 1,3-cyclohexanebis (methylamine), p-oxybenzoic acid, m-oxybenzoic acid,
Glycidyl ester compounds derived from aromatic carboxylic acids such as terephthalic acid and isophthalic acid, hydantoin epoxy compounds derived from 5,5-dimethylhydantoin, etc., 2,2-bis (3,4-epoxycyclohexyl) propane Alicyclic epoxy resins such as 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, There are N, N-diglycidylaniline and the like, and one or more of these epoxy resins are used. Among them, an o-cresol novolac epoxy resin and a polyhydric phenol glycidyl ether compound obtained by a condensation reaction of a phenol and an aromatic carbonyl compound are preferable from the viewpoint of curability and heat resistance.

As the epoxy curing agent of the component (D) used in the present invention, known ones can be used. Examples thereof include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, bis (4-
Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ethane, 1,3,3-trimethyl-1-m
-Hydroxyphenylindan-5 or 7-ol,
Polyphenol compounds such as 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone, catechol and phenol, phenols such as o-cresol, and phenols, which are reaction products of formaldehyde, such as novolac , Maleic acid,
Phthalic acid, nadic acid, methyl-tetrahydrophthalic acid,
Polycarboxylic acids such as methyl nadic and its anhydrides, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylenediamine, toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (each containing isomers) Examples thereof include polyamine compounds such as ethylenediamine and hexamethylenediamine, and active hydrogen-containing compounds capable of reacting with an epoxy group such as dicyandiamide and tetramethylguanidine. Among them, phenolic novolak resins are preferably used from the viewpoint of curability and moisture resistance.

In each 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 the encapsulating material, the curing accelerator is usually 1 to 3 parts by weight with respect to 100 parts by weight of the resin. In the composition of the present invention, the use ratio of each of the components (A), (B) and (D) can be appropriately selected according to the application, desired heat resistance and the like. However, it is generally preferred that the weight ratio of the unsaturated imide compound {(A) / [(A) + (C) + (D)]} is 90 to 10%. More preferably, 7
It is between 30% and 30%. If the blending ratio of the unsaturated imide compound deviates from the above range, the moisture resistance and heat resistance decrease, which is not preferable.

The epoxy resin as the component (C) and the curing agent as the component (D) are preferably mixed in equal amounts. If the blending amount of the component (C) and the component (D) deviates significantly from the equimolar blending amount, the moisture resistance and the heat resistance decrease, which is not preferable.

A filler may be added to the thermosetting resin composition of the present invention, if necessary. Examples of the filler include fused silica, crystalline silica, alumina, talc, calcium carbonate, titanium white, clay, asbestos, mica, red iron oxide, glass fiber, and the like. Among them, fused silica, crystalline silica, and alumina are preferably used. To be
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 present invention, if necessary, a natural wax, a synthetic wax, a higher fatty acid and a metal salt thereof, a release agent such as paraffin or a coloring agent such as carbon black, and a surface of a silane coupling agent or the like. A treating agent or the like may be added. 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. Further, for example, in order to reduce the stress, 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.

The thermosetting resin composition of the present invention is mainly used for sealing electronic parts such as semiconductors. In order to seal electronic parts such as semiconductors using the thermosetting resin composition according to the present invention, curing molding may be carried out by a conventionally known molding method such as transfer molding, compression molding or injection molding.

[0055]

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention is excellent in processability, and the cured product has excellent heat resistance, particularly strength and adhesiveness when heated, and is particularly superior to conventionally known heat resistant resins. It has excellent moisture resistance and is extremely useful as a sealing material composition.

[0056]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. The kneaded product and the cured molded product were evaluated by the following methods. -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 (SHIMADZU DT-
30).・ Barcol hardness: 1 according to ASTM D-648 with 935 type
It was measured under the condition of 75 ° C./3 minutes. Bending strength and flexural modulus: Measured with an Instron universal material testing machine (SHIMADZU IS-10T) according to JIS K-6911.・ Hygroscopic rate: 85 ° C using constant temperature and constant humidity (TABAI PR-2)
The weight change was measured under the condition of / 85% RH.・ Spiral flow: 175 ℃ / 7 according to EMMI-1-66
It was carried out under the condition of 0 kg / cm ² . -Adhesive strength (aluminum peel): A molded product was transfer-molded on a commercially available aluminum foil, and the peel strength was evaluated. -Solder cracking property: Simulated IC (52-pin QFP package: package thickness 2.05 mm) is 85 ° C / 85% RH /
The number of individual ICs in which cracks have occurred after being soaked in a solder bath at 240 ° C. for 30 seconds after being allowed to absorb moisture under the condition of 72 hours. 10 test individuals.

Reference Example 1 [N, N'-bis (4-aminophenoxyphenyl) menthane bismaleimide (hereinafter referred to as M
It may be abbreviated as PD. (1) Synthesis of raw material polyphenols; 188 g of phenol, 188 g of toluene, and 13 g of boron trifluoride ether complex are charged into a 1-liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and nitrogen is added. Dissolve under air flow. A solution of 136 g of dipentene dissolved in 136 g of toluene was added dropwise at a temperature of 0 to 5 ° C over 2 hours. The reaction was further continued at a temperature of 0 to 5 ° C for 2 hours and at room temperature for 2 hours, and then the temperature was raised to 60 ° C to complete the reaction. When 250 g of a 5% aqueous sodium hydroxide solution was added and stirring was continued at room temperature for 10 minutes, the brown solution became pale yellow. After liquid separation, the organic layer was washed with 250 g of pure water three times. The reaction solution was refluxed under reduced pressure using a Dean-Stark azeotropic dehydrator to separate and remove water. The solvent was concentrated under reduced pressure, and the concentrate was allowed to stand to obtain crystals. The crystals were heated under reduced pressure and dried to obtain a colorless transparent compound in an amount of 176.9 g (yield 61.0%). The hydroxyl equivalent of this product was 162 g / eq.

(2) Synthesis of aromatic nitro compounds as raw materials; 1 equipped with a thermometer, a stirrer, and a dropping funnel
In a liter four-necked flask, polyphenols 77.5, which is a reaction product of the dipentene and phenol obtained in (1) above
g, p-chloronitrobenzene 78.5 g, 1-methyl-
263.2 g of 2-pyrrolidone is charged and dissolved at 50 ° C. under a nitrogen stream. Add 20.6 g of 99% powdered caustic soda, and add 50
Incubate for half an hour at 80 ° C and then raise to 80 ° C
The reaction was continued for 3 hours, and the disappearance of the raw material polyphenols was confirmed by LC (high performance liquid chromatography, the same applies hereinafter). After the temperature is raised to 125 ° C. and kept for 3 hours, the internal pressure is gradually reduced to 200 Torr, and the water in the system generated by the reaction is recovered. Next, the internal pressure was carefully reduced to 125 Torr, and the reaction solvent, 1-methyl-2-pyrrolidone, was recovered to such an extent that the fluidity of the reaction mixture was not lost.
The reaction mixture was discharged into 600 g of pure water while stirring, and the precipitated crystals were separated by filtration and washed with 300 g of water. The crystals are then washed with 200 g of warm methanol. The crystals obtained were heated under reduced pressure and dried, yielding 133.5 g (yield 97.7%).
I got the target. This compound is bis (4-nitrophenoxyphenyl) menthane. The infrared absorption spectrum of this product showed absorption at 1340 and 1512 cm ^-1 (nitro group).

(3) Synthesis of raw material aromatic amino compound; 113.3 g of the aromatic nitro compound obtained in (2) above, 11 g of activated carbon, ferric chloride hexahydrate in a 3-liter four-necked flask. 0.65g, 2-methoxyethanol 566.5
g was charged and dissolved under a nitrogen stream. 40.0 g of hydrazine monohydrate was added dropwise at 70 to 80 ° C. over 3 hours and the reaction was continued at the same temperature, and it was confirmed by LC that the starting aromatic nitro compounds disappeared. After continuing the reaction for another 3 hours, 10%
After neutralizing with a caustic aqueous solution, activated carbon was filtered off by hot filtration. After 80% of the solvent was distilled off under reduced pressure, the reaction mixture was added dropwise to 2 kg of water while stirring. The pH of the aqueous layer was adjusted to 7.0 to 9.5 with a 10% caustic aqueous solution, and stirring was continued, and then crystals were filtered. The crystals were washed with water, heated under reduced pressure and dried to obtain 100.8 g of the desired product (yield 99.5 g).
%). This compound is bis (4-aminophenoxyphenyl) menthane. The physical properties of this product are as follows.

Mass spectrum M ⁺ = 506; Amine equivalent (by titration method) 254 g / eq; ¹ H-NMR spectrum δ: 0.6 to 2.1 ppm (m, aliphatic), 2.7 ppm (m, methine). , 3.5 ppm (brs, amino group), 6.6 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1228 cm ^-1 (ether bond), 3210, 3360, 3440 cm ^-1 (amino bond); Results (calculated as C ₃₄ H ₃₈ N ₂ O ₂ )

[0061]

[Table 1]

(4) Synthesis of N, N'-bis (4-aminophenoxyphenyl) menthane bismaleimide (MPD): A 300 ml four-necked flask was charged with 10.8 g of maleic anhydride and 25.2 g of acetone, and under a nitrogen stream. Stir to dissolve. A solution of 25.3 g of bis (4-aminophenoxyphenyl) menthane (amine equivalent 253 g / eq) in 59.1 g of acetone was added dropwise over 2 hours while maintaining the temperature at room temperature to 35 ° C. Stirring was continued for another 3 hours. Next, after adding 3.04 g of triethylamine and stirring at room temperature for half an hour, 0.11 g of nickel acetate was added and the temperature was raised to 40 ° C. After adding 13.3 g of acetic anhydride dropwise over 1 hour, the reaction was continued at the same temperature. After the reaction was completed, 200 g of pure water was added dropwise to crystallize the reaction mixture. The crystals were collected by filtration, washed with water, then with methanol and dried. This was recrystallized from methyl cellosolve / isopropanol to yield 23.5 g of yellow crystals (yield
70.6%). The physical properties of this product are shown below.

Mass spectrum M ⁺ = 666; Melting point 96 to 98 ° C. ¹ H-NMR spectrum δ: 0.6 to 2.1 ppm (m, aliphatic), 2.8 ppm (m, methine), 6.8 ppm (s, Imido group), 6.9 to 7.4 ppm (m, aromatic); Infrared absorption spectrum: 1238 cm ^-1 (ether bond), 1712 cm ^-1 (imide bond); Elemental analysis result (C ₄₂ H ₃₈ N ₂ O ₆ Calculated as)

[0064]

[Table 2]

Reference Example 2 [Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane bismaleimide (hereinafter sometimes abbreviated as MXD)] (1 ) Synthesis of raw material polyphenols: In the same manner as in Reference Example 1 (1), except that the phenol was changed to 2,6-xylenol and the reaction temperature was changed to 110 ° C., the same reaction operation and post-treatment were performed. The toluene solution of the reaction mixture was concentrated under reduced pressure to remove toluene. Subsequently, nitrogen was introduced under reduced pressure, and unreacted substances were removed by steam distillation to obtain a light brown crystal compound in an amount of 209.4 g (yield 55.1%). The hydroxyl equivalent of this product was 191 g / eq.

(2) Synthesis of aromatic nitro compounds as raw materials; Referential Example 1 except that 91.3 g of the reaction product of the dipentene obtained in the above (1) and 2,6-xylenol was used as polyphenols. Perform the same reaction operation as in (2),
The desired product was obtained with a yield of 146.6 g (yield 98.3%). This compound is bis [4- (4-nitrophenoxy) -3,5-dimethylphenyl] menthane. The infrared absorption spectrum of this product showed absorption at 1338 and 1515 cm ^-1 (nitro group).

(3) Synthesis of aromatic amino compounds as raw materials; hydrazine as in (3) of Reference Example 1 except that 120 g of the compound obtained in (2) above was used as the aromatic nitro compound. The reduction reaction was performed according to to obtain the desired product in an amount of 107.1 g (yield 98.8%). This compound is bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane. The physical properties of this product are shown below.

Mass spectrum M ⁺ = 562; Amine equivalent (by titration method) 282 g / eq; ¹ H-NMR spectrum δ: 0.5 to 2.4 ppm (m, aliphatic), 2.1 ppm (s, methyl). , 2.7 ppm (m, methine), 3.4 ppm (brs, amino group), 6.6 to 7.3 ppm (m,
Infrared absorption spectrum: 1218 cm ^-1 (ether bond), 3210, 3350, 3430 cm ^-1 (amino bond); Elemental analysis result (calculated as C ₃₈ H ₄₆ N ₂ O ₂ )

[0069]

[Table 3]

(4) Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane bismaleimide (MXD); 32.6 g of maleic anhydride in a 500 ml four-necked flask. And acetone 76g
Was charged and dissolved by stirring under a nitrogen stream. A solution of 84.9 g of bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] menthane (amine equivalent 281 g / eq) in 198 g of acetone was added dropwise over 2 hours while maintaining the temperature at room temperature to 35 ° C. . Stirring was continued for another 3 hours.
Next, after adding 3.04 g of triethylamine and stirring at room temperature for half an hour, 0.29 g of nickel acetate was added and the temperature was raised to 40 ° C.
After 40.1 g of acetic anhydride was added dropwise over 1 hour, the temperature was kept at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 600 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. The yield of yellow crystals was 108.0 g (98.9% yield). A portion was recrystallized from methyl cellosolve / isopropanol. The physical properties of this product are shown below.

Mass spectrum M ⁺ = 722; ¹ H-NMR spectrum δ: 0.6 to 2.2 ppm (m, aliphatic), 2.1 ppm (m, methyl group), 6.8 ppm (s, imide group), 6.8 to 7.2 ppm (m, aromatic); and infrared absorption spectrum: 1222cm ^-1 (ether bonds), 1716 cm ^-1 (imide bond); elemental analysis (calculated as _{C 46 H 46 N 2 O 6} )

[0072]

[Table 4]

Reference Example 3 [Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane bismaleimide (hereinafter sometimes abbreviated as MXP)] (1) Synthesis of raw material polyphenols; 2,6-xylenol 488 g and boron trifluoride ether complex 7.1 g were charged into a 1-liter four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, and under a nitrogen stream, Heat to dissolve. While keeping the internal temperature at 100 to 110 ° C, 132.2 g of dicyclopentadiene was added dropwise at a temperature of 100 to 110 ° C over 4 hours. After continuing the reaction at a temperature of 110 ° C. for 6 hours, 1200 g of toluene and 1000% of 10% sodium bicarbonate water are added.
When g was added and stirring was continued for 10 minutes at room temperature, the brown solution became pale yellow. After liquid separation, the organic layer was washed 3 times with 500 g of pure water. The reaction solution was refluxed under reduced pressure using a Dean-Stark azeotropic dehydrator to separate and remove water. The solvent was concentrated under reduced pressure, and then excess 2,6-xylenol was distilled off. Then, nitrogen was introduced under reduced pressure, and then unreacted substances were removed by steam distillation to obtain a light yellow solid target substance. Yield 328.3g
(Yield 87.2%). The hydroxyl equivalent of this product is 188
It was g / eq.

(2) Synthesis of aromatic nitro compounds as raw materials; Reference Example 1 except that 300 g of the reaction product of the dicyclopentadiene obtained in (1) above and 2,6-xylenol was used as the polyphenols. The same reaction operation as in (2) of (2) above was performed to obtain the target product with a yield of 482.3 g (yield 97.7%). This compound is bis [4- (4-nitrophenoxy)
-3,5-dimethylphenyl] dicyclopentane. The infrared absorption spectra of this product are 1338 and 151.
It showed absorption at 0 cm ^-1 (nitro group).

(3) Synthesis of raw material aromatic amino compounds: In the same manner as in (3) of Reference Example 1, except that 309.4 g of the compound obtained in (2) above was used as the aromatic nitro compounds. The reduction reaction with hydrazine was performed to obtain the desired product in an amount of 277.2 g (yield 99.2%). This compound is bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane. The physical properties of this product are shown below.

Mass spectrum M ⁺ = 558; Amine equivalent (by titration method) 280 g / eq; ¹ H-NMR spectrum δ: 1.1 to 3.5 ppm (m, aliphatic), 2.1 ppm (s, methyl). , 3.2 ppm (brs, amino group), 6.6 to 7.1 ppm (m, aromatic); ・ Infrared absorption spectrum: 1206 cm ^-1 (ether bond), 3200, 3350, 3430 cm ^-1 (amino bond); Results (calculated as C ₃₈ H ₄₂ N ₂ O ₂ )

[0077]

[Table 5]

(4) Synthesis of N, N'-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane bismaleimide (MXP); Maleic anhydride in a 1-liter four-necked flask. 51.3 g and acetone 119.7
g was charged and the mixture was stirred and dissolved under a nitrogen stream. Bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] dicyclopentane while maintaining the temperature at room temperature to 35 ° C.
132.5 g (amine equivalent 279 g / eq) was added to acetone 309.2
The solution dissolved in g was added dropwise over 2 hours. Stirring was continued for another 3 hours. Next, 14.4 g of triethylamine was added and stirred at room temperature for half an hour, 0.50 g of nickel acetate was added, and the temperature was raised to 40 ° C. After 63.0 g of acetic anhydride was added dropwise over 1 hour, the temperature was kept at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. Yield 141.7 g (83.0% yield) of the desired product as yellow crystals.
Got with. The physical properties of this product are shown below.

Mass spectrum M ⁺ = 718; ¹ H-NMR spectrum δ: 1.0 to 2.4 ppm (m, aliphatic), 2.1 ppm (m, methyl group), 2.7 ppm (m, methine), 6.8 ppm ( s, imide group), 6.6 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1222 cm ^-1 (ether bond), 1714 cm ^-1 (imide bond); ・ Elemental analysis result (C ₄₆ H ₄₂ N ₂ Calculated as O ₆ )

[0080]

[Table 6]

Reference Example 4 [4- (4-aminophenoxy)]
Synthesis of Maleimide Derived from Oligomer of 2,6-Xylenol and Dicyclopentadiene Having -3,5-Dimethylphenyl Group (Hereinafter, May be Abbreviated as MXPO)] (1) Aromatic Nitro Compound as a Raw Material Synthesis of compounds; As a polyphenol, a reaction product (oligomer) of 2,6-xylenol and dicyclopentadiene (manufactured by Nippon Oil Co., Ltd., trade name DXP-L-9-1, hydroxyl equivalent 191 g / eq) is used, The same reaction operation as in (2) of Reference Example 1 was performed to
An oligomer of dicyclopentadiene and 2,6-xylenol having a (4-nitrophenoxy) -3,5-dimethylphenyl group was obtained.

(2) Synthesis of raw material aromatic amino compounds: Using the compounds obtained in (1) above as aromatic nitro compounds, the same reaction procedure as in (3) of Reference Example 1 was carried out, 4- (4-aminophenoxy) -3,5 at both ends
An oligomer of 2,6-xylenol having a dimethylphenyl group and dicyclopentadiene was obtained. This is G
From PC measurement, bis [4- (4-aminophenoxy)-
90% 3,5-dimethylphenyl] dicyclopentane
Including. The amine equivalent of this product is 275 g / eq.

(4) 4- (4-aminophenoxy)-
Synthesis of maleimide (MXPO) derived from 2,6-xylenol having 3,5-dimethylphenyl group and an oligomer of dicyclopentadiene; 58.8 g of maleic anhydride and 137.2 g of acetone were charged into a 1-liter four-necked flask, and nitrogen was added. It was dissolved by stirring under an air stream. Room temperature ~ 35
With the 4- (4-aminophenoxy) -3,5-dimethylphenyl group synthesized in Reference Example 4 while being kept at 2,
Oligomer of 6-xylenol and dicyclopentane 15
A solution prepared by dissolving 0.0 g in 350 g of acetone was added dropwise to the flask over 2 hours. Stirring was continued for another 3 hours. Next, after adding 16.6 g of triethylamine and stirring at room temperature for half an hour,
0.58 g of nickel acetate was added and the temperature was raised to 40 ° C. After 72.4 g of acetic anhydride was added dropwise over 1 hour, the temperature was kept at the same temperature until the reaction was completed. After the reaction was completed, the reaction mixture was discharged into 1000 g of pure water. The crystals were collected by filtration, washed with water and then with methanol, heated under reduced pressure and dried. The desired product as yellow crystals was obtained in a yield of 189.4 g (97.9% yield). The physical properties of this product are shown below.

Mass spectrum M ⁺ = 718; ¹ H-NMR spectrum δ: 1.0 to 2.5 ppm (m, aliphatic), 2.7 ppm (m, methine), 6.8 ppm (s, imido group), 6.5 to 7.3 ppm (m, aromatic); ・ Infrared absorption spectrum: 1220 cm ^-1 (ether bond), 1714 cm ^-1 (imide bond);

Examples 1 to 10 MPD, MXD, MXP and MXPO obtained in Reference Examples 1 to 4 as unsaturated imide compounds; glycidyl ether of o-cresol novolac (trade name: Sumiepoxy ESCN- 195, Sumitomo Chemical Co., Ltd., epoxy equivalent 201 g / equivalent, hydrolyzable chlorine content 330 ppm) and polyphenol glycidyl ether obtained by condensation of phenols and hydroxybenzaldehyde (epoxy equivalent 213 g / equivalent, hydrolyzable chlorine Content 200 ppm, hereinafter referred to as PHG); Phenol novolac as an epoxy curing agent (manufactured by Arakawa Chemical Co., Ltd., trade name Tamanor 759, OH equivalent = 106 g /
eq), triphenylphosphine and triethylammonium tetraphenylborate as a curing accelerator; crushed fused silica (trade name FS-891, manufactured by Denki Kagaku Kogyo KK) as filler, spherical fused silica (trade name FS-74, Denka Kagaku Co., Ltd., carnauba wax as a release agent, coupling agent (trade name SH-6040, Toray Dow Corning Silicone and trade name KBS-573, Shin-Etsu Chemical Co., Ltd.)
Was produced in an amount (g) shown in Tables 7 and 8 and kneaded by heating with a roll to perform transfer molding. further,
Post-cure was performed at 200 ° C. for 5 hours to obtain a cured molded product. The compounding method, the physical properties of the thermosetting resin composition, and the physical properties of the cured molded product are shown in Tables 7 and 8.

Comparative Examples 1 and 2 Comparative Example 1 uses N, N'- as an unsaturated imide compound.
(4,4'-Diaminodiphenylmethane) Bismaleimide (Sumitomo Chemical Co., Ltd., trade name Bestlex BH-18
0), the above-mentioned Sumiepoxy ESCN-195X as an epoxy resin
L, using the above Tamanor 759 as an epoxy curing agent,
In Comparative Example 2, an epoxy resin and an epoxy curing agent were used among these, and a cured molded product was obtained by the same method as in Examples except for the above. Regarding post cure, Comparative Example 1 was 2
5 hours at 00 ° C and 5 hours at 180 ° C for Comparative Example 2.
I went on time. Table 8 shows the compounding method, the physical properties of the thermosetting resin composition, and the physical properties of the cured molded product.

[0087]

[Table 7]

[0088]

[Table 8]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication H01L 23/29 23/31 (72) Inventor Kazuo Takebe 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd. (72) Inventor Shinichiro Kitayama 6 Kitahara, Tsukuba, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (5)

[Claims] (A) General formula (1): [In formula, Q represents a C10-C15 bivalent organic group containing an alicyclic structure. A ₁ , A ₂ and A ₃ are each represented by the general formula (1) -1, the same (1) -2 and the same (1) -3. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated carbon atom having 1 to 6 carbon atoms. Represents a hydrogen group, and D represents a divalent unsaturated organic group having 2 to 24 carbon atoms). At least two of the groups including A ₁ , A ₂ and A ₃ each contain an imide group. x and y each independently represent an average repetition number of 0 to 10, and p, q, r and s each independently represent 1 to 20.
Represents the average number of repetitions of. t is 0 or 1. t =
When it is 0, a hydrogen atom is bonded to one of the three bonds from A ₃ . ] An unsaturated imide compound represented by
(B) A thermosetting resin composition containing a curing accelerator as an essential component. 2. A thermosetting resin composition containing (a) the unsaturated imide compound according to claim 1, (b) a curing accelerator, (c) an epoxy resin and (d) an epoxy resin curing agent as essential components. object. 3. The unsaturated imide compound is x = t = 0 and q = 1 in the general formula (1), and Q is the formula (a) or the formula (b). The thermosetting resin composition according to claim 1, which is a compound which is a group represented by. 4. An unsaturated imide compound in the general formula (1), wherein x = t = 0 and q = 1, and Q is represented by the formula (c): The thermosetting resin composition according to claim 1, which is a compound which is a group represented by. 5. An electronic component molded and sealed with the thermosetting resin composition according to claim 1.