JPH09227653A - Novel epoxy resin and epoxy resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin composition which can give cured products having excellent heat resistance and mechanical strengths without detriment to the toughness and having excellent dimensional stability, humidity resistance and noncorrosiveness to metals by selecting an epoxy resin having a structure represented by a specified formula. SOLUTION: This resin is represented by formula I [wherein R1 to R4 are each H, a 1-5C alkyl or an alkenyl; A is a structure having a selectivity of p-phenylene groups of 80% or below and represented by formula II (wherein R5 and R6 are each H or a 1-3C alkyl); and (l), (m) and (n) are each an integer of 0 or greater]. It sometimes happens that conventional cured epoxy resin products lack in toughness, heat resistance, humidity resistance, dimensional stability, etc. For example, when they are used as sealing agents for electronic components, the sealing materials are sometimes cracked. The above epoxy resin is prepared by introducing a suitably fixable bisphenol skeleton into an epoxy resin having a biphenyl skeleton, and therefore it can give cured products improved in toughness without detriment to the heat resistance and excellent in humidity resistance, dimensional stability, mechanical strengths, low corrosiveness to aluminum, etc.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel epoxy resin whose cured product is excellent in heat resistance and mechanical properties, and a resin composition containing the same. More specifically, the novel epoxy resin of the present invention, and the resin composition containing the same, are used for sealing materials for semiconductors and electronic components, paints, casting materials for electrical components, laminates, adhesives, etc. Or as a sealing material for electronic components.

[0002]

2. Description of the Related Art Conventionally, epoxy resins typified by bisphenol A type epoxy resins have excellent properties such as adhesiveness and electrical properties, so that they can be used for paints, casting materials for electrical parts,
Widely used for applications such as laminates, adhesives, and sealants for electronic components. However, conventional epoxy resins sometimes lack in toughness, heat resistance, dimensional stability, moisture resistance, and the like, and their use ranges are sometimes limited.
For example, when used as an encapsulant for electronic parts, the epoxy resin lacks heat resistance, toughness, or moisture resistance when exposed to high temperatures during the mounting of the electronic parts on the wiring board. Therefore, cracks may occur in the sealing material.

[0003] It is also known that when used as a casting material for electric parts such as capacitors, cracks occur in the epoxy cured product due to internal stress generated due to shrinkage during the curing reaction. As a method for improving toughness and shrinkage, a method of using an epoxy resin having a high molecular weight or a method of dispersing rubber in an epoxy resin (Japanese Patent Laid-Open No. 63-1)
99218) and the like have been studied, but in either case, there is a drawback that the heat resistance decreases. As a means for improving heat resistance, a method using a polyfunctional epoxy resin (Japanese Patent Laid-Open No. 3-11717) has been proposed. However, polyfunctional epoxy resins have improved heat resistance, but have reduced toughness, large shrinkage, and problems in dimensional stability and internal stress.

[0004]

SUMMARY OF THE INVENTION Therefore, the present invention improves the toughness without impairing the heat resistance, and improves the moisture resistance,
It is an object of the present invention to provide an epoxy resin having excellent dimensional stability, mechanical strength, and practical physical properties such as low corrosiveness to aluminum, which are required for a semiconductor sealing material.

[0005]

Means for Solving the Problems As a result of various studies on the above-mentioned problems, the present inventor has found that by introducing a bisphenol skeleton having a suitably flexible skeleton into an epoxy resin having a biphenyl skeleton, the epoxy resin can be added to the epoxy resin. The inventors have found that it is possible to improve toughness without impairing heat resistance, and to impart moisture resistance, dimensional stability, mechanical strength, low corrosion resistance to aluminum, and the like, and have completed the present invention.

That is, the present invention is: (A) New epoxy resin Formula (I)

[Chemical 6] (Wherein, R _{1 to} R ₄ are the same or different and represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group;
A represents the formula (II)

Embedded image (In the formula, R ₅ and R ₆ are the same or different hydrogen atoms,
It represents an alkyl group having 1 to 3 carbon atoms. ), P-
A structure having a phenylene selectivity of 80% or less, l,
m and n each represent an integer of 0 or more. The epoxy resin represented by this is provided.

In the epoxy resin (A) described above, the compound represented by the formula (XII)
I)

Embedded image (Wherein, R _{1 to} R ₆ are the same as those in formula (I), and o
Represents an integer of 1 or more, and k ′ to k ′ ″ represent an integer of 0 or more.) The content of the epoxy resin (B) having a structure of 40% or less is also characteristic. It is also characterized in that the content of the epoxy resin (B) is 20% or less.

The content of the epoxy resin (B) is 10%
The following points are also characteristic. It is also characterized in that it does not substantially contain the epoxy resin (B). It is also characterized in that the content of hydrolyzable chlorine is 1000 ppm or less. Another feature is that the number average molecular weight is 330 or more and 5000 or less. Another feature is that R ₁ , R ₂ , R ₃ , and R ₄ in Formula (1) are hydrogen atoms. It is also characterized in that R ₅ and R ₆ in the formula (II) are hydrogen atoms. Also,

(B) Method for producing a novel epoxy resin (10) Formula (III)

Embedded image (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as those in formula (I). K
Is an integer of 0 or more) and a glycidyl compound represented by the formula (IV):

Embedded image (Wherein R ₅ and R ₆ are the same as those of the formula (II)). A bisphenol compound having a p-position selectivity of 80% or less is reacted in the presence or absence of a catalyst. A method for producing the described epoxy resin is provided. (11) It is also characterized in that a glycidyl compound represented by the formula (III) having a hydrolyzable chlorine content of 1000 ppm or less is used. (12) It is also characterized in that a bisphenol compound represented by the formula (IV) having a polynuclear content of 40% or less is used. Also,

(C) Epoxy resin composition (13) The epoxy resin according to any one of (a) to (a),
(B) To provide an epoxy resin composition containing a curing agent as an essential component. Also, (14) the epoxy resin according to any one of (a) to
An epoxy resin composition comprising (b) a curing agent and (c) a curing accelerator as essential components is provided. (15) The epoxy resin according to any one of (a) to
Provided is an epoxy resin composition containing (b) a curing agent, (c) a curing accelerator, and (d) an inorganic filler as essential components.

Hereinafter, the present invention will be described in detail. (A) Novel epoxy resin (i) The epoxy resin of the present invention basically has the formula (I):

Embedded image (Wherein, R _{1 to} R ₄ are the same or different and represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group;
l, m, and n each represent an integer of 0 or more. A represents the formula (II)

Embedded image

(Wherein R ₅ and R ₆ represent the same or different hydrogen atoms and alkyl groups having 1 to 3 carbon atoms) and have a p-phenylene selectivity of 80% or less. ). In the structural formula of the formula (I), l, m, and n represent the number of repetitions and are integers of 0 or more, and this value is uniquely limited by the following number average molecular weight. The number of repetitions has the character of a number average value from the viewpoint that the produced epoxy resin itself is composed of various mixtures, but generally the average value of 1 is 0 to 1
0, preferably 0.005 to 1, more preferably 0.0
1 to 0.1, the average value of m is 0.01 to 30, preferably 0.1 to 20, more preferably 0.5 to 10, and the average value of n is 0.1 to 30, preferably Is 0.2-2
0, more preferably 0.5 to 10.

Further, the formulas (III), (XI) and (XII
In I), the number of repetitions o is an integer of 1 or more,
It has the character of a number average from the viewpoint of being composed of various mixtures, but generally the average is approximately 1-20.
Further, the number of repetitions k, k ′, k ″, and k ′ ″ are integers of 0 or more, and have a character of a number average from the viewpoint of being composed of various mixtures. It is approximately 0 to 30 independently.

Further, the epoxy resin of the present invention preferably includes the following epoxy resins. An epoxy resin in which R ₁ , R ₂ , R ₃ and R ₄ in the formula (I) are hydrogen atoms. An epoxy resin in which R ₅ and R ₆ are hydrogen atoms in the formula (II). The p-phenylene selectivity in the present invention is represented by the following formulas (V), (VI), and (VII) with respect to the positional relationship between a carbon atom directly bonded to a benzene nucleus and an oxygen atom in formula (II). It means the ratio (molar ratio) of the structure represented by the formula (V) to the entire structure.

Embedded image

Embedded image

Embedded image

(Ii) Consideration of the Epoxy Resin (A) of the Present Invention In the production of the epoxy resin (A) of the present invention, the bisphenol compound of the above formula (II) or (IV), which is one of the reaction raw materials, , Often as a subcomponent, the formula (X
I):

Embedded image (In the formula, R ₅ and R ₆ are the same as those in the formula (II), and o is an integer of 1 or more.)

In the present invention, it is preferable to use a reaction component containing as little as possible the polynuclear component for the following reasons. That is, the higher the content of these polynuclear components, the greater the change in viscosity of the epoxy resin in the course of the synthesis reaction of the epoxy resin of the present invention, which makes not only difficult to control the synthesis reaction, but also such polynuclear components. The mixture contains various complicated by-products, for example, the epoxy resin shown in (XIII), which adversely affects the performance and the like of the novel resin of the present invention.

Therefore, the epoxy resin (A) of the present invention has the formula (XIII)

Embedded image (Wherein, R _{1 to} R ₆ are the same as those in formula (I), and o
Represents an integer of 1 or more, and k ′ to k ′ ″ represent an integer of 0 or more.) Wherein the content of the epoxy resin (B) having a structure of 40% or less, preferably 20% or less, more preferably 1% or less.
It is important that the content is substantially 0% or less, more preferably 5% or less, still more preferably 2% or less, and particularly preferably substantially no epoxy resin (B). of course,
The epoxy resin (B) as a by-product is represented by the formula (XII)
Not only the epoxy resin represented by I) but also those having a structure in which a very small amount of a bisphenol compound of the formula (IV) or (XI) and an epoxy compound of the formula (III) are mixed and reacted.

The p-phenylene selectivity in the present invention is:
80% or less, preferably 70% or less, more preferably 6
0% or less. If the p-phenylene selectivity exceeds 80% and is too high, the melting point or softening point of the epoxy resin increases, so that it becomes necessary to cure the epoxy resin at a higher temperature, and therefore the epoxy resin is hardened. The curing reaction starts before the material is completely melted and uniformly mixed with the curing agent or the like. Accordingly, the obtained epoxy cured product is not preferable because mechanical properties such as toughness are reduced and a shrinkage ratio is increased.

In the present invention, the content of hydrolyzable chlorine is determined by a method for measuring the content of hydrolyzable chlorine described below. The hydrolyzable chlorine content in the present invention is 1000 ppm, preferably 700 ppm or less, more preferably 500 ppm or less, particularly preferably 300 ppm or less.
The following is desirable. Hydrolytic chlorine content is 1000pp
If it exceeds m, the heat resistance and moisture resistance of the epoxy cured product are lowered, or the aluminum wiring is corroded when used as a semiconductor encapsulant, which is not preferable.

The number average molecular weight of the epoxy resin in the present invention has the same property as the above-mentioned number of repetitions,
5000, preferably 350 to 3000, more preferably 400 to 1500, particularly preferably 500 to 1000
Is desirable. If the number average molecular weight is less than 330, the toughness of the cured product is not sufficiently improved, and if it exceeds 5,000, the heat resistance of the cured product is undesirably reduced. The number average molecular weight in the present invention is defined by the number of grams of the epoxy resin required to contain 2 moles of epoxy groups,
It is determined by the following equation using the epoxy equivalent determined by the measurement method described in the section of Examples. (Number average molecular weight) = (epoxy equivalent) × 2

(B) Production Method of Epoxy Resin The novel epoxy resin of the present invention can be basically easily produced by the following synthetic method. That is, the novel epoxy resin of the present invention has the formula (III):

Embedded image (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as those in formula (I). K
Is an integer of 0 or more) and a glycidyl compound represented by the formula (IV):

Embedded image (Wherein, R ₅ and R ₆ are the same as those of the formula (II)), by reacting a bisphenol compound having a p-position selectivity of 80% or less in the presence or absence of a catalyst. Can be.

The reaction ratio between the glycidyl compound and the bisphenol compound may be varied in a wide range according to the performance range of the epoxy resin to be obtained.
0.95, preferably 0.05 to 0.8, more preferably 0.1 to 0.7, and even more preferably 0.2 to 0.5. If the reaction ratio is less than 0.01, the effect of toughness of the cured product obtained by curing the epoxy resin is not exhibited, which is not preferable. If it exceeds 0.095, the heat resistance is reduced.

In the present invention, the p-position selectivity refers to the following formulas (VIII) and (I) contained in the bisphenol compound.
X), (X) (wherein R ₅ and R ₆ are the same as in formula (IV)), the carbon atom directly bonded to the benzene nucleus and the hydroxyl group are in the p-position relative to each other. And the respective molar ratios of formulas (VIII), (IX) and (X) are a, b and c, the p-position selectivity is defined by the following formula.

[Equation 1]

[0024]

Embedded image

[Chemical 21]

Embedded image The molar ratio of the formulas (VIII), (IX) and (X) is
The bisphenol compound can be determined by the area ratio when the bisphenol compound is analyzed by capillary gas chromatography using an FID detector.

Formula (IV) used in the present invention
Examples of the bisphenol compound represented by are bisphenol A, bisphenol F, bisphenol AD, and the like. On the other hand, these compounds often have the formula (XI):

Embedded image (In the formula, R ₅ and R ₆ are the same as in the formula (II), and o represents an integer of 1 or more.) In some cases, the polynuclear component represented by the formula: The viscosity change of the epoxy resin in the course of the synthesis reaction of the epoxy resin of the present invention becomes remarkable, and it becomes difficult to control the synthesis reaction.

Therefore, the lower the content of the polynuclear component represented by the formula (XI) in the bisphenol compound used, the better. Therefore, a bisphenol compound of 40% or less, more preferably 20% or less, still more preferably 10% or less, particularly preferably 5% or less, particularly preferably 2% or less is used. The polynuclear body content was determined by capillary gas chromatography of the bisphenol compound as F
It can be obtained from the area ratio when analyzed using an ID detector.

In the production of the epoxy resin of the present invention, the reaction can be carried out in an organic or inorganic solvent in which the starting materials are dissolved, but it is desirable to carry out the reaction without a solvent in view of the homogeneity of the reaction system. Examples of the catalyst used here include a basic catalyst, a quaternary ammonium salt-based catalyst, and a phosphorus-based catalyst. Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, tributylamine, triethylamine, triisopropylamine, benzyldiethylamine, 2-phenylimidazole, imidazole, N-methylimidazole and the like.
Tetramethylammonium chloride, benzyltrimethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride,
Tetrabutylammonium bromide and the like,
Examples of the phosphorus-based catalyst include triphenylphosphine, trimethylphosphine, benzyltriphenylphosphonium bromide, amyltriphenylphosphonium bromide, benzyltriphenylphosphonium iodide, and triphenylphosphonium iodide.

Although the present invention is not limited by the type of catalyst, it is particularly preferable to use a phosphorus-based catalyst such as triphenylphosphine since the corrosion of aluminum wiring is reduced when used as a sealing material for semiconductors. . The amount of the catalyst to be used is 1 ppm to 1 with respect to the glycidyl compound.
%, Preferably from 5 ppm to 1000 ppm, particularly preferably from 10 ppm to 500 ppm. If the amount of the catalyst used is too small, less than 1 ppm, the reaction rate will be slow, and if it exceeds 1% and too much, the amount of catalyst remaining in the produced epoxy resin will increase and the physical electrical properties of the cured epoxy resin will increase. Characteristics are deteriorated and the corrosiveness of aluminum wiring is increased, which is not preferable. The reaction temperature is 80
C. to 280C, preferably 100C to 220C, more preferably 120C to 180C. If the reaction temperature is less than 80 ° C., which is too low, the reaction proceeds too slowly, the viscosity of the reaction system increases, and stirring of the reaction system becomes difficult, and the reaction is difficult to complete.
On the other hand, if the reaction temperature exceeds 280 ° C. and is too high, the resin starts to thermally decompose, which is not preferable.

The glycidyl compound represented by the formula (III) is a biphenyl compound represented by the formula (XII):

Embedded image (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are the same as in formula (I).)
And an epihalohydrin such as epichlorohydrin, 2-methyl-1-chlorohydrin, epibromohydrin, etc. in the presence of a catalyst to form a halohydrin compound, followed by a dehydrochlorination reaction using a dehydrochlorination reagent. Can be obtained by:

The catalyst used in the addition reaction includes tetramethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium iodide, Ammonium salts such as tetrapropylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide and choline chloride; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide;

Alkaline earth metal hydroxides such as calcium hydroxide; basic organic compounds such as tributylamine, triisopropylamine, benzyldiethylamine, 2-phenylimidazole, imidazole, N-methylimidazole; triphenylphosphine, Examples thereof include phosphorus compounds such as trimethylphosphine, benzyltriphenylphosphonium bromide, amyltriphenylphosphonium bromide, and benzyltriphenylphosphonium iodide. It is desirable to use tetramethylammonium chloride or the like as the catalyst.

The reaction temperature during the addition reaction is from 20 ° C.
160 ° C, preferably 50 ° C to 140 ° C, more preferably 60 ° C to 130 ° C, particularly preferably 80 ° C to 120 ° C
It is. If the reaction temperature is too low, less than 20 ° C., the progress of the reaction may be too slow, the raw material biphenyl compound or the formed chlorohydrin compound may be precipitated from the reaction system, and the reaction may not be completed, or the reaction product may be isolated. Or become difficult. If the reaction temperature exceeds 160 ° C. and is too high, epihalohydrin evaporating from the reaction system will be aggregated and difficult to recover, which is not industrially preferable.

Examples of the dehydrochlorination reagent used in the dehydrochlorination reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide. However, it is particularly preferable to use sodium hydroxide. The dehydrochlorination reagent may be used as it is, or may be used by dissolving it in a solvent such as water, methanol or ethanol. The dehydrochlorination reaction is preferably carried out while removing water generated in the reaction or water accompanying the addition of the dehydrochlorination reactant to the outside of the reaction system.A method of removing water is to remove water in the reaction system. An example is a method of distilling off epihalohydrin with azeotropic distillation, separating the distillate into an aqueous phase and an organic phase, and then returning only the organic phase into the reaction system.

In addition, both the above addition reaction and dehydrochlorination reaction
Alternatively, a reaction solvent may be used when performing either of them. Examples of the reaction solvent used include non-polar solvents such as toluene and xylene; polar solvents such as methyl isobutyl ketone, dioxane, and dimethyl sulfoxide. Particularly, use of dimer sulfoxide is preferable since hydrolyzable chlorine can be reduced. . The hydrolyzable chlorine content of the glycidyl compound represented by the formula (III) is determined by performing a dehydrochlorination reaction on the obtained epoxy resin again and recrystallizing it from various organic solvents or water. Can also be reduced.

Examples of the organic solvent used in the recrystallization include methyl isobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonitrile acetone, holon, methyl cyclohexanone, acetophenone and the like. Ketones; ethers such as diethyl ether, diisopropyl ether, dioxane, furan, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and acetal;

Esters such as ethyl acetate, butyl acetate, diethylene glycol monoacetate, ethylene carbonate and propylene carbonate; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, 1-hexanol,
Alcohols such as -hexanol, 3-hexanol, 1-pentanol, 2-pentanol, 3-pentanol and glycerin; hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene and ethylbenzene; halogens such as chloroform, carbon tetrachloride, chlorobenzene and dichloroethane. Hydrocarbons; nitrogen compounds such as nitrobenzene, acetonitrile, pyridine, dimethylformamide and dimethylacetamide; and sulfur compounds such as dimethylsulfoxide. In particular, use of methyl isobutyl ketone is desirable. These organic solvents and water may be used alone, or may be used by mixing with each other.

The glycidyl compound represented by the formula (III) is a biphenyl compound represented by the formula (XII):

Embedded image (In the formula, R ₁ , R ₂ , R ₃ , and R ₄ are the same as in formula (I).)
And epihalohydrin represented by epichlorohydrin and an alkali metal hydroxide or an alkaline earth metal hydroxide in the presence or absence of a catalyst. Examples of the compound represented by the formula (XII) include 4,4′-bishydroxybiphenyl, 4,4′-bishydroxy-3,3 ′,
5,5'-tetramethylbiphenyl, 4,4'-bishydroxy-3,3 ', 5,5'-tetraphenylbiphenyl, 4,4'-bishydroxy-3,3', 5,5 '
-Tetraethylbiphenyl and the like, wherein
The use of 4,4'-bishydroxybiphenyl is preferred.

(C) Epoxy resin composition The epoxy resin composition of the present invention basically contains (a) the novel epoxy resin and (b) a curing agent as essential components. Further, (c) a curing accelerator and / or (d) an inorganic filler may be used as an essential component. As the component (a) constituting the main component of the epoxy resin composition of the present invention, the above-mentioned novel epoxy resin may be used alone, or may be used in combination with another epoxy resin as required.

Other epoxy resins that can be used in combination include, for example, the following. (A) diglycidyl ethers of bisphenol A,
(B) epoxy phenol novolaks, (c) epoxy cresol novolaks, (d) other; epoxy resin obtained from phthalic acid or hexahydrophthalic acid and epichlorohydrin, epoxy resin obtained from parahydroxybenzoic acid and epichlorohydrin, Epoxy resin obtained from aromatic amines such as toluidine and aniline and epichlorohydrin, vinylcyclohexene dioxide,
1,4-butanediol diglycidyl ether, 1,6
-Hexanediol diglycidyl ether and the like.

The curing agent (b) used in the present invention includes:
An amine-based curing agent, an acid anhydride-based curing agent, a phenol-based curing agent, an imidazole-based curing agent, and a cationic-based curing agent can be used, and the use of a phenol-based curing agent is particularly desirable. . Examples of the amine-based curing agent include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, Bis (hexamethylene) triamine, triethylenetetramine,

Tetrachloro-p-xylylenediamine,
m-xylylenediamine, p-xylylenediamine, m
-Phenylenediamine, o-phenylenediamine, p-
Phenylenediamine, 2,4-diaminoanisole,
2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,
4-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, m-aminophenol,

M-aminobenzylamine, triethylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, tomide (Fuji Kasei ), Versamide, genamide (Henkel Hakusui), lacqueride (Dainippon Ink), sunmide (Sanwa Chemical), polymide (Sanyo Kasei) and the like.

Examples of the acid anhydride-based curing agent include dodecenyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic anhydride, poly (ethyl octadecane diacid) anhydride, and poly (phenylhexadecane diacid). ) Anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, phthalic anhydride , Trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, hetic anhydride, tetrahydrophthalic anhydride, and the like. Particularly preferred is the use of methylhexahydrophthalic anhydride.

Examples of the phenolic curing agent include phenol novolak, cresol novolak, catechol novolak, and the like. Particularly, phenol novolak is preferably used. As an imidazole-based curing agent, for example,
1-methylimidazole, 2-methylimidazole, 2
-Ethyl-4-methylimidazole, 2-undecylimidazole, 2-hepdecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-ethyl-4-methylimidazole,

2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-
2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-
Phenylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl-S-triazine,

2,4-diamino-6- [2-ethyl-4
-Methylimidazolyl- (1)]-ethyl-S-triazine, 2,4-diamino-6- [2-undecylimidazolyl- (1)]-ethyl-S-triazine, 2-phenyl-4,5-methyl Imidazole, 2-phenyl-4
-Methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 1-dodecyl-2-methyl-
Examples thereof include 3-benzylimidazolium chloride and 1,3-dibenzyl-2-methylimidazolium chloride, and the use of 2-ethyl-4-methylimidazole is particularly preferable. Examples of the cationic curing agent include boron trifluoride and boron trifluoride-amine complex. Although the amount of the curing agent (b) varies depending on the degree of polymerization of the epoxy resin (a) and the type of the curing agent, it cannot be uniquely specified,
Generally, 0.1 to 20 per 100 parts by weight of epoxy resin
0 parts by weight, preferably 1 to 100 parts by weight.

Examples of the curing accelerator (c) used in the present invention include the compounds exemplified above as the amine-based curing agent and the imidazole-based curing agent, and phosphorus compounds such as triphenylphosphine and tributylphosphine. The use of a phosphorus compound is particularly desirable. The amount of the curing accelerator (c) varies depending on the degree of polymerization of the epoxy resin (a) and the type of the curing accelerator, but is 0.01 to 100 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the epoxy resin.
5

The inorganic filler (d) used in the present invention includes alumina, asbestos, carbon black, graphite, diatomaceous earth, magnesium oxide, titanium oxide, aluminum hydroxide, quartz powder, fused silica powder, talc, barite,
Mica and the like. The amount of the inorganic filler (d) is 50 to 90 parts by weight, preferably 60 to 85 parts by weight, per 100 parts by weight of the composition. Also, depending on the application colorant,
Coupling agents, flame retardants, release agents, coloring agents, leveling agents, anti-cissing agents, antifoaming agents, etc. are also added, and if necessary, glass fibers, glass cloth, carbon fibers, etc. can be contained. . In particular, examples of the release agent include natural wax, synthetic wax, higher fatty acid and its metal salt, and paraffin. Since carbon or the like has a function as a conductive agent as a coloring agent, it is particularly desirable for use in electric / electronic parts.

The flame retardant is preferably non-halogen, and examples thereof include inorganic fillers, antimony trioxide, antimony pentoxide, phosphoric acid and phosphorus compounds. As the coupling agent, for example, epoxy silane,
Examples thereof include vinyl silane, amino silane, borane compound, alkoxy titanate compound, and aluminum chelate compound.

To produce the epoxy resin composition of the present invention, the essential components (a) to (d) and, if necessary, other additional components are added, and a roller, extruder, kneader mixer, Henschel It can be easily manufactured by uniformly kneading using a mixing device such as a mixer. Of course, in the case of a low-viscosity liquid having a low repeating unit, such as when used for paints and laminates, it is used alone or dissolved in an organic solvent and diluted to a concentration that can be applied or impregnated. Although it can be used, it is desirable to use it in a solvent-free state by adjusting the degree of polymerization.

(D) Utility of New Epoxy Resin and Resin Composition Containing the Same The novel epoxy resin of the present invention and the resin composition containing the same have improved toughness without impairing heat resistance, and have improved moisture resistance, Excellent physical properties such as dimensional stability, mechanical strength, and low corrosiveness to aluminum required for semiconductor encapsulants, etc., so paints, casting materials for electric and electronic fields, semiconductors, electric and electronic It is useful for applications such as sealing materials for components, laminates and adhesives, and is particularly effective for applications such as sealing materials for semiconductors and electric / electronic components.

[0052]

The present invention will be described in detail below with reference to examples, but they do not limit the scope of the present invention. In the examples, "parts" indicates parts by weight. The curing reaction in the application examples and the application comparative examples was performed by adding a mixture of a resin, a curing agent, and the like to a preheated mold.
However, samples for the aluminum corrosion test were prepared by transfer molding. The evaluation of various physical properties in the examples was performed by the following methods. Epoxy equivalent The epoxy resin is dissolved with benzyl alcohol and 1-propanol. An aqueous solution of potassium iodide and a bromophenol blue indicator were added to this solution, and titration was performed with 1 N hydrochloric acid. The point at which the reaction system turned from blue to yellow was defined as the equivalent point. From the equivalent point, the epoxy equivalent of the resin is calculated according to the following equation. Epoxy equivalent (g / eq.) = 1000 × W / (V × N
× F) W: Weight of sample (g) V: Titration (ml) N: Normality of hydrochloric acid used for titration (N) F: Factor of hydrochloric acid used for titration

Hydrolysable chlorine content 0.1 to 3 g of a sample is dissolved in 50 ml of toluene,
After adding 20 ml of a 0.1 N KOH-methanol solution and boiling for 15 minutes, the sample was dissolved in toluene, and the inorganic chlorine content obtained by silver nitrate titration was directly determined from the chlorine content obtained by silver nitrate titration. The hydrolyzable chlorine content was determined by subtraction. Melting point Measured by a micro melting point measuring device MP-J3 manufactured by Yanaco. Softening point Measured according to JIS K-2207. Glass transition temperature (Tg) Measured by TMA in a compression mode.

Tensile strength, tensile elongation, flexural strength, flexural modulus, Izod strength Determined according to JIS K-6911. The Izod strength was measured with a notch. Fracture toughness (K _IC ) Measured according to ASTM D 5045. Water absorption rate Take out a test piece of 20 mm x 20 mm x 2 mm from the cured molded product, put it in a high-pressure steam environment tester, and continue the test until the weight of the test piece becomes constant at 121 ° C and 2 atm. The increase in weight of the test piece was expressed as a percentage.

Shrinkage rate The resin was cured in a stainless steel mold having a rectangular opening with a length of 5 cm and a width of 30 cm in the plane and a semi-cylindrical depression with an inner diameter of 5 cm, and was obtained. The difference between the length of the cured product and the length of the mold is divided by the length of the mold and expressed as a percentage. 10. Warp ratio The resin is cured in a stainless petri dish with an inner diameter of 5 cm, and the distance W (mm) between the surface of the stainless petri dish and the cured resin at the center of the obtained cured product is measured. , D (mm)
Was obtained by the following equation. Warpage rate = {W / (D × D)} × 100,000 11. Aluminum corrosion test A semiconductor element designed for corrosion study of an aluminum metal electrode was mold-coated by a transfer molding method. The obtained molded product was put into a high-pressure steam environment tester, and 12
Exposure to a pressure cooker at 1 ° C and 2 atm.
The corrosion of aluminum occurring after 00 hours was measured, and 5
It was expressed by the number of defective samples in 0 samples.

(Synthesis Reference Example 1) (Synthesis of 4,4'-dihydroxybiphenyldiglycidyl ether) 300 g of 4,4-dihydroxybiphenyl was placed in a 5-ml three-necked flask equipped with a stirrer and a thermometer.
(1.6 mol), 4441 g of epichlorohydrin (48
Mol) and 3.0 g of tetramethylammonium chloride were added and subjected to an addition reaction under heating and reflux for 2 hours. Next, the content was cooled to 60 ° C., and a moisture removal device was installed.
134.4 g (3.2 mol) of sodium hydroxide was added,
Reaction temperature 55-60 ° C, degree of reduced pressure 100-150 mmHg
The azeotropic removal of the water generated in the above was continuously performed, and the ring closure reaction was performed while returning the epichlorohydrin layer of the distillate to the reaction system. The point at which the amount of produced water reached 56.5 ml was taken as the end point of the reaction. Thereafter, filtration under reduced pressure and washing with water were repeated, and the remaining epichlorohydrin was recovered by distillation under reduced pressure. The crude glycidyl compound thus obtained was recrystallized from methyl ethyl ketone to obtain glycidyl compound A (epoxy equivalent: 154, hydrolyzable chlorine content: 1800 ppm). Glycidyl compound A, R _1, R of formula (III)
_It has a structure in which ₂ , R ₃ and R ₄ groups are H.

(Synthesis Reference Example 2) Glycidyl compound A10
0 parts were recrystallized from 500 parts of MEK, and glycidyl compound B (epoxy equivalent 152, hydrolyzable chlorine content 7
80 ppm). The glycidyl compound B has the formula (II
It has a structure in which the R ₁ , R ₂ , R ₃ , and R ₄ groups of I) are H. (Synthesis Reference Example 3) 100 parts of glycidyl compound B was added to 500 parts
Glycidyl compound C (epoxy equivalent 151, hydrolyzable chlorine content 156 ppm)
I got Glycidyl compound C is represented by R ₁ of the formula (III),
It has a structure in which the R ₂ , R ₃ , and R ₄ groups are H.

(Synthesis Example 1) A separable flask was charged with 100 parts of glycidyl compound B and 20 parts of bisphenol F (p-position selectivity 57%, polynuclear content 2%), and added 180 parts.
After melting at 150 ° C., the mixture was cooled, and 1.8 ml of a 25 mmol / L NaOH methanol solution was added at 150 ° C.
The mixture was reacted at 0 ° C. for 3 hours to obtain an epoxy resin 1 (number average molecular weight: 520, hydrolyzable chlorine content: 650 ppm). The epoxy resin 1 has the same structure as R ₁ in the formula (I),
It has a structure in which the R ₂ , R ₃ , and R ₄ groups are H, and in A represented by the formula (II), the R ₅ and R ₆ groups are H.

(Synthesis Examples 2 to 6, 8, and 9) Epoxy resins 2 to 6 and epoxy resins were prepared in the same manner as in Synthesis example 1 using the dihydroxy compound and the glycidyl compound of the types and ratios shown in Table 1. 8,9 were obtained. Table 1 shows the properties of the obtained resin. Epoxy resins 2 to 6, 8, 9
Is a compound represented by the formula (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are H
And has a structure in which R ₅ and R ₆ groups are H in A represented by the formula (II).

(Synthesis Example 7) An epoxy resin 7 was obtained in the same manner as in Synthesis Example 1 except that 0.5 part of triphenylphosphine was used as a catalyst. Table 1 shows the properties of the obtained resin. The epoxy resin 7 is represented by the formula (I):
It has a structure in which R ₁ , R ₂ , R ₃ , and R ₄ groups are H, and in A represented by the formula (II), R ₅ and R ₆ groups are H.

(Synthesis Comparative Example 1) 100 parts of glycidyl compound B and 33 parts of bisphenol F (p-selectivity 98%) were added to a separable flask, melted at 180 ° C, and then 25 mmol / L NaOH at 120 ° C. 1.8 ml of a methanol solution was added and reacted at 180 ° C. for 3 hours to obtain an epoxy resin 10 (number-average molecular weight: 788, hydrolyzable chlorine content: 655 ppm). Epoxy resin 10
In the formula (I), R ₁ , R ₂ , R ₃ and R ₄ groups are H,
In A represented by the formula (II), the compound has a structure in which the R ₅ and R ₆ groups are H.

(Synthesis Comparative Example 2) Epoxy resin 11 was obtained using the biphenyl compound and the glycidyl compound in the types and ratios shown in Table 1. The epoxy resin 11 has a structure in which R ₁ , R ₂ , R ₃ , and R ₄ groups are H in Formula (I), and R ₅ and R ₆ groups are H in A represented by Formula (II). Have.

[0063]

[Table 1]

(Application Examples 1 to 8) Epoxy resins 1 to
6, 8, and 9 are replaced by diaminodiphenylsulfone (DDS)
And a curing reaction was performed at 180 ° C. for 5 hours and at 200 ° C. for 17 hours. Table 2 shows the composition and physical properties of the obtained cured product. (Applied Comparative Examples 1 and 2) Epoxy resins 10 and 11 were prepared by using diaminodiphenylsulfone (DDS) as a curing agent.
The curing reaction was carried out at 80 ° C. for 5 hours and at 200 ° C. for 17 hours (however, epoxy resin 11 was 200 ° C. for 17 hours). Table 2 shows the composition and physical properties of the obtained cured product.

[0065]

[Table 2]

(Application Examples 9 to 11)
4 and 8 were treated with methylhexahydroxyphthalic anhydride (MHHPA) as a curing agent at 130 ° C. for 5 hours,
The curing reaction was performed at 70 ° C. for 17 hours. Table 3 shows the composition and the physical properties of the obtained cured product. (Applied Comparative Example 3) Epoxy resin 11 was treated with methylhexahydroxyphthalic anhydride (MHHPA) as a curing agent.
The curing reaction was performed at 200 ° C. for 22 hours. Table 3 shows the composition and the physical properties of the obtained cured product.

[0067]

[Table 3]

(Application Examples 12 to 15) Epoxy resins 3, 4, 7, and 9 were subjected to a curing reaction at 15 ° C. for 1 hour and at 170 ° C. for 6 hours using a phenol resin (PN) as a curing agent. Table 4 shows the composition and physical properties of the obtained cured product. (Application Comparative Example 4) A curing reaction was performed at 200 ° C. for 5 hours using the epoxy resin 11 as a phenol resin (PN) as a curing agent. Table 4 shows the composition and physical properties of the obtained cured product.

[0069]

[Table 4]

[0070]

As is clear from Tables 1 and 2, the novel epoxy resin of the present invention exhibits excellent heat resistance and mechanical strength without deteriorating toughness, and has a shrinkage ratio and a warpage ratio. It shows excellent properties in dimensional stability evaluated, moisture resistance evaluated by water absorption, and aluminum corrosion.

Claims (15)

[Claims] 1. (A) Formula (I): (Wherein, R _{1 to} R ₄ are the same or different and represent hydrogen, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group;
A is of the formula (II) (In the formula, R ₅ and R ₆ are the same or different hydrogen atoms,
It represents an alkyl group having 1 to 3 carbon atoms. ), P-
A structure having a phenylene selectivity of 80% or less, l,
m and n each represent an integer of 0 or more. ) It is represented by the epoxy resin. 2. The epoxy resin (A) according to claim 1, wherein the epoxy resin has the formula (XIII): (Wherein, R _{1 to} R ₆ are the same as those in formula (I), and o
Represents an integer of 1 or more, and k ′ to k ′ ″ represent an integer of 0 or more.) The content of the epoxy resin (B) having a structure of 40% or less. Epoxy resin. 3. The epoxy resin according to claim 1, wherein the content of the epoxy resin (B) is 20% or less. 4. The epoxy resin according to claim 1, wherein the content of the epoxy resin (B) is 10% or less. 5. The epoxy resin according to claim 1, wherein the epoxy resin (B) is not substantially contained. 6. The hydrolyzable chlorine content is 1000 ppm.
The epoxy resin according to claim 1, wherein: 7. The epoxy resin according to claim 1, which has a number average molecular weight of 330 or more and 5000 or less. 8. In the formula (I), R ₁ , R ₂ , R ₃ , R
The epoxy resin according to any one of claims 1 to 7, wherein ₄ is a hydrogen atom. 9. The epoxy resin according to claim 1, wherein R ₅ and R ₆ in the formula (II) are hydrogen atoms. 10. A compound of the formula (III) (Wherein R ₁ , R ₂ , R ₃ , and R ₄ are the same as those in formula (I). K
Is an integer of 0 or more) and a glycidyl compound represented by the formula (IV): (Wherein R ₅ and R ₆ are the same as those of the formula (II)), characterized by reacting a bisphenol compound having a p-position selectivity of 80% or less in the presence or absence of a catalyst. The method for producing an epoxy resin according to any one of claims 1 to 9. 11. A hydrolyzable chlorine content of 1000 pp.
The method for producing an epoxy resin according to claim 10, wherein a glycidyl compound represented by the following formula (III) is used. 12. The method for producing an epoxy resin according to claim 10, wherein a bisphenol compound represented by the formula (IV) having a polynuclear body content of 40% or less is used. 13. An epoxy resin composition comprising (a) the epoxy resin according to claim 1 and (b) a curing agent as an essential component. 14. An epoxy resin composition comprising (a) the epoxy resin according to any one of claims 1 to 9, (b) a curing agent, and (c) a curing accelerator as essential components. 15. (a) the epoxy resin according to any one of claims 1 to 9, (b) a curing agent, (c) a curing accelerator,
(D) An epoxy resin composition containing an inorganic filler as an essential component.