Epoxy resin composition, cured product, and electric and electronic parts

Abstract

To provide an epoxy resin composition which enables production of a cured product that has a small amount of hydrolyzable chlorine, and is excellent in electric characteristics and high temperature crack resistance, an epoxy resin composition further containing a curing agent, and a cured product of the same.SOLUTION: An epoxy resin composition (A) contains an epoxy resin represented by the following formula (1), and 4,4'-bishydroxy-3,3',5,5'-tetramethylbiphenyl diglycidyl ether. An epoxy resin composition (B) contains 0.01-1,000 pts.wt. of a curing agent with respect to 100 pts.wt. of the epoxy resin composition (A). In the formula, R1 is a linear aliphatic hydrocarbon group having 4 to 6 carbon atoms.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an epoxy resin composition capable of obtaining a cured product having a low hydrolyzable chlorine content, excellent electrical properties, and low elasticity and excellent crack resistance at high temperatures, and a cured product obtained by curing the epoxy resin composition. The present invention also relates to an electrical and electronic component made of the epoxy resin cured product.

Background Art

[0002] Epoxy resins are generally cured with various curing agents to form cured products having excellent mechanical properties, heat resistance, electrical properties, etc., and are thus used in a wide range of fields such as adhesives, paints, and electrical and electronic materials. In particular, among the fields of electrical and electronic materials, in the application of semiconductor encapsulants, tetramethylbiphenyl-type epoxy resins are frequently used because they can provide high-value-added encapsulants.

[0003] As a recent trend in the semiconductor field, it is required to use semiconductors in a high-temperature environment. For this reason, it is necessary that the cured product obtained by mixing and curing an epoxy resin used as a raw material for a semiconductor encapsulant is excellent in heat resistance and durability assuming use in a high-temperature environment.

[0004] Patent Document 1 describes the production of a tetramethylbiphenyl-type epoxy resin by the reaction of 4,4'-bishydroxy-3,3',5,5'-tetramethylbiphenyl and epichlorohydrin.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the tetramethylbiphenol type epoxy resin described in Patent Document 1, when it is cured together with a curing agent and used as a semiconductor encapsulant, corrosion of the copper wiring of the semiconductor tends to occur. As a reason, it has been found that a large amount of hydrolyzable chlorine that causes corrosion is contained in the epoxy resin. Further, when the cured product obtained by using the epoxy resin described in Patent Document 1 is used at high temperature as a semiconductor encapsulant, cracks may occur in the encapsulant, and the crack resistance at high temperature was not satisfactory either.

[0007] An object of the present invention is to provide an epoxy resin composition (A) capable of obtaining a cured product having a small amount of hydrolyzable chlorine, excellent electrical properties, and excellent high-temperature crack resistance, an epoxy resin composition (B) containing this epoxy resin composition (A) and a curing agent, and a cured product thereof. Another object of the present invention is to provide an electric and electronic component made of the epoxy resin cured product (B).

Means for Solving the Problems

[0008] As a result of intensive studies by the present inventors to solve the above problems, it has been found that an epoxy resin composition (A) containing an epoxy resin having a specific structure at a specific ratio, and an epoxy resin composition (B) containing this epoxy resin composition (A) and a curing agent can solve the above problems, and the present invention has been completed.

[0009] That is, the gist of the present invention resides in the following [1] to [9].

[0010] [1] An epoxy resin composition (A) characterized by containing an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2).

[0011]

Chemical formula

[0012] (In formula (1), R 1 represents a linear aliphatic hydrocarbon group having 4 to 6 carbon atoms.)

[0013] [Chemical formula]

[0014] (In formula (2), n represents an integer from 0 to 1.)

[0015] [2] The epoxy resin composition (A) according to [1], wherein the proportion of the epoxy resin represented by the formula (1) in the epoxy resin composition is 0.01 to 5.0% by weight.

[0016] [3] In the epoxy resin represented by the formula (2), the proportion of the epoxy resin with n = 0 in the epoxy resin composition (A) is 83.0 to 90.0% by weight and the proportion of the epoxy resin with n = 1 in the epoxy resin composition (A) is 2.0 to 9.9% by weight, the epoxy resin composition (A) according to [1] or [2].

[0017] [4] The epoxy resin composition (A) according to any one of [1] to [3], wherein the amount of hydrolyzable chlorine in the epoxy resin composition is 390 ppm by weight or less.

[0018] [5] An epoxy resin composition (B) containing 0.01 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin composition (A) according to any one of [1] to [4].

[0019] [6] The epoxy resin composition (B) according to [5], wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amine curing agents, acid anhydride curing agents, and amide curing agents.

[0020] [7] The epoxy resin composition (B) according to [5] or [6], further containing an epoxy resin different from the epoxy resin in the epoxy resin composition (A).

[0021] [8] A cured product obtained by curing the epoxy resin composition (B) according to any one of [5] to [7].

[0022] [9] An electrical and electronic component obtained by curing the epoxy resin composition (B) according to any one of [5] to [7].

Advantages of the Invention

[0023] According to the present invention, there are provided an epoxy resin composition (A) capable of obtaining a cured product having a lower hydrolyzable chlorine content, excellent electrical properties, and low elasticity and excellent crack resistance at high temperatures compared to conventional products, an epoxy resin composition (B) containing the epoxy resin composition (A) and a curing agent, and a cured product thereof. Since the epoxy resin cured products (A) and (B) of the present invention have the above-described effects, they can be particularly effectively applied to electrical and electronic components such as semiconductor encapsulants and laminates.

Embodiments for Carrying Out the Invention

[0024] Hereinafter, embodiments of the present invention will be described in detail. However, the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description as long as it does not exceed the gist thereof. In the present specification, when the expression "~" is used, it is used as an expression including the numerical values or physical property values before and after it.

[0025] 〔Epoxy Resin Composition (A)〕 The epoxy resin composition (A) of the present invention is characterized by containing an epoxy resin represented by the following formula (1) (hereinafter, may be referred to as "epoxy resin (1)") and an epoxy resin represented by the following formula (2) (hereinafter, may be referred to as "epoxy resin (2)").

[0026]

Chemical formula

[0027] (In formula (1), R 1 represents a linear aliphatic hydrocarbon group having 4 to 6 carbon atoms.)

[0028]

Chemical formula

[0029] (In Formula (2), n represents an integer from 0 to 1.)

[0030] Preferably, in the epoxy resin composition (A) of the present invention, the proportion of the epoxy resin (1) in the epoxy resin composition (A) is 0.01 to 5.0% by weight. Further, preferably, in the epoxy resin composition (A) of the present invention, among the epoxy resins (2), those with n = 0 in Formula (2) (hereinafter, may be referred to as "epoxy resin (2-0)") are 83.0 to 90.0% by weight, more preferably 83.9 to 88.3% by weight, in 100% by weight of the epoxy resin composition (A), and those with n = 1 in Formula (2) (hereinafter, may be referred to as "epoxy resin (2-1)") are 2.0 to 9.9% by weight, more preferably 4.7 to 9.3% by weight in 100% by weight of the epoxy resin composition (A).

[0031] The epoxy resin composition (A) of the present invention further contains other components (hereinafter, simply referred to as "other components") other than these epoxy resin (1), epoxy resin (2-0) and epoxy resin (2-1). The content of the other components in the epoxy resin composition (A) is preferably 8.0% by weight or less. When other components are included, the total of the epoxy resin (1), epoxy resin (2) and other components is 100% by weight.

[0032] Note that since the epoxy resin composition (A) of the present invention contains a plurality of components such as the epoxy resin (1) and the epoxy resin (2), it is defined as an "epoxy resin composition". However, in the technical field of epoxy resins, an "epoxy resin" is not composed of a single component but is obtained as a "composition" composed of multiple components. Therefore, the epoxy resin composition (A) of the present invention is expressed as an "epoxy resin" in the industry and may be sold as an "epoxy resin". Further, in the industry, an "epoxy compound (uncured)" is also referred to as an "epoxy resin". Therefore, the compound represented by the above formula (1) and the compound represented by the above formula (2) are also referred to as "epoxy resins".

[0033] [Mechanism] The epoxy resin composition (A) of the present invention containing an epoxy resin (2) having two glycidyl ether groups and an epoxy resin (1) having one glycidyl ether group has a small amount of hydrolyzable chlorine due to the structure of the epoxy resin (1) and excellent electrical properties. Further, when it is made into an epoxy resin composition (B) containing a curing agent, it becomes low elastic at high temperatures and gives a cured product excellent in crack resistance.

[0034] [Epoxy resin (1), epoxy resin (2), and other components] The epoxy resin composition (A) of the present invention preferably contains 0.01% by weight or more and 5.0% by weight or less of the epoxy resin (1). Further, from the viewpoint of reducing the amount of hydrolyzable chlorine in the epoxy resin composition (A), it is more preferably 0.10% by weight or more and 4.0% by weight or less, and still more preferably 0.20% by weight or more and 3.0% by weight or less. Further, the epoxy resin composition (A) of the present invention, as the epoxy resin composition (B) containing a curing agent described later, is more preferably 0.50% by weight or more and 4.5% by weight or less, and still more preferably 2.0% by weight or more and 4.0% by weight or less from the viewpoint of obtaining a cured product excellent in high-temperature crack resistance. The higher the content of the epoxy resin (1), the higher the amount of hydrolyzable chlorine in the epoxy resin composition (A) tends to be, and the cured product using the epoxy resin composition (A) and the epoxy resin composition (B) containing the cured product tends to have improved high-temperature crack resistance. On the other hand, the lower the content of the epoxy resin (1), the lower the amount of hydrolyzable chlorine in the epoxy resin composition (A) tends to be, and in addition, the elastic modulus of the cured product using the epoxy resin composition (A) and the epoxy resin composition (B) containing the cured product tends to be high at high temperatures. By controlling the content of the epoxy resin (1), it is possible to obtain an epoxy resin composition (A) having a small amount of hydrolyzable chlorine and excellent electrical properties, and a cured product excellent in high-temperature crack resistance as the epoxy resin composition (B) containing the epoxy resin composition (A) and a curing agent.

[0035] In the present invention, R in the formula (1) representing the epoxy resin (1) 1 is a linear aliphatic hydrocarbon group having 4 to 6 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, specifically, an n-butyl group, an n-pentyl group, or an n-hexyl group.

[0036] Further, the epoxy resin composition (A) of the present invention preferably contains 83.0% by weight or more and 90.0% by weight or less of the epoxy resin (2-0) and 4.0% by weight or more and 9.9% by weight or less of the epoxy resin (2-1). The content of these epoxy resins (2) is more preferably 83.9% by weight or more and 88.3% by weight or less of the epoxy resin (2-0) and 4.7% by weight or more and 9.3% by weight or less of the epoxy resin (2-1). The content of the epoxy resin (2) (total content of the epoxy resin (2-0) and the epoxy resin (2-1)) in the epoxy resin composition (A) of the present invention is preferably 87.0% by weight or more and 99.9% by weight or less, and preferably 88.6% by weight or more and 97.6% by weight or less.

[0037] When the content of the epoxy resin (2-0), the epoxy resin (2-1), and the epoxy resin (2) which is the total thereof is within the above range, when it is made into the epoxy resin composition (B) containing a curing agent, it gives a cured product having low elasticity at high temperature and excellent crack resistance.

[0038] Other components are components other than epoxy resin (1) and epoxy resin (2). Specifically, in the formula (2) generated during the production of the epoxy resin composition (A) of the present invention, epoxy resins with n of 2 or more, specific difficult-to-produce components (components that cannot be analyzed) and chlorine-containing organic components produced as by-products during the reaction process, etc. The content of other components in the epoxy resin composition (A) of the present invention is preferably 8% by weight or less, more preferably 7.1% by weight or less. When the content of other components is large, the amount of hydrolyzable chlorine in the epoxy resin composition (A) increases, the electrical properties deteriorate, and when it is made into an epoxy resin composition (B) containing a curing agent, a cured product excellent in high-temperature crack resistance may not be obtained. When the epoxy resin composition (A) of the present invention contains other components, as described above, the total of the above epoxy resin (1), epoxy resin (2) and other components is 100% by weight.

[0039] The content of each constituent component of the epoxy resin composition (A) of the present invention can be measured by, for example, high performance liquid chromatography analysis (hereinafter referred to as LC analysis).

[0040] [Epoxy equivalent] From the viewpoints of excellent electrical properties as an epoxy resin and obtaining a cured product excellent in high-temperature crack resistance as the epoxy resin composition (B) containing a curing agent, the epoxy equivalent of the epoxy resin composition (A) is preferably 180 to 193 g / equivalent. From the viewpoint of further enhancing the productivity during the production of the epoxy resin composition (A), when the usage amount of epichlorohydrin is reduced, the epoxy equivalent of the epoxy resin composition (A) of the present invention is more preferably 183 to 193 g / equivalent. By setting the epoxy equivalent within the above specific range, it is considered that the above excellent properties can be obtained.

[0041] In the present invention, the "epoxy equivalent" is defined as "the mass of an epoxy resin containing 1 equivalent of epoxy groups" and can be measured according to JIS K7236.

[0042] [Amount of hydrolyzable chlorine] The epoxy resin composition (A) of the present invention preferably has a hydrolyzable chlorine content (hereinafter sometimes referred to as "hydrolyzable chlorine amount") of 390 ppm by weight or less. Further, from the viewpoint of making the electrical properties better, the hydrolyzable chlorine amount in the epoxy resin composition (A) is more preferably 370 ppm by weight or less. The lower limit value of the hydrolyzable chlorine amount is not particularly limited, but 10 ppm by weight is preferable from the viewpoint of electrical reliability.

[0043] As a method for measuring the hydrolyzable chlorine amount, for example, about 0.5 g of an epoxy resin is dissolved in 20 ml of dioxane, refluxed with 5 ml of 1N KOH / ethanol solution for 30 minutes, and then quantified by titration with 0.01N silver nitrate solution.

[0044] In order to reduce the hydrolyzable chlorine amount of the epoxy resin composition (A), in the method for producing an epoxy resin described below, the produced epoxy resin may be purified by reacting with an alkali.

[0045] [Method for producing epoxy resin composition (A)] The method for producing the epoxy resin composition (A) of the present invention is not particularly limited. For example, 4,4'-bishydroxy-3,3',5,5'-tetramethylbiphenyl (hereinafter sometimes referred to as "tetramethylbiphenol (3)") represented by the following formula (3) and epihalohydrin are reacted in the presence of a primary alcohol having 4 to 6 carbon atoms to obtain a tetramethylbiphenol type epoxy resin. The obtained tetramethylbiphenol type epoxy resin is reacted with an alkali in order to control the contents of the epoxy resin (1) and the epoxy resin (2) in the epoxy resin composition (A).

[0046] [Chemical formula]

[0047] When producing the epoxy resin composition (A) by such a method, at least tetramethylbiphenol (3) and epihalohydrin are used as raw materials. However, a polyhydroxy compound other than tetramethylbiphenol (3) (hereinafter sometimes referred to as "other polyhydroxy compound") may be used in combination to produce an epoxy resin composition (A) which is a mixture of epoxy resin (1), epoxy resin (2) and other epoxy resins. However, from the viewpoint of enhancing the effects of the present invention, it is preferable to use tetramethylbiphenol (3) alone.

[0048] Here, the "polyhydroxy compound" is a general term for phenolic compounds having two or more hydroxyl groups. Examples of other polyhydroxy compounds include various polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcinol, methylresorcinol, biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin, etc. (however, excluding tetramethylbiphenol (3)), and polyhydric phenol resins obtained by condensation reactions of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal, etc., polyhydric phenol resins obtained by condensation reactions of xylene resins with phenols, and various phenolic resins such as co-condensation resins of heavy oils or pitches with phenols and formaldehydes.

[0049] Among these, preferred examples include phenol novolak resin, phenol aralkyl resin, polyhydric phenol resin obtained by the condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resin, naphthol aralkyl resin, etc.

[0050] In the reaction, tetramethylbiphenol (3) used as a raw material and other polyhydric hydroxy compounds used as necessary are dissolved in epihalohydrin and a primary alcohol having 4 to 6 carbon atoms to form a uniform solution.

[0051] As the epihalohydrin, epichlorohydrin or epibromohydrin is usually used, but epichlorohydrin is preferred in the present invention. The amount of epihalohydrin used is preferably an amount corresponding to usually 1.0 to 10.0 equivalents, particularly 2.9 to 5.9 equivalents, especially 3.0 to 5.0 equivalents, per equivalent of the hydroxyl group of the total polyhydric hydroxy compounds, which is the total of tetramethylbiphenol (3) used as a raw material and other polyhydric hydroxy compounds used as necessary. When the amount of epihalohydrin is not less than the above lower limit, it is preferable because the high molecular weight reaction can be easily controlled and the obtained epoxy resin can have an appropriate epoxy equivalent. On the other hand, when the amount of epihalohydrin is not more than the above upper limit, it is preferable because the production efficiency tends to improve.

[0052] As the primary alcohol having 4 to 6 carbon atoms to be present in the reaction system, specifically, it is preferable to use one or more alcohols selected from the group consisting of 1-butanol, 1-pentanol and 1-hexanol. These primary alcohols are usually used in an amount of 0.15 to 0.7 molar times, preferably 0.3 to 0.6 molar times, relative to the epihalohydrin used in the reaction. When the amount of the primary alcohol used is not more than the above upper limit, the amount of hydrolyzable chlorine can be reduced. Further, when the amount of the primary alcohol used is not less than the above lower limit, an epoxy resin composition (A) that gives a cured product excellent in high temperature crack resistance can be obtained. When 1-butanol is used as the primary alcohol, R in the formula (1) 1 becomes an n-butyl group, when 1-pentanol is used, R in the formula (1) 1 becomes an n-pentyl group, and when 1-hexanol is used, R in the formula (1) 1 becomes an n-hexyl group.

[0053] Next, while stirring the above solution, an alkali metal hydroxide in an amount corresponding to usually 0.5 to 2.0 equivalents, preferably 0.9 to 1.6 equivalents, per equivalent of the hydroxyl group of the raw material tetramethylbiphenol (3) (when a polyhydroxy compound is used in combination, per equivalent of the hydroxyl group of tetramethylbiphenol (3) and the polyhydroxy compound) is added in solid or aqueous solution for reaction. When the addition amount of the alkali metal hydroxide is at least the above lower limit, it is preferable because unreacted hydroxyl groups and the produced epoxy resin are less likely to react and the high molecular weight reaction is easy to control. Also, when the addition amount of the alkali metal hydroxide is at most the above upper limit, it is preferable because impurities due to side reactions are less likely to be generated. Examples of the alkali metal hydroxide used here usually include sodium hydroxide or potassium hydroxide.

[0054] This reaction can be carried out under normal pressure or reduced pressure. The reaction temperature is preferably 20 to 150 °C, more preferably 40 to 100 °C, and still more preferably 40 to 80 °C. When the reaction temperature is at least the above lower limit, it is preferable because the reaction proceeds easily and the reaction is easy to control. Also, when the reaction temperature is at most the above upper limit, it is preferable because side reactions are less likely to proceed and especially chlorine impurities are easily reduced.

[0055] The reaction is carried out while dehydrating by a method in which the reaction solution is azeotroped while maintaining a predetermined temperature as necessary, the volatilized vapor is cooled, the obtained condensate is subjected to oil / water separation, and the oil component from which water has been removed is returned to the reaction system. The alkali metal hydroxide is preferably added little by little intermittently or continuously over 0.1 to 8 hours, more preferably 0.5 to 6 hours, in order to suppress a rapid reaction. When the addition time of the alkali metal hydroxide is at least the above lower limit, it is preferable because the rapid progress of the reaction can be prevented and the control of the reaction temperature becomes easy. When the addition time is at most the above upper limit, it is preferable because chlorine impurities are less likely to be generated, and it is also preferable from the viewpoint of economy. After completion of the reaction, insoluble by-produced salts can be removed by filtration or by washing with water, and then unreacted epihalohydrin can be removed by distillation under reduced pressure.

[0056] In this reaction, catalysts such as quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide, tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine may also be used.

[0057] By reacting the epoxy resin produced as described above with an alkali again for purification, the epoxy resin composition (A) of the present invention containing epoxy resin (1), epoxy resin (2) and other components in the aforementioned contents can be obtained.

[0058] The treatment conditions with an alkali for producing the epoxy resin composition (A) of the present invention are described below. However, depending on the conditions, the reaction time may vary. Therefore, appropriate sampling is performed, and the desired epoxy resin composition (A) can be obtained by analyzing the amounts of each constituent component and the epoxy equivalent.

[0059] For the reaction between the epoxy resin and the alkali, an organic solvent for dissolving the epoxy resin may be used. The organic solvent used in the reaction is not particularly limited, but from the viewpoints of production efficiency, handleability, workability, etc., it is preferable to use a ketone-based organic solvent. Also, from the viewpoint of reducing the amount of hydrolyzable chlorine, an aprotic polar solvent may be used.

[0060] Examples of the ketone-based organic solvent include ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. From the viewpoints of effects and ease of post-treatment, methyl isobutyl ketone is particularly preferable. These may be used alone or in combination of two or more. Examples of the aprotic polar solvent include dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, etc. These may be used alone or in combination of two or more. Among these aprotic polar solvents, dimethyl sulfoxide is preferred because it is easily available and has excellent effects. When the above ketone-based organic solvent and aprotic polar solvent are used in combination, it is preferable to use them such that the proportion of the aprotic polar solvent is 1 to 30% by weight, preferably 5 to 20% by weight, based on the total of these.

[0061] The amount of the above solvent used is such that the concentration of the epoxy resin in the liquid to be treated with an alkali is usually 3 to 70% by weight, preferably 5 to 50% by weight, and more preferably 10 to 40% by weight.

[0062] As the alkali, a solid or solution of an alkali metal hydroxide can be used. Examples of the alkali metal hydroxide include potassium hydroxide, sodium hydroxide, etc., and sodium hydroxide is preferred. Further, the alkali metal hydroxide may be used in a form dissolved in an organic solvent or water. Preferably, the alkali metal hydroxide is used as a solution dissolved in an aqueous solvent or an organic solvent.

[0063] The amount of the alkali metal hydroxide used is preferably 0.1 part by weight or more and 6.0 parts by weight or less in terms of the solid content of the alkali metal hydroxide per 100 parts by weight of the epoxy resin. By setting the amount of the alkali metal hydroxide within this range, it becomes possible to easily adjust the proportion of each component of the obtained epoxy resin composition (A) within a suitable range. If the amount of the alkali metal hydroxide is outside the above range, it may not be possible to obtain the epoxy resin composition (A) containing the epoxy resin (1), the epoxy resin (2), and other components within the defined range of the present invention.

[0064] The reaction temperature is preferably 20 to 150 °C, more preferably 30 to 90 °C, and the reaction time is preferably 0.1 to 15 hours, more preferably 0.3 to 10 hours. If the reaction temperature is outside the above range, it may not be possible to obtain an epoxy resin containing epoxy resin (1), epoxy resin (2) and other components within the specified range of the present invention.

[0065] After the reaction, excess alkali metal hydroxide and by-products are removed by methods such as washing with water, and then the organic solvent is removed by distillation under reduced pressure and / or steam distillation to obtain the epoxy resin composition (A) of the present invention.

[0066] In such a method for producing the epoxy resin composition (A) of the present invention, the method for controlling the content of epoxy resin (1) in the epoxy resin composition (A) is not particularly limited. For example, a method of adjusting the charged amount of a primary alcohol having 4 to 6 carbon atoms when producing the epoxy resin composition (A) can be mentioned. That is, increasing the amount of the primary alcohol charged together with the epihalohydrin tends to increase the content of epoxy resin (1) in the obtained epoxy resin composition (A), and conversely, decreasing the amount of the primary alcohol tends to decrease it. Also, in the reaction of tetramethylbiphenol (3) and epihalohydrin in the presence of the above-mentioned primary alcohol having 4 to 6 carbon atoms, the higher the reaction temperature, the more the content of epoxy resin (1) in the obtained epoxy resin composition (A) tends to increase, and conversely, the lower the reaction temperature, the more it tends to decrease. Further, the more the amount of the alkali metal hydroxide used in this reaction, the more the content of epoxy resin (1) in the obtained epoxy resin composition (A) tends to increase, and conversely, the less the amount of the alkali metal hydroxide used, the more the content of epoxy resin (1) in the obtained epoxy resin composition (A) tends to increase. Also, by purifying the epoxy resin composition (A), the amounts of epoxy resin (1), epoxy resin (2), and other components can be controlled. The content of epoxy resin (1) in the epoxy resin composition (A) of the present invention can be controlled mainly by combining these conditions.

[0067] [Epoxy resin composition (B)] The epoxy resin composition (B) of the present invention contains at least the aforementioned epoxy resin composition (A) of the present invention and a curing agent. Further, in the epoxy resin composition (B) of the present invention, if necessary, other epoxy resins other than the epoxy resin contained in the epoxy resin composition (A) of the present invention (hereinafter, may be simply referred to as "other epoxy resins"), a curing accelerator, an inorganic filler, a coupling agent, etc. can be appropriately blended.

[0068] The epoxy resin composition (B) of the present invention containing the epoxy resin composition (A) of the present invention becomes low elastic at high temperatures and is excellent in crack resistance, and gives a cured product that sufficiently satisfies various physical properties required for various applications. As long as it is a cured product of the epoxy resin composition (B) of the present invention excellent in high-temperature crack resistance, it can be sufficiently applied to applications in a high-temperature environment.

[0069] [Curing agent] In the present invention, the curing agent refers to a substance that contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of the epoxy resin. In the present invention, usually, even if it is called a "curing accelerator", as long as it is a substance that contributes to the crosslinking reaction and / or chain length extension reaction between the epoxy groups of the epoxy resin, it shall be regarded as a curing agent.

[0070] In the epoxy resin composition (B) of the present invention, the content of the curing agent is preferably 0.1 to 1000 parts by weight based on 100 parts by weight of the total epoxy resin components as solid content. More preferably, it is 500 parts by weight or less, and still more preferably 300 parts by weight or less. In the present invention, "solid content" means the components excluding the solvent, and includes not only solid epoxy resins but also semi-solid or viscous liquid substances. Further, "total epoxy resin components" corresponds to the amount of epoxy resin contained in the epoxy resin composition (B) of the present invention. When the epoxy resin composition (B) of the present invention contains only the epoxy resin composition (A), it corresponds to the amount of epoxy resin (epoxy resin (1) and epoxy resin (2) and epoxy resins other than epoxy resin (1) and epoxy resin (2) in other components) in the epoxy resin composition (A). When the epoxy resin composition (A) and other epoxy resins are included, it corresponds to the total of the epoxy resin in the epoxy resin composition (A) and other epoxy resins.

[0071] There is no particular limitation on the curing agent, and any generally known epoxy resin curing agent can be used. For example, phenolic curing agents, amine-based curing agents such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazoles, etc. can be mentioned. Among these, by including a phenolic curing agent, the epoxy resin composition (B) of the present invention can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame retardancy, etc. Therefore, it is preferable to include a phenolic curing agent as the curing agent. Further, from the viewpoint of heat resistance and the like, it is preferable to include an acid anhydride-based curing agent and an amide-based curing agent. Also, using imidazoles is also preferable from the viewpoint of sufficiently advancing the curing reaction and improving heat resistance.

[0072] The curing agent may be used alone or in combination of two or more. When using two or more curing agents in combination, these may be mixed in advance to prepare a mixed curing agent and then used, or each component of the curing agent may be added separately and mixed simultaneously when mixing each component of the epoxy resin composition (B).

[0073] <Phenolic curing agent> Specific examples of phenolic curing agents include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenyl, tetramethylbiphenyl, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolak resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, trisphenol methane type resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin and other various polyhydric phenols, and various polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal, polyhydric phenol resins obtained by condensation reaction of xylene resin with phenols, co-condensation resins of heavy oil or pitches with phenols and formaldehydes, phenol-benzaldehyde-xylylene dimethoxide polycondensate, phenol-benzaldehyde-xylylene dichloride polycondensate, phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensate, phenol-benzaldehyde-4,4'-dichloride biphenyl polycondensate and other various phenol resins and the like. These phenolic curing agents may be used alone or in combination of two or more in any combination and blending ratio.

[0074] Among the above phenolic curing agents, from the viewpoints of heat resistance and curability after curing of the composition, phenol novolak resin (for example, the compound represented by the following formula (4)), phenol aralkyl resin (for example, the compound represented by the following formula (5)), biphenyl aralkyl resin (for example, the compound represented by the following formula (6)), naphthol novolak resin (for example, the compound represented by the following formula (7)), naphthol aralkyl resin (for example, the compound represented by the following formula (8)), trisphenol methane type resin (for example, the compound represented by the following formula (9)), phenol·benzaldehyde·xylylene dimethoxide polycondensate (for example, the compound represented by the following formula (10)), phenol·benzaldehyde·xylylene dichloride polycondensate (for example, the compound represented by the following formula (10)), phenol·benzaldehyde·4,4'-dimethoxide biphenyl polycondensate (for example, the compound represented by the following formula (11)), phenol·benzaldehyde·4,4'-dichloride biphenyl polycondensate (for example, the compound represented by the following formula (11)) and the like are preferable. Particularly, phenol novolak resin (for example, the compound represented by the following formula (4)), phenol aralkyl resin (for example, the compound represented by the following formula (5)), biphenyl aralkyl resin (for example, the compound represented by the following formula (6)), phenol·benzaldehyde·xylylene dimethoxide polycondensate (for example, the compound represented by the following formula (10)), phenol·benzaldehyde·xylylene dichloride polycondensate (for example, the compound represented by the following formula (10)), phenol·benzaldehyde·4,4'-dimethoxide biphenyl polycondensate (for example, the compound represented by the following formula (11)), phenol·benzaldehyde·4,4'-dichloride biphenyl polycondensate (for example, the compound represented by the following formula (11)) are preferable.

[0075]

Chem.

[0076] (However, in the above formulas (4) to (9), k1 to k6 each represent a number of 0 or more.)

[0077]

Chem.

[0078] (However, in the above formulas (10) and (11), k7, k8, l1, and l2 each represent a number of 1 or more.)

[0079] The compounding amount of the phenolic curing agent is preferably 0.1 to 1000 parts by weight, more preferably 500 parts by weight or less, still more preferably 300 parts by weight or less, and particularly preferably 100 parts by weight or less with respect to 100 parts by weight of the total epoxy resin components in the epoxy resin composition (B).

[0080] <Amine curing agent> Examples of the amine curing agent (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like.

[0081] Examples of the aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine, and the like.

[0082] Examples of the polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like.

[0083] Examples of alicyclic amines include isophoronediamine, metaxylylenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine, and the like.

[0084] Examples of aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldiphenylmethane, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, and the like.

[0085] The amine curing agents listed above may be used alone or in any combination and blending ratio of two or more.

[0086] It is preferable to use the above amine curing agent so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all the epoxy resin components contained in the epoxy resin composition (B) is in the range of 0.8 to 1.5. This is preferable because unreacted epoxy groups and functional groups of the curing agent are less likely to remain within this range.

[0087] Examples of tertiary amines include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and the like.

[0088] The tertiary amines listed above may be used alone or in any combination and blending ratio of two or more.

[0089] The above tertiary amine is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all the epoxy resin components contained in the epoxy resin composition (B) is in the range of 0.8 to 1.5. Being within this range is preferable because unreacted epoxy groups and functional groups of the curing agent are less likely to remain.

[0090] <Acid anhydride curing agent> Examples of the acid anhydride curing agent include acid anhydrides and modified products of acid anhydrides.

[0091] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly(ethyl octadecanedioic) anhydride, poly(phenyl hexadecanedioic) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol bistrimellitate dianhydride, het acid anhydride, nadic anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and the like.

[0092] Examples of modified acid anhydrides include those obtained by modifying the above-described acid anhydrides with glycols. Examples of glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol, and polyether glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Furthermore, copolymer polyether glycols of two or more of these glycols and / or polyether glycols can also be used.

[0093] In the modified product of the acid anhydride, it is preferable to modify with 0.4 mol or less of glycol per 1 mol of the acid anhydride. When the modification amount is below the above upper limit value, the viscosity of the epoxy resin composition does not become too high, and the workability tends to be good. Also, the rate of the curing reaction with the epoxy resin tends to be good.

[0094] The acid anhydride-based curing agents listed above may be used alone or in any combination and blending amount of two or more.

[0095] When using an acid anhydride-based curing agent, it is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all the epoxy resin components in the epoxy resin composition (B) is in the range of 0.8 to 1.5. This is preferable because unreacted epoxy groups and functional groups of the curing agent are less likely to remain within this range.

[0096] <Amide-based curing agent> Examples of amide-based curing agents include dicyandiamide and its derivatives, polyamide resins, and the like. The amide-based curing agent may be used alone or a mixture of two or more in any combination and ratio. When using an amide-based curing agent, it is preferably used so that the amide-based curing agent is 0.1 to 20% by weight based on the total of all the epoxy resin components and the amide-based curing agent in the epoxy resin composition (B).

[0097] <Imidazoles> Examples of imidazoles include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 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'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of epoxy resins and the above imidazoles. Since imidazoles have catalytic activity, they can generally be classified as curing accelerators, but in the present invention, they are classified as curing agents.

[0098] The imidazoles listed above may be used alone or in any combination and ratio of two or more. When using imidazoles, it is preferable to use them so that the imidazoles are 0.1 to 20% by weight based on the total of all epoxy resin components and imidazoles in the epoxy resin composition (B).

[0099] <Other curing agents> In the epoxy resin composition (B) of the present invention, other curing agents can be used in addition to the above curing agent. There are no particular restrictions on the other curing agents that can be used in the epoxy resin composition (B) of the present invention, and all those generally known as curing agents for epoxy resins can be used. These other curing agents may be used alone or in combination of two or more.

[0100] [Other epoxy resins] In addition to the epoxy resin composition (A), the epoxy resin composition (B) of the present invention can further contain other epoxy resins. By including other epoxy resins, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, etc. of the epoxy resin composition (B) of the present invention can be improved.

[0101] Other epoxy resins that can be used in the epoxy resin composition (B) of the present invention include all epoxy resins other than the epoxy resins (mainly epoxy resin (1) and epoxy resin (2)) contained in the epoxy resin composition (A). Specific examples include bisphenol A type epoxy resin, trisphenol methane type epoxy resin, anthracene type epoxy resin, phenol-modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropylidene resorcin type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, biphenol type epoxy resin, epoxy resin (1) in the epoxy resin composition (A),Tetramethylbiphenol type epoxy resins other than (2), tetramethyl bisphenol F type epoxy resins, dihydroxydiphenyl ether type epoxy resins, epoxy resins derived from thiodiphenols, dihydroxynaphthalene type epoxy resins, dihydroxyanthracene type epoxy resins, dihydroxydihydroanthracene type epoxy resins, dicyclopentadiene type epoxy resins, epoxy resins derived from dihydroxystilbenes, phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolak type epoxy resins, naphthol novolak type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, terpene phenol type epoxy resins, dicyclopentadiene phenol type epoxy resins, epoxy resins derived from condensates of phenol and hydroxybenzaldehyde, epoxy resins derived from condensates of phenol and crotonaldehyde, epoxy resins derived from condensates of phenol and glyoxal, epoxy resins derived from co-condensation resins of heavy oil or pitches, phenols and formaldehydes, epoxy resins derived from diaminodiphenylmethane, epoxy resins derived from aminophenol, epoxy resins derived from xylylenediamine, epoxy resins derived from methylhexahydrophthalic acid, epoxy resins derived from dimer acid, etc. may be mentioned., These may be used alone or in any combination and blending ratio of two or more kinds.,

[0102] Among these, from the viewpoints of the fluidity of the composition, and further the heat resistance, moisture absorption resistance, flame retardancy, etc. of the cured product, among the above epoxy resins, bisphenol A type epoxy resins, tetramethylbiphenol type epoxy resins other than the epoxy resins (1) and (2) in the epoxy resin composition (A), 4,4'-biphenol type epoxy resins, biphenyl aralkyl type epoxy resins, phenol aralkyl type epoxy resins, dihydroxyanthracene type epoxy resins, dicyclopentadiene type epoxy resins, orthocresol novolak type epoxy resins, and trisphenol methane type epoxy resins are particularly preferred.,

[0103] When the epoxy resin composition (B) of the present invention contains the above other epoxy resin, its content is preferably 0.01 to 60 parts by weight, more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and on the other hand, more preferably 1 part by weight or more, based on 100 parts by weight of all epoxy resin components in the composition.

[0104] [Curing accelerator] The epoxy resin composition (B) of the present invention preferably contains a curing accelerator. By containing a curing accelerator, it becomes possible to shorten the curing time and lower the curing temperature, and it is easier to obtain a desired cured product.

[0105] The curing accelerator is not particularly limited, and specific examples include phosphorus compounds such as organic phosphines and phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and boron halide amine complexes.

[0106] Examples of phosphorus compounds that can be used as a curing accelerator include organic phosphines such as triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl·alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, etc., or complexes of these organic phosphines with organic borons, or compounds formed by adding quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, etc., or compounds such as diazophenylmethane.

[0107] Among the curing accelerators listed above, organic phosphines and phosphonium salts are preferred, and organic phosphines are most preferred. Also, the curing accelerator may be used alone, or two or more thereof may be mixed in any combination and ratio.

[0108] The curing accelerator is preferably used in the range of 0.1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition (B). More preferably, it is 0.5 part by weight or more, still more preferably 1 part by weight or more. On the other hand, more preferably, it is 15 parts by weight or less, still more preferably 10 parts by weight or less. When the content of the curing accelerator is at least the above lower limit value, a good curing acceleration effect can be obtained. On the other hand, when it is at most the above upper limit value, it is preferable because the desired cured physical properties are easily obtained.

[0109] [Inorganic filler] An inorganic filler can be blended into the epoxy resin composition (B) of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, talc, boron nitride, and the like. These may be used alone or in combination of two or more in any combination and blending ratio. Among these, when used for semiconductor encapsulation, crushed and / or spherical, fused and / or crystalline silica powder fillers are preferred.

[0110] By using an inorganic filler, when the epoxy resin composition (B) is used as a semiconductor encapsulant, the thermal expansion coefficient of the semiconductor encapsulant can be made closer to that of the internal silicon chip or lead frame, and also the moisture absorption amount of the entire semiconductor encapsulant can be reduced, so that the solder crack resistance can be improved.

[0111] The average particle size of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, more preferably 2 to 30 μm. When the average particle size is at least the above lower limit value, the melt viscosity does not become too high and the fluidity is not easily reduced, which is preferable. Also, when the average particle size is at most the above upper limit value, the filler is less likely to clog the narrow gaps of the mold during molding, and the filling property of the material is easily improved, which is preferable.

[0112] When an inorganic filler is used in the epoxy resin composition (B) of the present invention, the inorganic filler is preferably blended in the range of 60 to 95% by weight of the entire epoxy resin composition.

[0113] [Release agent] A release agent can be blended into the epoxy resin composition (B) of the present invention. Examples of the release agent include natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate and their metal salts, and hydrocarbon-based release agents such as paraffin. These may be used alone or in combination of two or more in any combination and blending ratio.

[0114] When a release agent is blended into the epoxy resin composition (B) of the present invention, the blending amount of the release agent is preferably 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition (B). When the blending amount of the release agent is within the above range, it is preferable because good releasability can be exhibited while maintaining the curing characteristics of the epoxy resin composition (B).

[0115] [Coupling agent] It is preferable to blend a coupling agent into the epoxy resin composition (B) of the present invention. The coupling agent is preferably used in combination with an inorganic filler, and by blending the coupling agent, the adhesiveness between the epoxy resin as the matrix and the inorganic filler can be improved. Examples of the coupling agent include silane coupling agents and titanate coupling agents.

[0116] Examples of the silane coupling agent include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-ureidopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane; vinyl silanes such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; and further, epoxy-based, amino-based, and vinyl-based polymer types of silanes.

[0117] Examples of the titanate coupling agent include isopropyltriisostearoyl titanate, isopropyltri(N-aminoethylaminoethyl) titanate, diisopropylbis(dioctyl phosphate) titanate, tetraisopropylbis(dioctyl phosphite) titanate, tetraoctylbis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl) phosphite titanate, bis(dioctyl pyrophosphate) oxyacetate titanate, bis(dioctyl pyrophosphate) ethylene titanate, and the like.

[0118] Any of these coupling agents may be used alone, or two or more of them may be mixed and used in any combination and ratio.

[0119] When a coupling agent is used in the epoxy resin composition (B) of the present invention, the compounding amount is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the total epoxy resin components. When the compounding amount of the coupling agent is not less than the above lower limit value, the effect of improving the adhesion between the epoxy resin as the matrix and the inorganic filler due to the addition of the coupling agent tends to be improved. On the other hand, when the compounding amount of the coupling agent is not more than the above upper limit value, it is preferable because the coupling agent is less likely to bleed out from the obtained cured product.

[0120] [Other compounding components] Components other than those described above (which may be referred to as "other compounding components" in the present invention) can be compounded in the epoxy resin composition (B) of the present invention. Examples of other compounding components include flame retardants, plasticizers, reactive diluents, pigments, and the like, which can be appropriately compounded as necessary. However, the epoxy resin composition (B) of the present invention does not prevent the compounding of substances other than the components listed above.

[0121] Examples of the flame retardant used in the epoxy resin composition (B) of the present invention include halogen-based flame retardants such as brominated epoxy resins and brominated phenolic resins, antimony compounds such as antimony trioxide, red phosphorus, phosphorus-based flame retardants such as phosphate esters and phosphines, nitrogen-based flame retardants such as melamine derivatives, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0122] 〔Cured product〕 By curing the epoxy resin composition (B) of the present invention, a cured product having a low hydrolyzable chlorine content, excellent electrical properties, and excellent high-temperature crack resistance can be obtained.

[0123] The method for curing the epoxy resin composition (B) of the present invention is not particularly limited, but usually, a cured product can be obtained by a thermal curing reaction by heating. During the thermal curing reaction, it is preferable to appropriately select the curing temperature depending on the type of curing agent used. For example, when a phenolic curing agent is used, the curing temperature is usually 130 to 300°C. In addition, by adding a curing accelerator to these curing agents, it is also possible to lower the curing temperature. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and even more preferably 3 to 15 hours. When the reaction time is equal to or longer than the above lower limit value, the curing reaction tends to proceed sufficiently, which is preferable. On the other hand, when the reaction time is equal to or shorter than the above upper limit value, it is preferable because deterioration due to heating and energy loss during heating can be easily reduced.

[0124] 〔Applications〕 The epoxy resin composition (A) of the present invention has a low hydrolyzable chlorine content and excellent electrical properties. Further, according to the epoxy resin composition (B) of the present invention containing the epoxy resin composition (A) of the present invention, a cured product having excellent high-temperature crack resistance can be obtained.

[0125] Therefore, the epoxy resin composition (A), epoxy resin composition (B), and their cured products of the present invention can be effectively used in any application as long as the physical properties thereof are required. For example, in the field of paints such as electrodeposition paints for automobiles, heavy anti-corrosion paints for ships and bridges, and paints for inner surface coating of beverage cans; in the field of electric and electronic products such as laminates, semiconductor encapsulants, insulating powder paints, and coil impregnation; in the fields of civil engineering, architecture, and adhesives such as seismic reinforcement of bridges, concrete reinforcement, floor materials for buildings, lining of water supply facilities, drainage and permeable paving, and adhesives for vehicles and aircraft. Among these, it is particularly useful for electric and electronic applications such as semiconductor encapsulants and laminates. The epoxy resin composition (B) of the present invention may be used after curing for the above applications, or may be cured in the manufacturing process of the above applications.

Examples

[0126] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. In addition, the values of various manufacturing conditions and evaluation results in the following examples have the meaning as the preferable values of the upper limit or lower limit in the embodiments of the present invention, and the preferable range may be a range defined by the combination of the above-mentioned upper limit or lower limit values and the values of the following examples or the values between the examples.

[0127] [Manufacture and Evaluation of Epoxy Resin Composition (A)] [Measurement and Evaluation Methods] The measurement and evaluation of the physical properties of the epoxy resin composition (A) were carried out as follows.

[0128] [Composition of Epoxy Resin Composition (A)] Regarding the ratios of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1), and other components, LC analysis was performed according to JIS K0124 using the following apparatus and conditions, and the area percentages of each Area of the LC chart represented by epoxy resin (2-0), epoxy resin (2-1), and other components were used as the ratios (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1), and other components. Apparatus: High-performance liquid chromatography Waters 2690 manufactured by Waters Column: TSKgel ODS-120A manufactured by Tosoh Corporation (column dimensions 4.6 mm I.D. × 15 cm) Eluent: Gradient analysis with acetonitrile / water = 30 / 70 changed to 100 / 0 in 60 minutes Flow rate: 1 ml / min Detector: UV (280 nm) Temperature: 35 °C Sample concentration: 0.1% Injection volume: 10 μl Peak area analysis software: Empower2 manufactured by Waters

[0129] <Epoxy equivalent weight> It is defined as "the mass of an epoxy resin containing 1 equivalent of epoxy groups" and measured according to JIS K7236.

[0130] <Hydrolyzable chlorine content> 0.5 g of epoxy resin was dissolved in 20 ml of dioxane, refluxed with 5 ml of 1N KOH / ethanol solution for 30 minutes, and then titrated with 0.01N silver nitrate solution for quantification.

[0131] [Example 1] Into a 5 L four-necked flask equipped with a thermometer, a stirring device, and a cooling tube, 200 g of tetramethylbiphenol (manufactured by Mitsubishi Chemical Corporation), 765 g of epichlorohydrin (5.0 equivalents relative to 1 equivalent of the hydroxyl group of tetramethylbiphenol), and 183 g of 1-butanol (0.3 molar times 1-butanol relative to epichlorohydrin) were charged, heated to 40 °C and uniformly dissolved, and then 158 g of a 48.5 wt% aqueous sodium hydroxide solution (1.15 equivalents relative to 1 equivalent of the hydroxyl group of tetramethylbiphenol) was added dropwise over 90 minutes. Simultaneously with the addition dropwise, the temperature was raised from 40 °C to 65 °C over 90 minutes. Then, it was held at 65 °C for 30 minutes to complete the reaction, the reaction solution was transferred to a 5 L separatory funnel, 500 g of warm water at 65 °C was added, cooled to 65 °C, and allowed to stand for 1 hour. After standing, the aqueous layer was withdrawn from the separated oil layer and aqueous layer, and by-produced salts and excess sodium hydroxide were removed. Then, epichlorohydrin was completely removed under reduced pressure at 150 °C.

[0132] Thereafter, 434 g of methyl isobutyl ketone was charged (epoxy resin concentration 40 wt%), heated to 65 °C and uniformly dissolved, then 6.2 g of a 48.5 wt% aqueous sodium hydroxide solution (the amount of NaOH relative to the epoxy resin was 1.0 wt%) was charged, reacted for 60 minutes, and then washed 4 times with 400 g of water. Thereafter, methyl isobutyl ketone was completely removed under reduced pressure at 150 °C to obtain the epoxy resin composition (A-1) of Example 1.

[0133] Table 1 shows the composition (ratio (wt%) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (wt ppm) of the epoxy resin composition (A-1). Note that the epoxy resin (1) contained in the epoxy resin composition (A-1) was only the one in which R 1 was an n-butyl group in the formula (1).

[0134] [Example 2] In Example 1, an epoxy resin composition (A-2) was obtained in the same manner except that the amount of 1-butanol charged into the four-necked flask was 275 g (1-butanol was 0.45 molar times that of epichlorohydrin). Table 1 shows the composition of the epoxy resin composition (A-2) (the ratios (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (weight ppm). The epoxy resin (1) contained in the epoxy resin composition (A-2) was only the one in which R 1 was an n-butyl group in the formula (1).

[0135] [Example 3] In Example 1, an epoxy resin composition (A-3) was obtained in the same manner except that the amount of 1-butanol charged into the four-necked flask was 366 g (1-butanol was 0.6 molar times that of epichlorohydrin). Table 1 shows the composition of the epoxy resin composition (A-3) (the ratios (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (weight ppm). The epoxy resin (1) contained in the epoxy resin composition (A-3) was only the one in which R 1 was an n-butyl group in the formula (1).

[0136] [Example 4] In Example 1, an epoxy resin composition (A-4) was obtained in the same manner except that 218 g of 1-pentanol (1-pentanol was 0.3 molar times that of epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask. Table 1 shows the composition of the epoxy resin composition (A-4) (the ratios (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (weight ppm). The epoxy resin (1) contained in the epoxy resin composition (A-4) was only the one in which R 1It was only those having an n-pentyl group.

[0137] [Example 5] In Example 1, except that 326 g of 1-pentanol (1-pentanol was 0.45 molar times with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask, all were carried out in the same manner to obtain an epoxy resin composition (A-5). The composition of the epoxy resin composition (A-5) (the ratio (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (weight ppm) are shown in Table 1. The epoxy resin (1) contained in the epoxy resin composition (A-5) was such that in the above formula (1), R 1 It was only those having an n-pentyl group.

[0138] [Example 6] In Example 1, except that 435 g of 1-pentanol (1-pentanol was 0.6 molar times with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask, all were carried out in the same manner to obtain an epoxy resin composition (A-6). The composition of the epoxy resin composition (A-6) (the ratio (weight %) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / equivalent), and hydrolyzable chlorine content (weight ppm) are shown in Table 1. The epoxy resin (1) contained in the epoxy resin composition (A-6) was such that in the above formula (1), R 1 It was only those having an n-pentyl group.

[0139] [Example 7] In Example 1, except that 252 g of 1-hexanol (1-hexanol was 0.3 molar times with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask, all were carried out in the same manner to obtain an epoxy resin composition (A-7). Composition of epoxy resin composition (A-7) (ratios (wt%) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / eq), hydrolyzable chlorine content (wt ppm) are shown in Table 1. The epoxy resin (1) contained in the epoxy resin composition (A-7) is, in the formula (1), R 1 was only the one in which R is an n-hexyl group.

[0140] [Example 8] In Example 1, 378 g of 1-hexanol (0.45 mol times 1-hexanol with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask, and otherwise carried out in the same manner to obtain an epoxy resin composition (A-8). Composition of epoxy resin composition (A-8) (ratios (wt%) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / eq), hydrolyzable chlorine content (wt ppm) are shown in Table 1. The epoxy resin (1) contained in the epoxy resin composition (A-8) is, in the formula (1), R 1 was only the one in which R is an n-hexyl group.

[0141] [Example 9] In Example 1, 504 g of 1-hexanol (0.6 mol times 1-hexanol with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask, and otherwise carried out in the same manner to obtain an epoxy resin composition (A-9). Composition of epoxy resin composition (A-9) (ratios (wt%) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / eq), hydrolyzable chlorine content (wt ppm) are shown in Table 1. The epoxy resin (1) contained in the epoxy resin composition (A-9) is, in the formula (1), R 1 was only the one in which R is an n-hexyl group.

[0142] [Comparative Example 1] In Example 1, an epoxy resin composition (A-10) was obtained in the same manner except that 1-butanol was not charged into the four-necked flask. Table 1 shows the composition of the epoxy resin composition (A-10) (the ratio (% by weight) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / eq), and hydrolyzable chlorine content (ppm by weight).

[0143] [Comparative Example 2] In Example 1, an epoxy resin composition (A-11) was obtained in the same manner except that 298 g of 2-propanol (0.6 molar times 2-propanol with respect to epichlorohydrin) was charged instead of 183 g of 1-butanol charged into the four-necked flask. Table 1 shows the composition of the epoxy resin composition (A-11) (the ratio (% by weight) of epoxy resin (1), epoxy resin (2-0), epoxy resin (2-1) and other components), epoxy equivalent (g / eq), and hydrolyzable chlorine content (ppm by weight).

[0144] [Table 1]

[0145] [Production of Epoxy Resin Composition (B) and Evaluation of Elastic Modulus] [Examples 10 to 18 and Comparative Examples 3 to 4] [Measurement of Elastic Modulus (E' at 250 °C)] At the ratios shown in Table 2, the epoxy resin compositions (A-1) to (A-11) of Examples 1 to 9 and Comparative Examples 1 to 2 were blended with a curing agent (phenol aralkyl resin (trade name MEH7800SS, manufactured by Meiwafosis Co., Ltd.)) and a curing catalyst (triphenylphosphine (trade name Hokko TPP, manufactured by Hokuko Chemical Industry Co., Ltd.)), heated to 100°C and stirred until uniform to obtain epoxy resin compositions (B-1) to (B-11), respectively. The obtained epoxy resin compositions (B-1) to (B-11) were cured by heating at 120°C for 2 hours and at 175°C for 6 hours to obtain cured products. The obtained cured products were cut into test pieces with a length of 5 cm, a width of 1 cm, and a thickness of 5 mm, and analyzed by a thermomechanical analyzer (DMS: EXSTAR6100 manufactured by Seiko Instruments Inc.) in a three-point bending mode under the following measurement conditions, and the elastic modulus at 250°C (E') at 1 Hz was determined. Heating rate: 5°C / min Measurement temperature range: 30°C to 300°C The results are shown in Table 2. Note that "parts" in Table 2 represents "parts by weight".

[0146]

Table 2

[0147] 〔Evaluation of Results〕 From Table 1, it can be seen that the epoxy resin compositions (A) of Examples 1 to 9 containing epoxy resin (1) have less hydrolyzable chlorine content compared to the epoxy resin compositions (A) of Comparative Examples 1 to 2, and thus are excellent in electrical properties. Also, from Table 2, it can be seen that the epoxy resin compositions (B) of Examples 10 to 18 are excellent in high-temperature crack resistance because they have a lower elastic modulus at a high temperature of 250°C compared to the epoxy resin compositions (B) of Comparative Examples 3 to 4.

Claims

1. An epoxy resin composition (A) characterized by containing an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2). 【Chemical 1】 (In formula (1), R １ represents a linear aliphatic hydrocarbon group having 4 to 6 carbon atoms.) 【Chemical Formula 2】 (In formula (2), n represents an integer from 0 to 1.)

2. The epoxy resin composition (A) according to claim 1, wherein the proportion of the epoxy resin represented by the formula (1) in the epoxy resin composition is 0.01 to 5.0% by weight.

3. In the epoxy resin represented by the formula (2), the proportion of the epoxy resin with n = 0 in the epoxy resin composition (A) is 83.0 to 90.0% by weight and the proportion of the epoxy resin with n = 1 in the epoxy resin composition (A) is 2.0 to 9.9% by weight. The epoxy resin composition (A) according to claim 1 or 2.

4. The epoxy resin composition (A) according to any one of claims 1 to 3, wherein the hydrolyzable chlorine content in the epoxy resin composition is 390 ppm by weight or less.

5. An epoxy resin composition (B) containing 0.01 to 1000 parts by weight of a curing agent with respect to 100 parts by weight of the epoxy resin composition (A) according to any one of claims 1 to 4.

6. The epoxy resin composition (B) according to claim 5, wherein the curing agent is at least one selected from the group consisting of phenolic curing agents, amine curing agents, acid anhydride curing agents, and amide curing agents.

7. The epoxy resin composition (B) according to claim 5 or 6, further containing an epoxy resin different from the epoxy resin in the epoxy resin composition (A).

8. A cured product obtained by curing the epoxy resin composition (B) according to any one of claims 5 to 7.

9. An electrical and electronic component obtained by curing the epoxy resin composition (B) according to any one of claims 5 to 7.

Images