Epoxy resin composition, cured product, and electrical/electronic component
阅读说明：本技术 环氧树脂组合物、固化物及电气电子部件 (Epoxy resin composition, cured product, and electrical/electronic component ) 是由 太田员正 于 2018-12-10 设计创作，主要内容包括：本发明涉及一种环氧树脂组合物(A)和一种环氧树脂组合物(B),所述环氧树脂组合物(A)含有下式(1)所示的环氧树脂和下式(2)所示的环氧树脂,且下式(1)所示的环氧树脂的含量为0.01～0.99重量％,所述环氧树脂组合物(B)相对于环氧树脂组合物(A)100重量份,含有固化剂0.01～1000重量份。(The present invention relates to an epoxy resin composition (A) containing an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2), wherein the content of the epoxy resin represented by the following formula (1) is 0.01 to 0.99% by weight, and an epoxy resin composition (B) containing a curing agent in an amount of 0.01 to 1000 parts by weight based on 100 parts by weight of the epoxy resin composition (A).)
1. An epoxy resin composition A comprising an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2), wherein the content of the epoxy resin represented by the following formula (1) is 0.01 to 0.99% by weight,
[ solution 1]
Wherein in the formula (2), n represents an integer of 0to 2.
2. The epoxy resin composition A according to claim 1, which comprises 49.2 to 89.0% by weight of the epoxy resin represented by the formula (2) wherein n is 0, 8.2 to 39.2% by weight of the epoxy resin wherein n is 1, and 0.1 to 7.5% by weight of the epoxy resin wherein n is 2.
3. The epoxy resin composition A according to claim 2, which comprises 51.9 to 87.9% by weight of the epoxy resin represented by the formula (2) wherein n is 0, 8.9 to 37.4% by weight of the epoxy resin wherein n is 1, and 0.2 to 7.1% by weight of the epoxy resin wherein n is 2.
4. An epoxy resin composition B comprising 0.01 to 1000 parts by weight of a curing agent per 100 parts by weight of the epoxy resin composition A as defined in any one of claims 1 to 3.
5. The epoxy resin composition B according to claim 4, wherein the curing agent is at least one selected from the group consisting of a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent and an amide-based curing agent.
6. The epoxy resin composition B according to claim 4 or claim 5, further comprising an epoxy resin different from the epoxy resin in the epoxy resin composition A.
7. A cured product obtained by curing the epoxy resin composition B according to any one of claims 4 to 6.
8. An electrical/electronic component obtained by curing the epoxy resin composition B according to any one of claims 4 to 6.
Technical Field
The present invention relates to an epoxy resin composition that provides a cured product having excellent workability and curability and excellent heat resistance, and a cured product obtained by curing the epoxy resin composition. The present invention also relates to an electrical and electronic component comprising the cured epoxy resin.
Background
Epoxy resins are cured with various curing agents to form cured products generally excellent in mechanical properties, heat resistance, electrical properties, and the like, and therefore are used in a wide range of fields such as adhesives, paints, and electrical and electronic materials. Particularly in the field of electric and electronic materials, in the field of semiconductor encapsulating materials, epoxy resins of the tetramethylbiphenol type are widely used as providing high-value-added encapsulating materials.
The epoxy resin of tetramethylbiphenol type has a rigid tetramethylbiphenyl skeleton, is excellent in both heat resistance and moisture absorption resistance, and has a low melt viscosity at 150 ℃, so that it can be used as a semiconductor encapsulating material to realize high filling of a filler and can effectively prevent lead displacement when molded into an encapsulating material on a semiconductor, but has the following disadvantages.
That is, the epoxy resin of the tetramethylbiphenol type is a bifunctional epoxy resin, and therefore, the crosslinking density is low, and the heat resistance is insufficient for the use in electric and electronic materials. Further, since the epoxy equivalent is high, the amount of secondary hydroxyl groups generated after the curing reaction is large and the moisture absorption rate is high. Further, the level of the amount of hydrolyzable chlorine cannot be considered to be sufficient in terms of low chlorination required in recent years.
Patent document 1 describes production of a tetramethylbiphenol-type epoxy resin by reaction of 4,4 ' -dihydroxy-3, 3 ', 5,5 ' -tetramethylbiphenyl with epichlorohydrin.
Patent document 2 describes that a tetramethylbiphenol-type epoxy resin is produced by the reaction of 4,4 ' -dihydroxy-3, 3 ', 5,5 ' -tetramethylbiphenyl with epichlorohydrin, and dimethyl sulfoxide is used as a co-catalyst for the reaction.
Patent document 3 describes that a commercially available tetramethylbiphenol-type epoxy resin ("Epikote YX 4000", epoxy equivalent 186, total organic halogen content 1180ppm) is reacted with KOH or a NaOH/isopropanol solution in a mixed solvent of isobutyl ketone and dimethyl sulfoxide at 70 ℃ or 60 ℃ to obtain an epoxy resin.
Patent document 4 discloses a method for producing a high-purity epoxy resin containing a specific polyfunctional epoxy resin by reacting an epoxy compound in the presence of an alkali metal hydroxide at a specific temperature range. Patent document 4 describes that the specific polyfunctional epoxy resin is preferably contained in an amount of 1 to 10%, and if it is less than 1%, it is not preferable from the viewpoint of heat resistance.
Patent document 5 describes a crystalline epoxy resin showing a specific GPC analysis peak obtained in the reaction of 4,4 ' -dihydroxy-3, 3 ', 5,5 ' -tetramethylbiphenyl with epichlorohydrin.
Patent document 6 describes a tetramethylbiphenol-type epoxy resin having a specific molecular weight and a small content of hydrolyzable chlorine, which is produced by reacting 4,4 ' -dihydroxy-3, 3 ', 5,5 ' -tetramethylbiphenyl with epichlorohydrin.
Disclosure of Invention
Problems to be solved by the invention
However, it can be confirmed in the comparative examples described later that the epoxy resin of the present invention is not produced in the production methods described in patent documents 1 to 5.
In the epoxy resin described in patent document 6, it was confirmed that the workability, curability, and heat resistance were insufficient.
The problem to be solved by the present invention is to provide an epoxy resin composition (a) having excellent handling properties as an epoxy resin, and to provide an epoxy resin composition (B) having excellent curability and capable of providing a cured product having excellent heat resistance by containing the epoxy resin composition (a) and a curing agent, and a cured product thereof. The present invention also provides an electrical and electronic component comprising the cured epoxy resin.
Technical scheme for solving problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that the above problems can be solved by an epoxy resin composition (A) containing an epoxy resin having a specific structure in a specific amount and an epoxy resin composition (B) containing the epoxy resin composition (A) and a curing agent, and have completed the present invention.
That is, the main contents of the present invention include the following [1] to [8 ]:
[1] an epoxy resin composition (A) comprising an epoxy resin represented by the following formula (1) and an epoxy resin represented by the following formula (2), wherein the content of the epoxy resin represented by the following formula (1) is 0.01 to 0.99% by weight.
[ solution 1]
(in the formula (2), n represents an integer of 0to 2.)
[2] The epoxy resin composition (A) according to [1], which contains 49.2 to 89.0% by weight of an epoxy resin having n-0, 8.2 to 39.2% by weight of an epoxy resin having n-1, and 0.1 to 7.5% by weight of an epoxy resin having n-2 in the epoxy resin represented by the formula (2).
[3] The epoxy resin composition (A) according to [2], which contains 51.9 to 87.9 wt% of an epoxy resin having n-0, 8.9 to 37.4 wt% of an epoxy resin having n-1, and 0.2 to 7.1 wt% of an epoxy resin having n-2, in the epoxy resin represented by the formula (2).
[4] An epoxy resin composition (B) comprising 0.01 to 1000 parts by weight of a curing agent per 100 parts by weight of the epoxy resin composition (A) according to any one of [1] to [3 ].
[5] The epoxy resin composition (B) according to [4], wherein the curing agent is at least one selected from the group consisting of a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent and an amide-based curing agent.
[6] The epoxy resin composition (B) according to [4] or [5], which further contains an epoxy resin different from the epoxy resin in the epoxy resin composition (A).
[7] A cured product obtained by curing the epoxy resin composition (B) according to any one of [4] to [6 ].
[8] An electrical/electronic component obtained by curing the epoxy resin composition (B) according to any one of [4] to [6 ].
Effects of the invention
The present invention provides an epoxy resin composition (a) having superior handling properties, an epoxy resin composition (B) having superior curability, and an epoxy resin cured product having superior heat resistance, compared to conventional products.
The epoxy resin composition of the present invention has the above-mentioned effects, and therefore can be effectively used in electric and electronic parts such as semiconductor sealing materials and laminated sheets.
Drawings
FIG. 1 shows the preparation of an epoxy resin (1) in the epoxy resin composition obtained in example 11H-NMR spectrum.
Detailed Description
The following description will explain embodiments of the present invention in detail, but the following description is an example of the embodiments of the present invention, and the present invention is not limited to the following description unless departing from the gist thereof. In the present specification, the expression "to" is used as an expression including a numerical value or a physical property value before and after the expression.
[ epoxy resin composition (A) ]
The epoxy resin composition (A) of the present invention contains an epoxy resin represented by the following formula (1) (hereinafter sometimes referred to as "epoxy resin (1)") and an epoxy resin represented by the following formula (2), and the content of the epoxy resin (1) is 0.01 to 0.99% by weight.
The epoxy resin composition (a) of the present invention contains an epoxy resin in which n is 0 (hereinafter, may be referred to as "epoxy resin (2-0)") among the epoxy resins represented by the following formula (2), preferably 49.2 to 89.0% by weight, particularly preferably 51.9 to 87.9% by weight; the epoxy resin having n of 1 (hereinafter sometimes referred to as "epoxy resin (2-1)") is preferably 8.2 to 39.2% by weight, and particularly preferably 8.9 to 37.4% by weight; the epoxy resin having n-2 (hereinafter sometimes referred to as "epoxy resin (2-2)") is preferably 0.1 to 7.5% by weight, and particularly preferably 0.2 to 7.1% by weight.
Hereinafter, the epoxy resin (2-0), the epoxy resin (2-1) and the epoxy resin (2-2) will be collectively referred to as "epoxy resin (2)".
[ solution 2]
(in the formula (2), n represents an integer of 0to 2.)
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), and is defined as an "epoxy resin composition", but in the technical field of epoxy resins, the "epoxy resin" is obtained not as a single component but as a "composition" composed of a plurality of components. Accordingly, the epoxy resin composition (a) of the present invention is expressed as "epoxy resin" in the art, and is sometimes sold as "epoxy resin". Further, the "epoxy compound (uncured)" is referred to as "epoxy resin" in the art.
[ mechanism ]
The epoxy resin composition (A) of the present invention containing the epoxy resin (1) having a radiation structure at a specific ratio to the epoxy resin (2) having a linear structure becomes solid after 24 hours in an environment of 0to 30 ℃ from a 150 ℃ molten state due to the epoxy resin (1) contained at the specific ratio. Further, the epoxy resin composition (B) containing a curing agent has excellent curing properties and provides a cured product having excellent heat resistance, while having a melting temperature of 100 ℃ or lower and excellent handling properties.
[ epoxy resin (1), epoxy resin (2), and other ingredients ]
The epoxy resin composition (a) of the present invention needs to contain the epoxy resin (1) in an amount of 0.01 wt% or more and 0.99 wt% or less from the viewpoint of obtaining excellent workability, excellent curability as the epoxy resin composition (B) containing a curing agent described later, and excellent heat resistance as a cured product thereof, and from the viewpoint of improving the above characteristics, the epoxy resin (1) is preferably contained in an amount of 0.1 wt% or more and 0.9 wt% or less, and more preferably contained in an amount of 0.3 wt% or more and 0.7 wt% or less. The content of the epoxy resin (1) is less than or greater than the above upper limit, and the workability, curability, and heat resistance are insufficient.
The epoxy resin composition (a) of the present invention preferably contains 49.2 wt% or more and 89.0 wt% or less of the epoxy resin (2-0), 8.2 wt% or more and 39.2 wt% or less of the epoxy resin (2-1), and 0.1 wt% or more and 7.5 wt% or less of the epoxy resin (2-2). The content of the epoxy resin (2) is more preferably 51.9% by weight or more and 87.9% by weight or less of the epoxy resin (2-0), 8.9% by weight or more and 37.4% by weight or less of the epoxy resin (2-1), 0.2% by weight or more and 7.1% by weight or less of the epoxy resin (2-2); particularly preferably, the epoxy resin (2-0) is 55.2 to 80.3 wt%, the epoxy resin (2-1) is 14.8 to 35.2 wt%, and the epoxy resin (2-2) is 1.4 to 6.3 wt%, and the total content of the components of the epoxy resin (2) (epoxy resin (2-0), epoxy resin (2-1), and epoxy resin (2-2)) in the epoxy resin composition (a) of the present invention is preferably 96.4 to 97.3 wt%, particularly preferably 96.4 to 97.0 wt%, and particularly preferably 96.5 to 97.0 wt%.
When the content of each epoxy resin (2) is within the above range, the following effects of the present invention can be obtained more reliably: excellent in workability, excellent in curing characteristics when the epoxy resin composition (B) containing a curing agent is prepared, and capable of providing a cured product excellent in heat resistance.
The epoxy resin composition (a) of the present invention preferably contains other components (hereinafter, simply referred to as "other components") in addition to the epoxy resin (1) and the epoxy resin (2). The content of other components is preferably 3.0% by weight or less, and the total of the components is preferably 100% by weight.
The other component is an epoxy resin of the formula (2) produced in the production process of the epoxy resin composition (a) of the present invention, in which n is 3 or more, a hardly-identifiable component (a component incapable of analysis) by-produced in the reaction process, or a chlorine-containing organic component, and the content of the other component in the epoxy resin composition (a) of the present invention is preferably 3% by weight or less, more preferably 2.8% by weight or less, and further preferably 2.6% by weight or less. If the content of the other components is large, the necessary content of the epoxy resin (1) and the epoxy resin (2) cannot be secured, and the effects of improving the workability, curability, and heat resistance cannot be sufficiently obtained.
In the epoxy resin composition (a) of the present invention, the total of the epoxy resin (1), the epoxy resin (2) and other components is 100% by weight.
The content of each constituent component of the epoxy resin composition (a) of the present invention can be measured by high performance liquid chromatography analysis (hereinafter referred to as LC analysis).
[ epoxy equivalent ]
The epoxy resin composition (a) preferably has an epoxy equivalent of 191 to 320 g/eq from the viewpoint of obtaining excellent workability as an epoxy resin, excellent curability as a curing agent-containing epoxy resin composition (B), and excellent heat resistance as a cured product thereof, and more preferably 191 to 236 g/eq from the viewpoint of further improving workability. It is considered that the above-mentioned excellent characteristics can be obtained by setting the oxygen equivalent to the above-mentioned specific range.
In the present invention, "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.
[ method for producing epoxy resin composition (A) ]
The method for producing the epoxy resin composition (a) of the present invention is not particularly limited, and for example, it is produced by producing a tetramethylbiphenol-type epoxy resin (hereinafter, sometimes referred to as "crude epoxy resin") by a specific method and then reacting the resin with an alkali metal hydroxide.
[ production of crude epoxy resin ]
The method for producing the crude epoxy resin is not particularly limited, and examples thereof include a one-step production method described below.
< one-step Process of production >
In the one-step production method, a crude epoxy resin, which is a raw material of the epoxy resin of the present invention, is produced by reacting 4,4 ' -dihydroxy-3, 3 ', 5,5 ' -tetramethylbiphenyl (hereinafter, may be referred to as "tetramethylbiphenol (3)") represented by the following formula with epihalohydrin.
[ solution 3]
In the case of producing a crude epoxy resin by the one-step process, at least tetramethylbiphenol (3) and epihalohydrin are used as raw materials, but a polyhydric hydroxyl compound other than tetramethylbiphenol (3) (hereinafter, sometimes referred to as "other polyhydric hydroxyl compound") may be used in combination to produce a mixture of epoxy resin (1) and epoxy resin (2) with other epoxy resins.
However, from the viewpoint of enhancing the effect of the present invention, the proportion of tetramethylbiphenol (3) is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more, based on the total amount of the polyhydric hydroxyl compounds used as the raw material. The upper limit is 100 mol%, and 100 mol% is particularly preferable.
The term "polyhydric hydroxyl compound" as used herein refers to a generic term for dihydric or higher phenolic compounds and dihydric or higher alcohols.
Other polyhydric hydroxyl compounds can be exemplified by: various polyphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcinol, methylresorcinol, biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenol, 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 and the like (excluding tetramethyl diphenol (3)), and various resols obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal and the like, various resols obtained by condensation reaction of xylene resin with phenols, various cocondensates of heavy oils or bitumens with phenols and formaldehydes and the like, and chain aliphatic diols such as ethylene glycol, trimethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, and 1, 6-hexanediol, cyclic aliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether diols such as polyethylene ether diol, polyoxytrimethylene ether diol, and polypropylene ether diol.
Among them, preferable examples of the polyhydric hydroxyl compound include: phenol novolac resins, phenol aralkyl resins, polyhydric phenol resins obtained by condensation reaction of phenol with hydroxybenzaldehyde, biphenyl aralkyl resins, naphthol aralkyl resins, ethylene glycol, trimethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 3-pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, chain aliphatic diols such as 1, 6-hexanediol, cyclic aliphatic diols such as cyclohexanediol and cyclodecanediol, and polyalkylene ether diols such as polyvinyl ether diol, polyoxytrimethylene ether diol and polypropylene ether diol.
Tetramethylbiphenol (3) used as a raw material and other polyhydric hydroxyl compounds used as needed were dissolved in epihalohydrin in an amount corresponding to 1 equivalent of hydroxyl groups of the total polyhydric hydroxyl compounds with respect to the total sum of these hydroxyl compounds to prepare a homogeneous solution: usually 1.0 to 10.0 equivalents, preferably 2.9 to 5.9 equivalents, and more preferably 3.0 to 5.0 equivalents. When the amount of epihalohydrin is not less than the lower limit, the reaction for increasing the molecular weight can be easily controlled, and the epoxy resin obtained can have an appropriate epoxy equivalent weight, which is preferable. On the other hand, if the amount of epihalohydrin is not more than the above upper limit, the production efficiency tends to be improved, and therefore it is preferable.
In the epihalohydrin used in the reaction, epichlorohydrin or epibromohydrin is generally used.
Then, while stirring the solution, an alkali metal hydroxide is added thereto as a solid or an aqueous solution to react, wherein the amount of the alkali metal hydroxide is an amount corresponding to the following amount, with respect to 1 equivalent of hydroxyl groups of the total polyhydric hydroxyl compounds of the raw materials: usually 0.5 to 2.0 equivalents, preferably 0.7 to 1.8 equivalents, and more preferably 0.9 to 1.6 equivalents. When the amount of the alkali metal hydroxide is not less than the lower limit, the reaction with the epoxy resin formed from unreacted hydroxyl groups is difficult, and the reaction for increasing the molecular weight is easily controlled, which is preferable. Further, if the amount of the alkali metal hydroxide is less than the above upper limit, impurities resulting from side reactions are less likely to be generated, which is preferable. As the alkali metal hydroxide used herein, there may be mentioned, in general: sodium hydroxide or potassium hydroxide.
The reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is preferably 20-150 ℃, more preferably 40-100 ℃, and further preferably 40-80 ℃. If the reaction temperature is not lower than the lower limit, the reaction is easily advanced and the reaction can be easily controlled, which is preferable. Further, if the reaction temperature is not higher than the upper limit, the side reaction is difficult to proceed, and particularly, chlorine impurities are easily reduced, which is preferable.
The reaction is carried out while dehydrating by a method of azeotroping the reaction solution while maintaining a predetermined temperature as necessary, separating oil/water from a condensate obtained by cooling the volatilized vapor, and returning the oil from which water has been removed to the reaction system. In order to suppress the rapid reaction, the alkali metal hydroxide is added intermittently or continuously in a small amount preferably for 0.1 to 8 hours, more preferably for 0.1 to 7 hours, and further preferably for 0.5 to 6 hours. If the time for adding the alkali metal hydroxide is not less than the lower limit, the reaction can be prevented from rapidly proceeding, and the reaction temperature can be easily controlled, which is preferable. If the addition time is less than the upper limit, chlorine impurities are less likely to be generated, which is preferable, and further preferable from the viewpoint of economy. After the reaction is completed, the insoluble by-product salt is removed by filtration or washing with water, and then unreacted epihalohydrin is distilled off under reduced pressure to obtain the objective crude epoxy resin.
In addition, 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; phosphines such as triphenylphosphine, and the like.
In addition, in the reaction, alcohol such as ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dioxane and ethylene glycol dimethyl ether; glycol ethers such as methoxypropanol; aprotic polar solvents such as dimethyl sulfoxide and dimethylformamide.
[ production of epoxy resin composition (A) ]
The crude epoxy resin produced as described above is reacted with a strong base to obtain the epoxy resin composition (a) of the present invention containing the epoxy resin (1), the epoxy resin (2) and other components in the above-described amounts. Further, the epoxy equivalent can be adjusted within the preferable range specified in the present invention by the reaction with the strong base.
That is, for example, the epoxy equivalent can be increased by increasing the temperature, increasing the resin content and the amount of alkali with respect to the solvent, and conversely, the epoxy equivalent can be decreased by decreasing the temperature, decreasing the resin content and the amount of alkali with respect to the solvent.
The following describes the detailed conditions for producing the epoxy resin composition (a) of the present invention, but depending on the conditions, the reaction time varies, and therefore, the desired epoxy resin composition (a) can be obtained by appropriately sampling and analyzing the amounts of the respective constituent components, the epoxy equivalent weight, and the like.
In the reaction of the crude epoxy resin with a strong base, an organic solvent for dissolving the epoxy resin may also be used. The organic solvent used in the reaction is not particularly limited, but a mixed solvent of an aprotic polar solvent and an inert organic solvent other than the aprotic polar solvent is preferred in view of production efficiency, operability, workability, and the like.
The aprotic polar solvent includes, for example: dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, and the like. These may be used singly or in combination of two or more. Among these aprotic polar solvents, dimethyl sulfoxide is preferable because it is easily available and has excellent effects.
Examples of the organic solvent used together with the aprotic polar solvent include: ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. From the viewpoints of the effect and the easiness of post-treatment, a ketone solvent is preferable, and methyl isobutyl ketone is particularly preferable. These may be used singly or in combination of two or more.
The aprotic polar solvent and the other organic solvent are preferably used in such a manner that the ratio of the aprotic polar solvent to the total amount thereof is 1 to 30% by weight, particularly 10to 20% by weight.
The organic solvent is used in an amount such that the concentration of the crude epoxy resin is usually 3 to 70% by weight, preferably 5 to 50% by weight, and more preferably 10to 40% by weight.
The strong base is a solution of an alkali metal hydroxide. Alkali metal hydroxides, there may be mentioned: potassium hydroxide, sodium hydroxide, and the like.
The alkali metal hydroxide is dissolved in an organic solvent.
The amount of the alkali metal hydroxide used is preferably 0.01 parts by weight or more and 0.49 parts by weight or less based on 100 parts by weight of the crude epoxy resin in terms of solid content of the alkali metal hydroxide. If the amount of the alkali metal hydroxide used is set in this range, the ratio of each constituent component and the epoxy equivalent of the obtained epoxy resin may be easily adjusted within the above preferred ranges, and if the amount of the alkali metal hydroxide is not within the above ranges, an epoxy resin containing the epoxy resin (1), the epoxy resin (2) and other components within the ranges specified in the present invention may not be obtained.
The reaction temperature is preferably 70-90 ℃, and more preferably 75-85 ℃; the reaction time is preferably 0.1 to 15 hours, more preferably 0.3 to 12 hours. If the reaction temperature is outside the above range, an epoxy resin containing the epoxy resin (1), the epoxy resin (2) and other components within the range specified in the present invention may not be obtained.
After the reaction, excess alkali metal hydroxide, by-product salt and the like can be removed by a method such as washing with water, and the organic solvent can be further removed by distillation under reduced pressure and/or steam distillation to obtain the epoxy resin composition (A) of the present invention.
[ epoxy resin composition (B) ]
The epoxy resin composition (B) of the present invention contains at least the above-mentioned epoxy resin composition (a) of the present invention and a curing agent. In the epoxy resin composition (B) of the present invention, if necessary, other epoxy resins (hereinafter, simply referred to as "other epoxy resins") than the epoxy resin composition (a) of the present invention, curing accelerators, inorganic fillers, coupling agents and the like may be appropriately blended.
The epoxy resin composition (B) of the present invention containing the epoxy resin composition (a) of the present invention is excellent in curing characteristics such as curability, and can provide a cured product that sufficiently satisfies various physical properties required for various applications. The epoxy resin composition (B) of the present invention having excellent curability can improve productivity when applied to various applications.
[ curing agent ]
The curing agent in the present invention means a substance which contributes to a crosslinking reaction and/or a chain extension reaction between epoxy groups of an epoxy resin. In the present invention, a substance called a "curing accelerator" may be generally used as a curing agent as long as it contributes to a crosslinking reaction and/or a chain extension reaction between epoxy groups of an epoxy resin.
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 in terms of solid content. Further, it is more preferably 500 parts by weight or less, and still more preferably 300 parts by weight or less. In the present invention, the "solid component" means a component other than the solvent, and includes not only solid epoxy resin but also epoxy resin in a semisolid or viscous liquid state. The "total epoxy resin component" corresponds to the amount of the epoxy resin contained in the epoxy resin composition (B) of the present invention, and corresponds to the amount of the epoxy resin (1) and epoxy resin (2) in the epoxy resin composition (a) when the epoxy resin composition (B) of the present invention contains only the epoxy resin composition (a) and the amount of the epoxy resin other than the epoxy resin (1) and epoxy resin (2) in the other components, and corresponds to the total amount of the epoxy resin and the other epoxy resin in the epoxy resin composition (a) when the epoxy resin composition (a) and the other epoxy resin are contained.
The curing agent is not particularly limited, and any of those conventionally known as curing agents for epoxy resins can be used. Examples thereof include: phenol curing agents, amine curing agents such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles, and the like.
Among them, the epoxy resin composition (B) of the present invention can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame retardancy and the like by containing a phenol-based curing agent, and therefore the curing agent preferably contains a phenol-based curing agent. Further, from the viewpoint of heat resistance and the like, it is preferable to contain an acid anhydride curing agent and an amide curing agent. Furthermore, imidazoles are also preferably used from the viewpoint of sufficiently advancing the curing reaction and improving the heat resistance.
The curing agent may be used alone or in combination of two or more. When two or more curing agents are used in combination, they may be mixed in advance to prepare a mixed curing agent and used, or the components of the curing agent may be added to each of the components of the epoxy resin composition (B) and mixed simultaneously.
< phenol curing agent >
Specific examples of the phenol curing agent include: bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, trisphenol methane type resins, naphthol novolac resins, brominated bisphenol A, brominated phenol novolac resins, and the like, and polyphenol novolac resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal, and the like, polyphenol novolac resins obtained by condensation reaction of xylene resins with phenols, heavy oils or bitumens, and co-condensation resins of phenols and formaldehydes, phenol resins such as phenol-benzaldehyde-xylylene oxide polycondensate, phenol-benzaldehyde-xylylene dihalide polycondensate, phenol-benzaldehyde-4, 4 '-dimethoxybiphenyl polycondensate, phenol-benzaldehyde-4, 4' -dihalobiphenyl polycondensate, and the like.
These phenolic curing agents may be used alone, or two or more of them may be used in combination in any combination and blending ratio.
Among the above phenol-based curing agents, preferred are phenol novolac resins (e.g., a compound represented by the following formula (4)), phenol aralkyl resins (e.g., a compound represented by the following formula (5)), biphenyl aralkyl resins (e.g., a compound represented by the following formula (6)), naphthol novolac resins (e.g., a compound represented by the following formula (7)), naphthol aralkyl resins (e.g., a compound represented by the following formula (8)), triphenol methane resins (e.g., a compound represented by the following formula (9)), phenol-benzaldehyde-xylylene oxide polycondensates (e.g., a compound represented by the following formula (10)), phenol-benzaldehyde-xylylene dihalide polycondensates (e.g., a compound represented by the following formula (10)), phenol-benzaldehyde-4, examples of the phenol-benzaldehyde-4, 4 ' -dihalobiphenyl polycondensate include a phenol novolac resin (e.g., a compound represented by the following formula (4)), a phenol-benzaldehyde-4, 4 ' -dihalobiphenyl polycondensate (e.g., a compound represented by the following formula (11)), a phenol aralkyl resin (e.g., a compound represented by the following formula (5)), a biphenyl aralkyl resin (e.g., a compound represented by the following formula (6)), a phenol-benzaldehyde-xylylene oxide polycondensate (e.g., a compound represented by the following formula (10)), a phenol-benzaldehyde-4, 4 ' -dimethoxybiphenyl polycondensate (e.g., a compound represented by the following formula (11)), and the like, Phenol-benzaldehyde-4, 4' -dihalobiphenyl polycondensate (e.g., a compound represented by the following formula (11)).
[ solution 4]
(wherein, in the above formulae (4) to (9), k1～k6Each represents a number of 0 or more. )
[ solution 5]
(wherein, in the above formulae (10) and (11), k7、k8、l1、l2Each represents a number of 1 or more. )
The amount of the phenolic curing agent blended is preferably 0.1 to 1000 parts by weight, more preferably 500 parts by weight or less, further preferably 300 parts by weight or less, and particularly preferably 100 parts by weight or less, based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition (B).
< amine-based curing agent >
Examples of the amine-based curing agent (excluding tertiary amine) include: aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like.
Aliphatic amines, which may be exemplified by: ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminopropane, hexamethylenediamine, 2, 5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetrakis (hydroxyethyl) ethylenediamine, and the like.
Polyetheramines, which may be exemplified by: triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like.
Alicyclic amines, which may be exemplified by: isophorone diamine, menthane diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro (5,5) undecane, norbornene diamine, and the like.
Aromatic amines, which may be exemplified by: tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2, 4-diaminoanisole, 2, 4-tolylenediamine, 2, 4-diaminodiphenylmethane, 4' -diamino-1, 2-diphenylethane, 2, 4-diaminodiphenylsulfone, 4,4 '-diaminodiphenyl sulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α - (m-aminophenyl) ethylamine, α - (p-aminophenyl) ethylamine, diaminodiethyldimethyldiphenylmethane, α' -bis (4-aminophenyl) p-diisopropylbenzene, and the like.
The amine-based curing agent may be used alone, or two or more thereof may be used in combination in any combination and blending ratio.
The amine-based curing agent is preferably used in such a manner that the equivalent ratio of the functional group in the curing agent to the epoxy group in the total epoxy resin component contained in the epoxy resin composition (B) is in the range of 0.8 to 1.5. When the amine-based curing agent is within this range, unreacted epoxy groups and functional groups of the curing agent do not easily remain, and therefore, this is preferable.
Tertiary amines, which may be exemplified by: 1, 8-diazabicyclo (5,4,0) undec-7-ene, triethylene diamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like.
The tertiary amines listed above may be used alone, or two or more thereof may be used in combination in any combination and blending ratio.
The tertiary amine is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in the total epoxy resin components contained in the epoxy resin composition (B) is in the range of 0.8 to 1.5. If the tertiary amine is within this range, unreacted epoxy groups and functional groups of the curing agent do not easily remain, and therefore, it is preferable.
< curing agent of acid anhydride group >
Examples of the acid anhydride curing agent include: acid anhydrides, modified acid anhydrides, and the like.
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 (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexanedicarboxylic anhydride, methylcyclohexanetetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, chlorendic anhydride, nadic anhydride, methylnadic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic anhydride, 3, 4-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, and the like.
Examples of the modified product of the acid anhydride include a product obtained by modifying the acid anhydride with a diol. Examples of the diols 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. In addition, two or more kinds of these diols and/or copolyether diols of polyether diols may also be used.
Among the modified acid anhydrides, it is preferable to modify the acid anhydride with 0.4 mol or less of a diol based on 1 mol of the acid anhydride. If the modification amount is less than the above upper limit, the viscosity of the epoxy resin composition does not become too high, workability tends to be good, and the speed of the curing reaction with the epoxy resin tends to be good.
The acid anhydride curing agent mentioned above may be used alone, or two or more kinds may be used in combination in an arbitrary combination and blending amount.
When an acid anhydride-based curing agent is used, it is preferably used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in the total epoxy resin component in the epoxy resin composition (B) is in the range of 0.8 to 1.5. When the acid anhydride-based curing agent is within this range, unreacted epoxy groups and functional groups of the curing agent do not easily remain, and therefore, this is preferable.
< amide curing agent >
Examples of the amide curing agent include: dicyandiamide and derivatives thereof, polyamide resins, and the like.
The amide curing agent may be used alone, or two or more thereof may be used in combination and ratio.
When the amide curing agent is used, the amide curing agent is preferably used in an amount of 0.1 to 20% by weight based on the total amount of the total epoxy resin components and the amide curing agent in the epoxy resin composition (B).
< imidazoles >
Imidazoles, which may be exemplified by: 2-phenylimidazole, 2-ethyl-4- (5) -methylimidazole, 2-phenyl-4-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 adduct of epoxy resin and the imidazoles. Since imidazoles have catalytic ability, imidazoles are generally classified as curing accelerators, but they are classified as curing agents in the present invention.
The above-listed imidazoles may be used alone, or two or more kinds thereof may be mixed in any combination and ratio.
When imidazoles are used, they are preferably used in such a manner that the imidazoles are 0.1 to 20% by weight based on the total amount of the epoxy resin components and the imidazoles in the epoxy resin composition (B).
< other curing agent >
In the epoxy resin composition (B) of the present invention, other curing agents may be used in addition to the above curing agents. Other curing agents that can be used in the epoxy resin composition (B) of the present invention are not particularly limited, and those 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.
[ other epoxy resins ]
The epoxy resin composition (B) of the present invention may further contain another epoxy resin in addition to the epoxy resin composition (a). The epoxy resin composition (B) of the present invention can improve heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like by containing another epoxy resin.
As for the other epoxy resins that can be used in the epoxy resin composition (B) of the present invention, all epoxy resins other than the epoxy resins (mainly, the epoxy resin (1) and the epoxy resin (2)) contained in the epoxy resin composition (a) are applicable, and specific examples thereof include: bisphenol A-type epoxy resin, trishydroxyphenylmethane-type epoxy resin, anthracene-type epoxy resin, phenol-modified xylene resin-type epoxy resin, bisphenol cyclododecyl-type epoxy resin, bisphenol diisopropylidenediphenol-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AD-type epoxy resin, hydroquinone-type epoxy resin, methylhydroquinone-type epoxy resin, dibutylhydroquinone-type epoxy resin, resorcinol-type epoxy resin, methylresorcinol-type epoxy resin, biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin other than epoxy resins (1) and (2) in epoxy resin composition (A), tetramethylbisphenol F-type epoxy resin, dihydroxydiphenyl ether-type epoxy resin, epoxy resin derived from thiodiphenol, dihydroxynaphthalene-type epoxy resin, dihydroxyanthracene-type epoxy resin, dihydroxydihydroanthracene-type epoxy resin, phenol-modified xylene resin-type epoxy resin, bisphenol cyclododecyl-type epoxy resin, bisphenol diisopropylidenediphenol-type epoxy resin, bisphenol F-type epoxy resin, and the, Dicyclopentadiene type epoxy resin, dihydroxy stilbene-derived epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, terpene phenol type epoxy resin, dicyclopentadiene phenol type epoxy resin, epoxy resin derived from phenol-hydroxybenzaldehyde condensate, epoxy resin derived from phenol-croton aldehyde condensate, epoxy resin derived from phenol-glyoxal condensate, epoxy resin derived from heavy oil or asphalt with phenol and formaldehyde co-condensation resins, epoxy resin derived from diaminodiphenylmethane, epoxy resin derived from aminophenol, epoxy resin derived from xylylenediamine, epoxy resin derived from xylylene diamine, epoxy resin derived from cresol novolac resin, epoxy resin derived from phenol, epoxy resin derived from xylylene diamine, epoxy, Epoxy resins derived from methylhexahydrophthalic acid, epoxy resins derived from dimer acid, and the like.
These may be used alone, or two or more kinds may be used in any combination and mixing ratio.
Among these, bisphenol a type epoxy resins, tetramethyl biphenyl diphenol type epoxy resins other than the epoxy resins (1) and (2) in the epoxy resin composition (a), 4' -biphenyl diphenol type epoxy resins, biphenyl aralkyl type epoxy resins, phenol aralkyl type epoxy resins, dihydroxyanthracene type epoxy resins, dicyclopentadiene type epoxy resins, o-cresol novolac type epoxy resins, and trisphenol methane type epoxy resins are particularly preferable from the viewpoint of the fluidity of the composition, and further from the viewpoint of the heat resistance, moisture absorption resistance, flame retardancy and the like of the cured product.
When the epoxy resin composition (B) of the present invention contains the other epoxy resin, the content thereof is preferably 0.01 to 60 parts by weight, more preferably 40 parts by weight or less, further preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, and further preferably 1 part by weight or more, based on 100 parts by weight of the total epoxy resin components in the composition.
[ curing accelerators ]
The epoxy resin composition (B) of the present invention preferably contains a curing accelerator. By including the curing accelerator, the curing time can be shortened, the curing temperature can be lowered, and a desired cured product can be easily obtained.
The curing accelerator is not particularly limited, and specific examples thereof include: phosphorus compounds such as organophosphines and phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and halogenated boron-amine complexes.
Examples of the phosphorus-based compound that can be used as a curing accelerator include: organic phosphines such as triphenylphosphine, diphenyl (p-tolyl) phosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, tri (alkyl-alkoxyphenyl) phosphine, tri (dialkylphenyl) phosphine, tri (trialkylphenyl) phosphine, tri (tetraalkylphenyl) phosphine, tri (dialkoxyphenyl) phosphine, tri (trialkoxyphenyl) phosphine, tri (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, and alkyldiarylphosphine; complexes of these organophosphines with organoborons; and compounds obtained by adding a quinone compound 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, or phenyl-1, 4-benzoquinone, or a compound such as diazabenzene to these organic phosphines.
Among the above-mentioned curing accelerators, organic phosphines and phosphonium salts are preferable, and organic phosphines are most preferable. The curing accelerator may be used alone or in combination of two or more kinds thereof at any ratio.
The curing accelerator is preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition (B). The content is more preferably 0.5 parts by weight or more, and still more preferably 1 part by weight or more, and on the other hand, is more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. When the content of the curing accelerator is not less than the lower limit, a good curing accelerating effect can be obtained, while when the content is not more than the upper limit, desired curing physical properties can be easily obtained, which is preferable.
[ inorganic Filler ]
The epoxy resin composition (B) of the present invention may contain an inorganic filler. Examples of the inorganic filler include: fused silica, crystalline silica, glass frit, alumina, calcium carbonate, calcium sulfate, talc, boron nitride, and the like. These may be used alone, or two or more kinds may be used in combination in an arbitrary combination and blending ratio. Among these, when used for semiconductor packaging applications, a fused and/or crystalline silica powder filler of a fracture type and/or a spherical shape is preferable.
When the epoxy resin composition (B) is used as a semiconductor encapsulating material, the inorganic filler can make the thermal expansion coefficient of the semiconductor encapsulating material close to that of the internal silicon chip or lead frame, and can reduce the moisture absorption amount of the entire semiconductor encapsulating material, thereby improving solder crack resistance.
The average particle diameter of the inorganic filler is usually 1 to 50 μm, preferably 1.5 to 40 μm, and more preferably 2 to 30 μm. When the average particle diameter is not less than the lower limit, the melt viscosity is not excessively high and the fluidity is not easily lowered, which is preferable; further, if the average particle diameter is not more than the above upper limit, the filler is less likely to block a narrow gap of the mold during molding, and the filling property of the material is more likely to be improved, which is preferable.
When an inorganic filler is used in the epoxy resin composition (B) of the present invention, the inorganic filler is preferably added in an amount of 60 to 95 wt% based on the whole epoxy resin composition.
[ Release agent ]
A release agent may be blended in 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, metal salts thereof, and hydrocarbon-based release agents such as paraffin wax. These may be used alone or in combination of two or more in any combination and blending ratio.
When a release agent is added to the epoxy resin composition (B) of the present invention, the amount of the release agent added 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). If the compounding amount of the release agent is within the above range, good releasability can be exhibited while maintaining the curing characteristics of the epoxy resin composition (B), and therefore, it is preferable.
[ coupling agent ]
The epoxy resin composition (B) of the present invention is preferably compounded with a coupling agent. The coupling agent is preferably used with an inorganic filler material. By adding a coupling agent, the adhesiveness between the epoxy resin as a matrix and the inorganic filler can be improved. Examples of the coupling agent include: silane coupling agents, titanate coupling agents, and the like.
Examples of the silane coupling agent include: epoxy silanes such as gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, etc., aminosilanes such as gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, etc., mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, etc., vinylsilanes such as p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (beta-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, gamma-methacryloxypropyltrimethoxysilane, etc., and epoxy, amino, and vinyl polymer silanes.
Titanate coupling agents, for example, include: isopropyltriisostearoyltitanate, isopropyltris (N-aminoethyl) titanate, diisopropylbis (dioctylphosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) acyloxytitanate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylenetitanate, and the like.
These coupling agents may be used alone, or two or more of them may be mixed in combination in an arbitrary combination and blending ratio.
When the coupling agent is used in the epoxy resin composition (B) of the present invention, the amount of the coupling agent is preferably 0.1 to 3.0 parts by weight based on 100 parts by weight of the total epoxy resin components. If the amount of the coupling agent is not less than the lower limit, the effect of improving the adhesion between the epoxy resin as the matrix and the inorganic filler tends to be high, while if the amount of the coupling agent is not more than the upper limit, the coupling agent is less likely to bleed out of the cured product obtained, which is preferable.
[ other compounding ingredients ]
Other components (sometimes referred to as "other blending components" in the present invention) than the above may be blended into the epoxy resin composition (B) of the present invention. Other compounding ingredients include, for example: flame retardants, plasticizers, reactive diluents, pigments and the like can be appropriately blended as necessary. However, the epoxy resin composition (B) of the present invention does not have any hindrance to the incorporation of components other than the above-mentioned components.
Examples of the flame retardant used in the epoxy resin composition (B) of the present invention include: halogen flame retardants such as brominated epoxy resins and brominated phenol resins, antimony compounds such as antimony trioxide, phosphorus flame retardants such as red phosphorus, phosphate esters and phosphines, nitrogen flame retardants such as melamine derivatives, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
[ cured product ]
The cured product of the present invention can be obtained by curing the epoxy resin composition (B) of the present invention. The cured product of the present invention obtained by curing the epoxy resin composition (B) of the present invention has excellent characteristics in heat resistance.
The method for curing the epoxy resin composition (B) of the present invention is not particularly limited, and a cured product can be obtained by a thermal curing reaction by heating in general. In the case of heat curing reaction, the curing temperature is preferably selected appropriately according to the kind of the curing agent used. For example, when a phenolic curing agent is used, the curing temperature is usually 130 to 300 ℃. In addition, by adding a curing accelerator to these curing agents, the curing temperature can be lowered. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, and further preferably 3 to 15 hours. If the reaction time is not less than the lower limit, the curing reaction tends to proceed sufficiently, and therefore, it is preferable. On the other hand, if the reaction time is not more than the upper limit, deterioration due to heating and energy loss during heating are likely to be reduced, and therefore, such is preferable.
A cured product using the epoxy resin composition (B) of the present invention can provide a cured product having excellent heat resistance and preferably having a glass transition temperature (Tg) of 150 ℃ or higher. The higher the glass transition temperature of the cured product, the less likely it is to be subjected to thermal stress in the resin to be sealed in the production of a semiconductor sealing material or the like, and the less likely problems such as blunting, chip damage, sliding of aluminum wiring, and package cracking occur, and therefore, this is preferable.
Here, the glass transition temperature (Tg) was measured by the method described in the following example.
[ use ]
The epoxy resin composition (a) of the present invention is excellent in handling properties, the epoxy resin composition (B) of the present invention which comprises the epoxy resin composition (a) of the present invention is excellent in curability, and the cured product of the epoxy resin composition (B) of the present invention is further excellent in heat resistance.
Therefore, the epoxy resin composition (a), the epoxy resin composition (B) and the cured product thereof of the present invention can be effectively used in any applications as long as these physical properties are required. For example, it can be suitably applied to any of the following fields: in the fields of coating materials such as electrodeposition coating materials for automobiles, multilayer anticorrosive coating materials for ships and bridges, coating materials for coating the inner surface of cans for beverages, and the like; electrical and electronic fields such as laminated boards, semiconductor sealing materials, insulating powder coating materials, and coil impregnation; seismic reinforcement of bridges, concrete reinforcement, floor materials for buildings, linings for water supply facilities, drainage/permeable pavements, adhesives for vehicles/aircrafts, and the like. Among them, the resin composition is particularly useful for electrical and electronic applications such as semiconductor sealing materials and laminated boards.
The epoxy resin composition (B) of the present invention may be used after curing for the above-mentioned applications, or may be cured in a production process for the above-mentioned applications.