JP2021031566A - Epoxy resin composition, cured product, and electric/electronic component - Google Patents

Abstract

To provide: an epoxy resin composition that is excellent in electrical reliability and excellent in thermal decomposition resistance and adhesiveness of resulting cured product; a cured product thereof; and an electric/electronic component.SOLUTION: Provided is an epoxy resin composition containing an o,o'-dibenzamide diphenyl disulfide having a total chlorine content of 1,500 ppm or less, and an epoxy resin and a curing agent. It is preferable that the concentration of o,o'-dibenzamide diphenyl disulfide for 100 wt.% of the total of epoxy resin, curing agent, curing accelerator and o,o'-dibenzamide diphenyl disulfide is 0.34 to 0.70 wt.%, and the weight ratio of o,o'-dibenzamide diphenyl disulfide/epoxy resin is 0.54 to 1.10 wt.%.SELECTED DRAWING: None

Description

The present invention relates to epoxy resin compositions, cured products and electrical / electronic components. More specifically, the present invention relates to an epoxy resin composition having excellent electrical reliability, a cured product obtained by curing this epoxy resin composition and having excellent heat-degradability and adhesiveness, and electrical / electronic parts.

Epoxy resins generally become cured products with excellent mechanical properties, heat resistance, electrical properties, etc. by curing with various curing agents, and therefore, they are used in a wide range of fields such as adhesives, paints, and electrical / electronic materials. It is used in. In particular, in the field of encapsulants represented by semiconductor devices and the like, orthocresol novolac type epoxy resins are widely used.

With the remarkable development of the electronic industry in recent years, further improvement in heat-decomposability and adhesiveness required for semiconductor encapsulant materials is required.

In response to such demands, for example, Patent Document 1 and Patent Document 2 contain epoxy resin, phenol resin, o, o'-dibenzamide diphenyl disulfide and an inorganic filler as essential components, and o, o'-di. A sealing resin composition containing a specific amount of benzamide diphenyl disulfide is disclosed. In Patent Documents 1 and 2, the total amount of chlorine of o, o'-dibenzamide diphenyl disulfide used is not examined at all. For example, in Patent Document 2, the reagent o, o'-dibenzamide diphenyl disulfide is used. Although it is used as it is, in general, commercially available o, o'-dibenzamide diphenyl disulfide contains a chlorine component of 2000 ppm or more in total chlorine content.

JP-A-2002-3704 Japanese Unexamined Patent Publication No. 2005-272739

Although it is possible to improve the adhesiveness and the moisture absorption / reflow resistance to some extent by using the epoxy resin composition containing o, o'-dibenzamide diphenyldisulfide and the cured product thereof described in Patent Document 1 and Patent Document 2. In recent years, various semiconductors have been developed, and in a situation where higher thermal decomposition resistance and improvement of adhesiveness are required, these conventional epoxy resin compositions sufficiently satisfy the required characteristics in thermal decomposition resistance and adhesiveness. I couldn't meet.

The present invention is an epoxy resin composition containing o, o'-dibenzamide diphenyl disulfide, which has excellent electrical reliability, and a cured product obtained by curing the epoxy resin composition has excellent heat-decomposability and adhesiveness. The purpose is to provide a cured product thereof and electrical / electronic parts.

As a result of diligent studies to solve the above problems, the present inventor has determined the total amount of chlorine contained in o, o'-dibenzamide diphenyl disulfide, the epoxy resin composition containing the chlorine resin composition, and the heat-degradability and adhesiveness of the cured product thereof. We found that there was a correlation between. Then, they have found that by using o, o'-dibenzamide diphenyl disulfide in which the total amount of chlorine is controlled, higher thermostable decomposition property and adhesiveness than before can be exhibited, and the present invention has been completed.

That is, the gist of the present invention lies in the following [1] to [7].

[1] An epoxy resin composition containing o, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1,500 ppm or less, an epoxy resin, and a curing agent.

[2] The epoxy resin composition according to [1], which further contains a curing accelerator.

[3] The concentration of the o, o'-dibenzamide diphenyl disulfide is 0.34 to 100% by weight of the total of the epoxy resin, the curing agent, the curing accelerator, and the o, o'-dibenzamide diphenyl disulfide. The epoxy resin composition according to [2], which is 0.70% by weight.

[4] The epoxy resin composition according to any one of [1] to [3], wherein the weight ratio of the o, o'-dibenzamide diphenyl disulfide / the epoxy resin is 0.54 to 1.10% by weight. ..

[5] A cured product obtained by curing the epoxy resin composition according to any one of [1] to [4].

[6] An electrical / electronic component obtained by curing the epoxy resin composition according to any one of [1] to [4].

[7] O, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1,500 ppm or less.

According to the present invention, it is possible to provide an epoxy resin composition having excellent electrical reliability and the obtained cured product having excellent heat-degradability and adhesiveness, and the cured product and electric / electronic parts thereof.

The embodiments of the present invention will be described in detail below, 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 as long as the gist of the present invention is not exceeded. Absent. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

[O, o'-dibenzamide diphenyl disulfide]
First, the o, o'-dibenzamide diphenyl disulfide of the present invention having a total chlorine content of 1,500 ppm or less used in the epoxy resin composition of the present invention will be described.
The o, o'-dibenzamide diphenyl disulfide of the present invention reduces the total amount of chlorine with respect to commercially available o, o'-dibenzamide diphenyl disulfide or o, o'-dibenzamide diphenyl disulfide produced according to a conventional method. It can be obtained by subjecting the treatment.

As the o, o'-dibenzamide diphenyl disulfide as a raw material for the o, o'-dibenzamide diphenyl disulfide of the present invention, commercially available products can be used. For example, o, o'-dibenzamide diphenyl disulfide manufactured by Tokyo Chemical Industry Co., Ltd. and Noctizer SS manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. can be mentioned.

Generally, in an industrial method for producing o, o'-dibenzamide diphenyl disulfide, benzoyl chloride is used as a starting material to produce o, o'-dibenzamide diphenyl disulfide. Etc., remain in a small amount in the product o, o'-dibenzamide diphenyl disulfide, so that ordinary o, o'-dibenzamide diphenyl disulfide contains chlorine. For example, the total chlorine content of o, o'-dibenzamide diphenyl disulfide manufactured by Tokyo Chemical Industry Co., Ltd., which is a commercially available o, o'-dibenzamide diphenyl disulfide, is 2300 ppm as described later.

The chlorine content in o, o'-dibenzamide diphenyl disulfide can be reduced to some extent by washing the product with water, but the epoxy resin composition having excellent electrical reliability of the present invention and heat-resistant decomposition property In order to obtain a cured product having excellent adhesiveness, a lower total chlorine content of o, o'-dibenzamide diphenyl disulfide is required, and the total chlorine content is from the viewpoint of obtaining excellent electrical reliability. It is required to be 1500 ppm or less. From the viewpoint of further enhancing electrical reliability, the total chlorine content of o, o'-dibenzamide diphenyl disulfide used in the present invention is preferably 1000 ppm or less, more preferably 50 ppm or less. There is no particular limitation on the lower limit of the total chlorine content of o, o'-dibenzamide diphenyl disulfide, and the lower it is, the more preferable it is from the viewpoint of electrical reliability and the like.
In the present invention, the "total chlorine amount" can be measured according to JIS K7243-3.

The method for obtaining o, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1500 ppm or less is not particularly limited, but when the o, o'-dibenzamide diphenyl disulfide is washed with water, an organic solvent is used. A method of extracting and removing chlorine in the aqueous layer by oil-water separation is preferable. At this time, the organic solvent used is not particularly limited, but an aromatic organic solvent such as toluene and a ketone solvent such as methyl ethyl ketone and cyclohexanone are preferable from the viewpoint of solubility. Only one kind of these organic solvents may be used, or two or more kinds thereof may be mixed and used.

The amount of the organic solvent used is not particularly limited, but is preferably 10 to 10000 parts by weight, more preferably 100 to 2000 parts by weight, based on 100 parts by weight of o, o'-dibenzamide diphenyl disulfide.

Specifically, as a water washing method using an organic solvent, a predetermined amount of an organic solvent is added to o, o'-dibenzamide diphenyl disulfide, the mixture is heated to about 40 to 100 ° C., and then water having the same temperature is added. In addition, there is a method of mixing, then allowing to stand to separate oil and water, removing the aqueous layer, and then distilling off the organic solvent from the oil layer. In this case, the amount of water used is preferably 100 to 50,000 parts by weight, particularly 600 to 12,000 parts by weight, based on 100 parts by weight of o, o'-dibenzamide diphenyl disulfide.

Further, such washing with an organic solvent and water may be repeated a plurality of times, or after washing with an organic solvent and water, washing with water may be performed a plurality of times. For example, an organic solvent and water are added to o, o'-dibenzamide diphenyl disulfide and mixed, and then oil-water separation is performed. After removing the water layer, water is further added to the oil layer and mixed, and oil-water separation and water layer removal are performed. After repeating the washing with water a plurality of times, the organic solvent may be distilled off from the oil layer.
In such a cleaning operation, the larger the amount of organic solvent and water used and the larger the number of washings, the more the total chlorine amount of the obtained o, o'-dibenzamide diphenyl disulfide can be reduced, and the total chlorine can be reduced. It is also possible to reduce the total chlorine content, which is the detection limit of analysis, to about 10 ppm or less.

As a water washing method that does not use an organic solvent, water can be poured over powdered o, o'-dibenzamide diphenyl disulfide to remove chlorine.

[Epoxy resin composition]
[O, o'-dibenzamide diphenyl disulfide]
The epoxy resin composition of the present invention contains o, o'-dibenzamide diphenyl disulfide, an epoxy resin and a curing agent having a total chlorine content of 1,500 ppm or less, and preferably further contains a curing accelerator, and is an epoxy resin. The content of o, o'-dibenzamide diphenyl disulfide is preferably 0.34 to 0.70% by weight based on 100% by weight of the total of the composition, the curing agent, the curing accelerator and the o, o'-dibenzamide diphenyl disulfide. is there. The content of the o, o'-dibenzamide diphenyl disulfide is more preferably 0.38 to 0.66% by weight, still more preferably 0.45, from the viewpoint of improving the adhesiveness while maintaining the thermostable decomposition property. ~ 0.59% by weight. When the content of o, o'-dibenzamide diphenyl disulfide is less than the lower limit of the above range, the adhesiveness is inferior, and when it exceeds the upper limit of the above range, the heat-decomposability and the adhesiveness are inferior.

Further, in the epoxy resin composition of the present invention, the weight ratio of o, o'-dibenzamide diphenyl disulfide / epoxy resin (weight percentage of o, o'-dibenzamide diphenyl disulfide to epoxy resin) in the composition is 0. It is preferably 54 to 1.10% by weight. From the viewpoint of improving the adhesiveness while maintaining the heat-decomposability, this weight ratio is more preferably 0.60 to 1.03% by weight, and further preferably 0.71 to 0.93% by weight. If this weight ratio is less than the lower limit of the above range, the adhesiveness is inferior, and if it exceeds the upper limit of the above range, the heat-resistant decomposition property and the adhesiveness are inferior.

[Epoxy resin]
The epoxy resin composition of the present invention contains an epoxy resin. The epoxy resin is not particularly limited, and any epoxy resin generally known as an epoxy resin can be used.

Examples of the epoxy resin that can be used include phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, including phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, and epoxy resin having a triphenylmethane skeleton. And / or naphthols such as α-naphthol, β-naphthol, dihydroxynaphthalene and compounds having aldehyde groups such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are condensed or co-condensed under an acidic catalyst. Epoxyized novolak resin obtained by the above process, diglycidyl ether such as bisphenol A, bisphenol F, bisphenol S, alkyl-substituted or unsubstituted biphenol, stillben-type epoxy resin, hydroquinone-type epoxy resin, phthalic acid, dimer acid, etc. Glycidyl ester type epoxy resin obtained by the reaction of polybasic acid and epichlorohydrin, glycidylamine type epoxy resin obtained by the reaction of polyamine such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin, and epoxy of cocondensation resin of dicyclopentadiene and phenols. Epoxy products, aralkyl type phenolic resins such as naphtholene ring-containing epoxy resin, xylylene skeleton, biphenylene skeleton-containing phenol aralkyl resin, naphthol aralkyl resin, trimethylolpropane type epoxy resin, terpen-modified epoxy resin, olefin bond Examples thereof include a linear aliphatic epoxy resin or an alicyclic epoxy resin obtained by oxidizing with a peracid such as acetic acid, and a sulfur atom-containing epoxy resin. These epoxy resins may be used alone or in combination of two or more.

Among them, biphenyl type epoxy resin, bisphenol F type epoxy resin, stillben type epoxy resin and sulfur atom-containing epoxy resin are preferable from the viewpoint of fluidity and reflow resistance, and novolak type epoxy resin is preferable from the viewpoint of curability. Dicyclopentadiene type epoxy resin is preferable from the viewpoint of low moisture absorption, naphthalene type epoxy resin and triphenylmethane type epoxy resin are preferable from the viewpoint of heat resistance and low warpage, and biphenylene type epoxy is preferable from the viewpoint of flame retardancy. Resins and naphthol aralkyl type epoxy resins are preferred.
Therefore, the epoxy resin composition of the present invention preferably contains at least one of these epoxy resins.

[Curing agent]
In the present invention, the curing agent refers to a substance that contributes to the cross-linking reaction and / or the chain length extension reaction between the epoxy groups of the epoxy resin. In the present invention, even if it is usually called a "curing accelerator", if it is a substance that contributes to the cross-linking reaction and / or the chain length extension reaction between the epoxy groups of the epoxy resin, it is regarded as a curing agent. To do.

In the epoxy resin composition of the present invention, the content of the curing agent is preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the total epoxy resin component as a solid content. Further, it is more preferably 500 parts by mass or less, and further preferably 300 parts by mass or less. In the present invention, the "solid content" means a component excluding the solvent, and includes not only a solid epoxy resin but also a semi-solid or a viscous liquid substance. Further, the "total epoxy resin component" corresponds to the total amount of epoxy resins contained in the epoxy resin composition of the present invention.

The curing agent is not particularly limited, and any curing agent generally known as an epoxy resin curing agent can be used. For example, phenol-based curing agents, aliphatic amines, polyether amines, alicyclic amines, amine-based curing agents such as aromatic amines, acid anhydride-based curing agents, amide-based curing agents, tertiary amines, imidazoles, etc. Can be mentioned.

Of these, the epoxy resin composition of the present invention can obtain excellent thermal decomposition resistance, adhesiveness, etc. by containing a phenol-based curing agent, and therefore, it is preferable to include a phenol-based curing agent as the curing agent. .. Further, from the viewpoint of heat resistance and the like, it is preferable to contain an acid anhydride-based curing agent and an amide-based curing agent. It is also preferable to use imidazoles from the viewpoint of sufficiently advancing the curing reaction and improving heat resistance.

One type of curing agent may be used alone, or two or more types may be used in combination. When two or more kinds of curing agents are used in combination, these may be mixed in advance to prepare a mixed curing agent before use, or when each component of the epoxy resin composition is mixed, each component of the curing agent is used. They may be added separately and mixed at the same time.

<Phenol-based curing agent>
Specific examples of the phenol-based curing agent include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcin, methylresolsin, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, and the like. Cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpenphenol resin, dicyclopentadienephenol resin, bisphenol A novolak resin, trisphenol methane type resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolac Polyvalent phenol resins such as resins, polyphenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glioxal, xylene resins and phenols. Polyhydric phenol resins, heavy oils or pitches, co-condensation resins of phenols and formaldehydes, phenol-benzaldehyde / xylylene dimethoxide polycondensate, phenol / benzaldehyde / xylylene range halide weight Examples thereof include various phenol resins such as condensates, phenol / benzaldehyde / 4,4'-dimethoxyside biphenyl polycondensate, and phenol / benzaldehyde / 4,4'-dihalide biphenyl polycondensate.

These phenolic curing agents may be used alone or in combination of two or more in any combination and blending ratio.

The blending 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, based on 100 parts by weight of the total epoxy resin component in the epoxy resin composition. Parts or less, particularly preferably 100 parts by weight or less.

<Amine-based curing agent>
Examples of amine-based curing agents (excluding tertiary amines) include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like.

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

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

Examples of alicyclic amines include isophorone diamine, metacene diamine, N-aminoethyl piperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, and 3,9-bis (3-amino). Examples thereof include propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and norbornene diamine.

Examples of aromatic amines include tetrachloro-p-xylene diamine, m-xylene diamine, p-xylene diamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisol, 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) Examples thereof include ethylamine, diaminodiethyldimethyldiphenylmethane, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene and the like.

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

The above amine-based curing agent may be used so that the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all the epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.

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

The tertiary amines mentioned above may be used alone or in combination of two or more in any combination and blending ratio.

The above tertiary amine may be used so 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 is in the range of 0.8 to 1.5. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.

<Acid anhydride-based curing agent>
Examples of the acid anhydride-based curing agent include acid anhydrides and modified products of acid anhydrides.
Examples of the acid anhydride include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, dodecenyl succinic acid anhydride, polyazipic acid anhydride, polyazereic acid anhydride, and polysebacic acid. Anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , Methylhymic acid anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimeritate dianhydride, het acid anhydride, nadic acid anhydride, Methylnadic acid anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride, 3,4-dicarboxy-1,2, Examples thereof include 3,4-tetrahydro-1-naphthalene succinate dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic hydride and the like.

Examples of the modified acid anhydride include those obtained by modifying the above-mentioned acid anhydride with glycol. Here, 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. Can be mentioned. Furthermore, copolymerized polyether glycols of two or more kinds of these glycols and / or polyether glycols can also be used.

The modified acid anhydride is preferably modified with 0.4 mol or less of glycol per 1 mol of the acid anhydride. When the amount of modification is not more than the above upper limit, the viscosity of the epoxy resin composition does not become too high, the workability tends to be good, and the speed of the curing reaction with the epoxy resin tends to be good. ..

The acid anhydride-based curing agent mentioned above may be used alone or in combination of two or more in any combination and blending amount.

When an acid anhydride-based curing agent is used, it should be used so that the equivalent ratio of the functional groups in the curing agent to the epoxy groups in all the epoxy resin components in the epoxy resin composition is in the range of 0.8 to 1.5. Is preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.

<Amide-based curing agent>
Examples of the amide-based curing agent include dicyandiamide and its derivatives, polyamide resins and the like.
The amide-based curing agent may be used alone or in combination of two or more in any combination and ratio.
When an amide-based curing agent is used, it is preferable to use the amide-based curing agent in an amount of 0.1 to 20% by weight based on the total of all the epoxy resin components in the epoxy resin composition and the amide-based curing agent.

<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 trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 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 Examples thereof include −dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and adducts of an epoxy resin and the above-mentioned imidazoles. Since imidazoles have catalytic ability, they can be generally classified as curing accelerators, but in the present invention, they are classified as curing agents.

The above-mentioned imidazoles may be used alone or in admixture of two or more in any combination and ratio.

When imidazoles are used, it is preferable to use imidazoles in an amount of 0.1 to 20% by weight based on the total of all the epoxy resin components in the epoxy resin composition and the imidazoles.

<Other hardeners>
In the epoxy resin composition of the present invention, other curing agents can be used in addition to the curing agent. The other curing agents that can be used in the epoxy resin composition of the present invention are not particularly limited, and all generally known curing agents for epoxy resins can be used.
These other curing agents may be used alone or in combination of two or more.

[Curing accelerator]
The epoxy resin composition of the present invention preferably contains a curing accelerator. By including the curing accelerator, the curing time can be shortened and the curing temperature can be lowered, so that a desired cured product can be easily obtained.
The curing accelerator is not particularly limited, and specific examples thereof include organic phosphines, phosphorus compounds such as phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, and boron halide amine complexes.

Examples of phosphorus-based compounds that can be used as a curing accelerator include triphenylphosphine, diphenyl (p-tryl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, and tris (tris). Dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkyl Organic phosphines such as arylphosphine and alkyldiarylphosphine, complexes of these organic phosphines with organic borons, these organic phosphines and maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 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 Examples thereof include quinone compounds such as, and compounds obtained by adding a compound such as diazophenylmethane.

Among the curing accelerators listed above, organic phosphines and phosphonium salts are preferable, and organic phosphines are most preferable.
Further, as the curing accelerator, only one of the above-mentioned ones may be used, or two or more kinds may be mixed and used in any combination and ratio.

The curing accelerator is preferably used in the range of 0.1% by weight or more and 20 parts by weight or less with respect to 100 parts by weight of all the epoxy resin components in the epoxy resin composition. It is more preferably 0.5 parts by weight or more, further preferably 1 part by weight or more, and more preferably 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 promoting effect can be obtained, while when it is at least the above upper limit value, desired cured physical properties can be easily obtained, which is preferable.

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

By using the inorganic filler, when the epoxy resin composition is used as the semiconductor encapsulant, the coefficient of thermal expansion of the semiconductor encapsulant can be brought close to that of the internal silicon chip or lead frame, and the semiconductor encapsulant can be used. Since the amount of moisture absorbed by the entire stopper can be reduced, the solder crack resistance can be improved.

The average particle size 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 size is equal to or more than the above lower limit, the melt viscosity does not become too high and the fluidity does not easily decrease. Therefore, when the average particle size is equal to or less than the above upper limit, a narrow gap in the mold is formed during molding. This is preferable because the filler is less likely to be clogged and the filling property of the material is easily improved.

When an inorganic filler is used in the epoxy resin composition 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.

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

The flame retardants used in the epoxy resin composition of the present invention include halogen-based flame retardants such as brominated epoxy resin and brominated phenol resin, antimony compounds such as antimon trioxide, red phosphorus, phosphate esters, phosphines and the like. Examples thereof include phosphorus-based flame retardants, nitrogen-based flame retardants such as melamine derivatives, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[Cured product]
By curing the epoxy resin composition of the present invention, the cured product of the present invention can be obtained. The cured product of the present invention obtained by curing the epoxy resin composition of the present invention has excellent properties in heat decomposition resistance and adhesiveness.

The method for curing the epoxy resin composition of the present invention is not particularly limited, but usually, a cured product can be obtained by a thermosetting reaction by heating. At the time of the thermosetting reaction, it is preferable to appropriately select the curing temperature depending on the type of the curing agent used. For example, when a phenolic curing agent is used, the curing temperature is usually 130 to 300 ° C. It is also possible to lower the curing temperature by adding a curing accelerator to these curing agents. The reaction time is preferably 1 to 20 hours, more preferably 2 to 18 hours, still more preferably 3 to 15 hours. When the reaction time is at least the above lower limit value, the curing reaction tends to proceed sufficiently, which is preferable. On the other hand, when the reaction time is not more than the above upper limit value, deterioration due to heating and energy loss during heating can be easily reduced, which is preferable.

The cured product using the epoxy resin composition of the present invention is excellent in thermostable decomposition property, and according to the epoxy resin composition of the present invention, it is preferably measured by the method described in the section of Examples described later. A cured product having a 5% weight loss temperature of 370 ° C. or higher can be provided. The higher the 5% weight loss temperature of the cured product, the less stress is applied at the interface due to the volatile components when used as a semiconductor encapsulant, and the less likely it is that defects such as peeling will occur, which is preferable.

Further, the cured product using the epoxy resin composition of the present invention has excellent adhesiveness, and according to the epoxy resin composition of the present invention, it is preferably measured by the method described in the section of Examples described later. It is possible to provide a cured product having a nickel adhesive strength of 12 MPa or more. The higher the nickel adhesive strength of the cured product, the less likely it is that defects such as peeling will occur when used as a semiconductor encapsulant, which is preferable.

[Use]
The cured product using the epoxy resin composition of the present invention is excellent in heat degradability and adhesiveness.
Therefore, the epoxy resin composition of the present invention and the cured product thereof can be effectively used in any application as long as these physical properties are required. For example, paint fields such as electrodeposition paints for automobiles, heavy-duty anticorrosion paints for ships and bridges, paints for inner surface coating of beverage cans; Fields: Suitable for all applications such as seismic reinforcement of bridges, concrete reinforcement, flooring of buildings, lining of water supply facilities, drainage / water permeable pavement, civil engineering / construction / adhesive field of vehicle / aircraft adhesives. be able to. Among these, it is particularly useful for electrical / electronic component applications such as semiconductor encapsulants and laminated plates.

The epoxy resin composition of the present invention may be used after being cured for the above-mentioned application, or may be cured or used in the manufacturing process of the above-mentioned application.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples as long as the gist thereof is not exceeded.

[Production of low chlorine o, o'-dibenzamide diphenyl disulfide and measurement of total chlorine content]
[Example 1]
50 g of o, o'-dibenzamide diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 g of toluene were placed in a 1 L separable flask and heated to 70 ° C. with stirring. Then, 300 g of water at 70 ° C. was added, the mixture was stirred for 10 minutes, allowed to stand, and separated into an oil layer and an aqueous layer. After discarding the aqueous layer, the oil layer was heated to 150 ° C. and reduced pressure with a vacuum pump to distill off toluene to obtain low chlorine o, o'-dibenzamide diphenyl disulfide.

[Example 2]
50 g of o, o'-dibenzamide diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 g of toluene were placed in a 1 L separable flask and heated to 70 ° C. with stirring. Then, 300 g of water at 70 ° C. was added, the mixture was stirred for 10 minutes, allowed to stand, and separated into an oil layer and an aqueous layer. After discarding the aqueous layer, 300 g of water at 70 ° C. was added, the mixture was stirred for 10 minutes, allowed to stand, separated into an oil layer and an aqueous layer, and the aqueous layer was discarded. Then, the oil layer was heated to 150 ° C. and reduced under reduced pressure with a vacuum pump to distill off toluene to obtain low chlorine o, o'-dibenzamide diphenyl disulfide.

[Example 3]
50 g of o, o'-dibenzamide diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 g of toluene were placed in a 5 L separable flask and heated to 70 ° C. with stirring. Then, 2000 g of water at 70 ° C. was added, the mixture was stirred for 10 minutes, allowed to stand, and separated into an oil layer and an aqueous layer. After discarding the aqueous layer, 2000 g of water at 70 ° C. was added, the mixture was stirred for 10 minutes, allowed to stand, separated into an oil layer and an aqueous layer, and the aqueous layer was discarded. Then, 2000 g of water at 70 ° C. was added again, the mixture was stirred for 10 minutes, allowed to stand, and separated into an oil layer and an aqueous layer. After discarding the aqueous layer, the oil layer was heated to 150 ° C. and reduced pressure with a vacuum pump to distill off toluene to obtain low chlorine o, o'-dibenzamide diphenyl disulfide.

[Comparative Example 1]
O, o'-dibenzamide diphenyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as o, o'-dibenzamide diphenyl disulfide of Comparative Example 1.

The total chlorine content of the low chlorine o, o'-dibenzamide diphenyl disulfide obtained in Examples 1 to 3 and the o, o'-dibenzamide diphenyl disulfide of Comparative Example 1 was measured according to JIS K7243-3, and the results were obtained. Is shown in Table 1.

[Manufacturing of epoxy resin composition and evaluation of cured product]
[Examples 4 to 10, Comparative Example 2]
Using the low chlorine o, o'-dibenzamide diphenyl disulfide produced in Example 1 having a total chlorine content of 1500 ppm, an epoxy resin composition was produced by uniformly blending with the formulation shown in Table 2. The following were used as the epoxy resin composition, the curing agent, and the curing accelerator.
Epoxy resin: "YX4000" manufactured by Mitsubishi Chemical Corporation (biphenyl type epoxy resin)
Hardener: "PSM4261" manufactured by Gun Ei Chemical Industry Co., Ltd. (phenol novolac hardener)
Curing accelerator: "Triphenylphosphine" manufactured by Tokyo Chemical Industry Co., Ltd.

The obtained epoxy resin composition was evaluated as follows, and the results are shown in Table 2.

(1) 5% weight reduction temperature Prepare two glass plates to which the release pet film is attached, adjust the distance between the two glass plates to 4 mm with the release pet film side inside, and place the mold. It was created. The epoxy resin composition was cast into this mold and heated at 120 ° C. for 2 hours and then at 175 ° C. for 6 hours to obtain a cured product.
The obtained cured product was cut out to obtain a sample weighing 10 mg.
This sample was subjected to thermal analysis using a thermal analyzer (TG / DTA: "EXSTAR7200" manufactured by Seiko Instruments Inc.) (heating rate: 10 ° C./min, measurement temperature range: 30 ° C. to 400 ° C., Air: Flow rate 200 mL / min). The temperature at the time when the weight of the cured product was reduced by 5% was measured and used as the 5% weight loss temperature.

(2) Nickel Adhesive Strength 70 epoxy resin compositions are applied to an area of 25 mm in length and 12.5 mm in width from the horizontal end of a nickel-plated plate (thickness 1.6 mm, length 25 mm, width 100 mm) manufactured by Yutaka Panel Service Co., Ltd. It was applied while heating at ° C. A nickel-plated plate on which nothing was applied was attached to the coated surface to prepare a test piece, and the shear adhesive strength was measured according to JIS K6850.

[Measurement example of the amount of chlorine in extracted water]
Epoxy resin (“YX4000” manufactured by Mitsubishi Chemical Corporation) and o, o'-dibenzamide diphenyl disulfide obtained in Examples 1 to 3 and Comparative Example 1 are uniformly blended by heating to 120 ° C. at the ratio shown in Table 3. Then, it was cooled to obtain a solid substance. The solid matter was crushed with a wonder blender (manufactured by Osaka Chemical Co., Ltd.), and the crushed solid matter was prepared through a 20-mesh wire mesh.
40 g of this solid matter was weighed in a polyethylene bottle, 80 mL of ultrapure water was added, the mixture was sealed, and the mixture was heated in a dryer at 70 ° C. After heating for 20 hours, the mixture was cooled to room temperature, and the contents were filtered through filter paper 5A to obtain extracted water.
1 g of the obtained extracted water was placed in a beaker, 100 mL of acetone and 25 mL of acetic acid were added, and the amount of chlorine was measured by a potential differential titration method using a silver nitrate solution having a concentration of 0.002 mol / L.
The results are shown in Table 3.

[Evaluation of results]
From the results in Table 1, the total chlorine content of o, o'-dibenzamide diphenyl disulfide of Examples 1 to 3 was significantly reduced as compared with the o, o'-dibenzamide diphenyl disulfide of Comparative Example 1. It can be seen that the electrical reliability is excellent.
Further, from the results in Table 2, the cured products of Examples 5 to 9 in which the composition of the epoxy resin composition is within the preferable range of the present invention have excellent thermal decomposition resistance and adhesive strength with respect to the cured product of Comparative Example 2. It turns out that it also has. Example 4 is an example in which the content of o, o'-dibenzamide diphenyl disulfide is less than the preferable range, and although the thermostable decomposition property is the same as that of Comparative Example 2, the adhesive strength is improved. In Example 10, the content of o, o'-dibenzamide diphenyl disulfide is larger than the preferable range, the heat-resistant decomposition property is slightly low, but the adhesiveness is higher than that of Comparative Example 2.
Further, from the results in Table 3, the epoxy resin composition using o, o'-dibenzamide diphenyl disulfide of Examples 1 to 3 has an epoxy resin composition using o, o'-dibenzamide diphenyl disulfide of Comparative Example 1. It can be seen that the amount of chlorine is small and the electrical reliability is excellent compared to the product.
No. in Table 3 Since the values of the amount of chlorine in the extracted water in Tables 1 to 4 correlate with the total amount of chlorine in o, o'-dibenzamide diphenyl disulfide of Examples 1 to 3 and Comparative Example 1 in Table 1, the amount of chlorine in the extracted water The value of is presumed to be the chlorine content derived from benzoyl chloride, which is the raw material of the o, o'-dibenzamide diphenyl disulfide used, and thus the o, o'-dibenzamide diphenyl disulfide.

Based on these results, by using o, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1500 ppm by weight or less, excellent thermal degradability and adhesiveness to the conventional epoxy resin composition and its cured product are obtained. It can be seen that it can have.

Claims (7)

An epoxy resin composition containing o, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1,500 ppm or less, an epoxy resin, and a curing agent. The epoxy resin composition according to claim 1, further comprising a curing accelerator. The concentration of the o, o'-dibenzamide diphenyl disulfide is 0.34 to 0.70 with respect to 100% by weight of the total of the epoxy resin, the curing agent, the curing accelerator, and the o, o'-dibenzamide diphenyl disulfide. The epoxy resin composition according to claim 2, which is% by weight. The epoxy resin composition according to any one of claims 1 to 3, wherein the weight ratio of the o, o'-dibenzamide diphenyl disulfide / the epoxy resin is 0.54 to 1.10% by weight. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4. An electrical / electronic component obtained by curing the epoxy resin composition according to any one of claims 1 to 4. O, o'-dibenzamide diphenyl disulfide having a total chlorine content of 1,500 ppm or less.