JP2005307032A - One-component epoxy resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-component epoxy resin composition which is excellent in flow property and shelf stability, especially when stored at room temperature, and yields a cured product excellent in flexibility, toughness, adhesion property and mechanical strengths, and the cured product obtained using the same. <P>SOLUTION: The one-component epoxy resin composition contains a liquid epoxy resin (X) and a hardener (Y), wherein the liquid epoxy resin (X) is obtained by converting modified polyphenols (A), obtained through acetalization of a polyphenol (a1) and polyvalent vinyl ethers (a2), into glycidyl ethers. The cured product is obtained by curing the same. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a one-component liquid epoxy resin composition that gives a cured product that is excellent in storage stability and fluidity, and is excellent in flexibility, adhesion, mechanical properties, and the like, and a cured product obtained by curing the same.

  Liquid epoxy resin is excellent in fluidity and is easy to handle and work when used in paints, adhesives, molding materials, etc. Also excellent. In general, epoxy resin compositions such as paints, adhesives, and liquid encapsulants are broadly divided into one-part type in which a curing agent is blended in advance and two-part type in which a curing agent is blended before use. Therefore, a one-pack type epoxy resin composition is desired because it does not take a long time and is easy to be mechanized (lined). However, in the conventional one-pack type epoxy resin composition, the epoxy resin and the curing agent react during storage, and the storage stability during storage is poor. In order to improve storage stability, a method of freezing and storing at 10 ° C. or lower, preferably −20 ° C. or lower has been conventionally employed. However, storage and distribution in a frozen state are problematic in terms of cost and complexity. In addition, since the stability after returning to room temperature before use is low, it is difficult to manage the pot life, and defects due to thickening of the composition often occur. Especially in flip chip underfill applications where the sealing material is filled by capillarity, the gap between the chip and the substrate is only a few tens of microns. It has been demanded. In order to improve these, the composition which paid attention to the latent hardening | curing agent is proposed (for example, refer patent document 1).

  However, in the recent electronics field and high-performance paint field, components such as semiconductors and printed wiring boards have been made finer for the purpose of downsizing and speeding up, and the sealing materials and adhesives used therefor are high. Flowability is required, and the cured product obtained is required to have excellent toughness, adhesion, and mechanical properties. The epoxy resin composition proposed in the above-mentioned patent document does not reach a practical level, and There is a need for improvements.

JP 2000-80153 A (pages 3 to 8)

  Accordingly, the object of the present invention is to provide a one-pack type epoxy resin which is excellent in fluidity and storage stability during storage, particularly at room temperature, and excellent in flexibility, toughness, adhesion and mechanical strength of the resulting cured product. It is providing the composition and the hardened | cured material obtained using it.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a liquid epoxy resin obtained by glycidyl etherification of a modified polyphenol obtained by acetalizing a polyhydric phenol and a polyvalent vinyl ether and curing. The present invention was completed by finding that a one-pack type epoxy resin composition containing an agent can solve the above-mentioned problems.

  That is, the present invention relates to a liquid epoxy resin (X) obtained by glycidyl etherification of a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2). The present invention provides a one-pack type epoxy resin composition characterized by containing a curing agent (Y) and a cured product obtained by curing the same.

  The one-pack type epoxy resin composition obtained by the present invention is a cured product having excellent fluidity and storage stability during storage, and excellent in flexibility, toughness, adhesiveness, mechanical strength, moisture resistance, dielectric properties, etc. Can be provided. Therefore, it is extremely useful as a high-quality paint, semiconductor encapsulant, printed wiring board, composite material, etc. that are excellent in workability, productivity, and cured material properties.

Hereinafter, the present invention will be described in detail.
The one-pack type epoxy resin composition of the present invention is obtained by glycidyl etherification of a modified polyphenol (A) obtained by acetalizing a polyhydric phenol (a1) and a polyvalent vinyl ether (a2). The liquid epoxy resin (X) and the curing agent (Y) are contained.

  In the liquid epoxy resin (X), an aromatic hydroxyl group in the polyhydric phenol (a1) and a vinyl ether group in the polyvalent vinyl ether (a2) are subjected to an addition reaction, and the polyhydric phenol is bonded by an acetal group. This is obtained by glycidyl etherification of the hydroxyl group in the modified polyphenols (A) obtained by extending the molecular chain with epihalohydrin.

  The acetalization reaction here refers to the chemical reaction formula (1)

で表される反応であり、芳香族性水酸基とビニルエーテル基が付加反応して生成するアセタール基を介して結合する化学反応を示す。

It shows a chemical reaction in which an aromatic hydroxyl group and a vinyl ether group are bonded via an acetal group generated by an addition reaction.

  The polyhydric phenols (a1) are not particularly limited as long as they are aromatic compounds containing more than one aromatic hydroxyl group in one molecule. For example, hydroquinone, resorcin, catechol, and substituents thereof. Dihydroxybenzenes such as inclusions; 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene Dihydroxynaphthalenes such as those containing substituents thereof; bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis ( 3-methyl-4-hydroxyphenyl) propane (bisphenol) C), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), bis (4-hydroxyphenyl) Bisphenols such as sulfone (bisphenol S) and their substituents; bisnaphthols such as bis (2-hydroxy-1-naphthyl) methane and bis (2-hydroxy-1-naphthyl) propane, phenol / formaldehyde heavy Condensate, orthocresol / formaldehyde polycondensate, 1-naphthol / formaldehyde polycondensate, 2-naphthol / formaldehyde polycondensate, phenol / acetaldehyde polycondensate, orthocresol / acetaldehyde polycondensate, 1-naphthol / acetaldehyde polycondensate Shrinkage Products, 2-naphthol / acetaldehyde polycondensate, phenol / salicylaldehyde polycondensate, orthocresol / salicylaldehyde polycondensate, 1-naphthol / salicylaldehyde polycondensate, 2-naphthol / salicylaldehyde polycondensate and the like Phenols (naphthols) / aldehydes polycondensates such as those containing substituents of: phenol / dicyclopentadiene polyadducts, phenol / tetrahydroindene polyadducts, phenol / 4-vinylcyclohexene polyadducts, phenol / 5-vinyl noborna-2-ene polyadduct, phenol / α-pinene polyadduct, phenol / β-pinene polyadduct, phenol / limonene polyadduct, orthocresol / dicyclopentadiene polyadduct, orthocresol / tetrahydro Inden polyaddition Orthocresol / 4-vinylcyclohexene polyadduct, orthocresol / 5-vinyl noborna-2-ene polyadduct, orthocresol / α-pinene polyadduct, 1-naphthol / dicyclopentadiene polyadduct, 1-naphthol / 4-vinylcyclohexene polyadduct, 1-naphthol / 5-vinylnorbornadiene polyadduct, 1-naphthol / α-pinene polyadduct, 1-naphthol / β-pinene polyadduct, 1-naphthol / limonene polyaddition , Orthocresol / β-pinene polyadduct, orthocresol / limonene polyadduct, etc., and phenols (naphthols) / diene polyadducts such as these substituents, phenol / p-xylene dichloride heavy Condensate, 1-naphthol / p-xylene dichloride polycondensate, 2-naphthol / p- Syrene dichloride polycondensate, phenol / bischloromethylbiphenyl polycondensate, orthocresol / bischloromethylbiphenyl polycondensate, 1-naphthol / bischloromethylbiphenyl polycondensate, 2-naphthol / bischloromethylbiphenyl polycondensate And polycondensates of these substituent-containing products such as phenols / aralkyl resins. Examples of substituents in these substituent-containing products include alkyl groups, aryl groups, cycloalkyl groups, alkoxy groups, alkoxycarbonyl groups, acyl groups, halogen atoms, etc., alone or in a mixture of two or more. Can also be used.

  Among these, dihydric phenols are preferable because a liquid low-viscosity epoxy resin can be obtained even if the vinyl ethers modification rate is increased. Among dihydric phenols, bisphenols such as bisphenol A and bisphenol F are preferable because of their excellent toughness and the like. From the viewpoint of strong fluidity, dihydroxybenzenes such as hydroquinone, resorcin, and catechol, 1,6 -Dihydroxynaphthalene such as dihydroxynaphthalene is particularly preferred.

  The polyvalent vinyl ethers (a2) are not particularly limited as long as they are compounds containing more than one vinyl ether group in one molecule. For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether , Tetraethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol glycol divinyl ether, polypropylene glycol glycol divinyl ether, polytetramethylene glycol divinyl ether Divinyl ethers containing a (poly) oxyalkylene group such as glycero Rudivinyl ether, triglycerol divinyl ether, 1,3-butylene glycol divinyl ether, 1,4-butanedidiol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10-decane Divinyl ethers having an alkylene group such as diol divinyl ether, neopentyl glycol divinyl ether, and hydroxypivalic acid neopentyl glycol divinyl ether; 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecane Diol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclopen Divinyl ethers containing a cycloalkane structure such as decanediol divinyl ether; bisphenol A divinyl ether, ethylene oxide modified bisphenol A divinyl ether, propylene oxide modified bisphenol A divinyl ether, bisphenol F divinyl ether, ethylene oxide modified bisphenol F divinyl ether, Divinyl ethers such as propylene oxide modified bisphenol F divinyl ether; trimethylol propane trivinyl ether, ethylene oxide modified trimethylol propane trivinyl ether, propylene oxide modified trimethylol propane trivinyl ether, trivalent vinyl ethers such as pentaerythritol trivinyl ether; Pentaerythritol Examples include tetravalent vinyl ethers such as travinyl ether, pentaerythritol ethoxytetravinyl ether, and ditrimethylolpropane tetravinyl ether; dipentaerythritol hexa (penta) vinyl ether polyvalent vinyl ethers, etc., either alone or as a mixture of two or more. it can.

  Among these, divinyl ethers are preferred because a low-viscosity liquid epoxy resin can be obtained even if the vinyl ethers modification rate is increased. Divinyl ethers may be selected appropriately in consideration of the desired properties of the resulting epoxy resin. Of these, divinyl ethers containing a polyoxyalkylene skeleton are preferred when a low-viscosity epoxy resin is desired and the flexibility, flexibility, toughness, adhesion, etc. of the cured product are desired. Since the hydrophilicity of the polyether skeleton is high, an aqueous or emulsion type epoxy resin composition can be easily prepared. If excellent moisture resistance and dielectric properties are desired, cycloalkane skeleton-containing divinyl ethers are preferred.

  The reaction method of the polyhydric phenols (a1) and the polyvalent vinyl ethers (a2) is not particularly limited as long as it conforms to the reaction conditions of an aromatic hydroxyl group and a vinyl ether group. For example, there is a method in which a polyhydric phenol (a1) and a polyvalent vinyl ether (a2) are charged and heated with stirring and mixing to obtain the target modified polyphenol (A). In this case, an organic solvent and a catalyst can be used as needed. The organic solvent that can be used is not particularly limited, but aromatic organic solvents such as benzene, toluene, xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, Examples thereof include alcohol-based organic solvents such as isopropyl alcohol and normal butanol, and may be appropriately selected in consideration of properties such as solubility of raw materials and products used, reaction conditions, economy, and the like. The amount of the organic solvent is preferably 5 to 500% by weight based on the weight of the raw material.

  Regarding the catalyst, the reaction proceeds normally even in a non-catalytic system, but depending on the type of raw material used, the desired properties of the resulting modified polyphenols (A), the desired reaction rate, etc. May be used. The type of the catalyst is not particularly limited as long as it is a catalyst usually used for the reaction of a hydroxyl group and a vinyl ether group. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, toluenesulfonic acid, Methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid and other organic acids, aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide Lewis acids such as boron trifluoride ether complex and boron trifluoride phenol complex can be used, and the addition amount can be in the range of 10 ppm to 1 wt% with respect to the total weight of the raw material. However, in the catalyst addition system, it is necessary to select the type, addition amount, and reaction conditions so as not to cause a vinyl group nucleus addition reaction to the aromatic ring.

  The reaction conditions between the aromatic hydroxyl group and the vinyl ether group are usually room temperature to 200 ° C., preferably 50 to 150 ° C., and may be heated and stirred for about 0.5 to 30 hours. In this case, in order to prevent the self-polymerization of vinyl ethers, the reaction in an oxygen-containing atmosphere is preferable. The progress of the reaction can be traced by measuring the residual amount of the raw material using gas chromatography, liquid chromatography or the like. When an organic solvent is used, it is removed by distillation or the like. When a catalyst is used, it is deactivated with a deactivator if necessary, and then removed by washing with water or filtering. However, in the case of an organic solvent or catalyst (including a deactivated catalyst residue) that does not adversely affect the epoxidation reaction in the next step, there is no need for purification.

  The reaction ratio between the polyhydric phenols (a1) and the polyvalent vinyl ethers (a2) in the above reaction is such that one or more aromatic hydroxyl groups remain in one molecule of the reaction product. Although not specifically limited, the types and combinations of the raw material polyhydric phenols (a1) and polyvalent vinyl ethers (a2), and the desired vinyl ether modification rate, molecular weight, hydroxyl group equivalent of the resulting modified polyphenols (A) It may be determined according to the physical property values such as the acetal conversion rate depending on the reaction conditions. For example, if the effects such as flexibility, moisture resistance, and dielectric properties due to vinyl ether modification are to be remarkably enhanced, the amount of polyvalent vinyl ethers (a2) may be increased. Specifically, with respect to the aromatic hydroxyl group of the polyhydric phenol (a1), the vinyl ether group of the polyvalent vinyl ether (a2) is [aromatic hydroxyl group of the polyhydric phenol] / [polyhydric vinyl ether]. Vinyl ether group] = 80/20 to 50/50 (molar ratio) is preferable. Further, in the case of reaction conditions such that the conversion rate of vinyl ether is low due to the influence of side reaction, the above ratio is [aromatic hydroxyl group of polyhydric phenol] / [vinyl ether group of polyvalent vinyl ether] = 50 / More than 50 (molar ratio), the vinyl ether group excess charge condition may be used. On the other hand, when it is desired to emphasize other physical property balances such as curability and heat resistance, the ratio is [aromatic hydroxyl group of polyhydric phenol] / [vinyl ether group of polyvalent vinyl ether] = 95 / 5-80 / A range of 20 (molar ratio) is preferred.

Next, the method for producing the liquid epoxy resin (X) used in the present invention will be described in detail. Although it does not specifically limit as this manufacturing method, For example, sodium hydroxide, potassium hydroxide is added to the melt | dissolution mixture of modified | denatured polyhydric phenols (A) obtained above, and epihalohydrins, such as epichlorohydrin and epibromohydrin. The method of making it react at 20-120 degreeC for 1 to 10 hours, adding alkali metal hydroxides, such as these, is mentioned. The added amount of epihalohydrin is usually in the range of 0.3 to 20 equivalents with respect to 1 equivalent of hydroxyl group in the raw material modified polyphenols (A). When the epihalohydrin is less than 2.5 equivalents, an epoxy group and an unreacted hydroxyl group are likely to react with each other. Therefore, a group formed by an addition reaction between an epoxy group and an unreacted hydroxyl group (—CH ₂ CR (OH) CH ₂ —, A high molecular weight product containing R: a hydrogen atom or an organic carbon group is obtained. On the other hand, in the case of 2.5 equivalents or more, the content of the low molecular weight epoxy resin having a structure in which the hydroxyl group of the raw material modified polyphenols (A) is substituted with a glycidyl group becomes high. The amount of epihalohydrin may be appropriately adjusted according to desired characteristics.

  As the alkali metal hydroxide, an aqueous solution thereof may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously added under reduced pressure or normal pressure. May be distilled off, and the liquid may be further separated to remove water and the epihalohydrin to be continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the modified polyphenol (A) and epihalohydrin at 50 to 150 ° C. for 1 to 5 hours. Add a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenols (A) obtained by the reaction, and react again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure). The method may be used.

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering epihalohydrin or the like is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali such as sodium hydroxide or potassium hydroxide is obtained. An aqueous solution of a metal hydroxide can be added and further reacted to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by weight with respect to the crude epoxy resin.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and the target liquid epoxy resin (X) can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  Of course, it is possible to use rational means such as preparing the modified polyhydric phenols (A) and charging raw materials such as epihalohydrins as they are without removing them from the reactor and continuously converting them to glycidyl ether.

  The liquid epoxy resin (X) used in the present invention has the following general formula (2)

｛式中、Ｘは２価の有機基を示し、両末端の酸素原子（＊）は芳香族環と直接結合している。｝
で表されるジアセタール構造を分子内に含有するエポキシ樹脂である。官能基濃度（エポキシ当量）や官能基数（１分子中のエポキシ基の平均個数）に関しては、特に限定されるものではないが、エポキシ当量に関しては、１５０〜２、０００ｇ／ｅｑ．の範囲であることが樹脂の粘度が低く、硬化性に優れ、靭性、柔軟性、耐湿性、誘電特性等のバランスに優れた硬化物が得られる点から好ましく、官能基濃度に関しては、１＜官能基数（個）≦２０の範囲が同様な特性バランスに優れることから好ましい。また前記液状エポキシ樹脂（Ｘ）の２５℃における粘度としては、液状の組成物を得るためには１，０００〜５０，０００ｍＰａ・ｓの範囲であるものが好ましい。

{In the formula, X represents a divalent organic group, and oxygen atoms (*) at both ends are directly bonded to an aromatic ring. }
It is an epoxy resin containing a diacetal structure represented by The functional group concentration (epoxy equivalent) and the number of functional groups (average number of epoxy groups in one molecule) are not particularly limited, but the epoxy equivalent is 150 to 2,000 g / eq. It is preferable from the point of obtaining a cured product having a low resin viscosity, excellent curability, and excellent balance of toughness, flexibility, moisture resistance, dielectric properties, etc. With regard to the functional group concentration, 1 < The range of the number of functional groups (pieces) ≦ 20 is preferable because the same characteristic balance is excellent. The viscosity of the liquid epoxy resin (X) at 25 ° C. is preferably in the range of 1,000 to 50,000 mPa · s in order to obtain a liquid composition.

  The one-pack type epoxy resin composition of the present invention can be used in combination with other epoxy resins in addition to the liquid epoxy resin (X) as long as the effects of the present invention are not impaired. When used in combination, the proportion of the liquid epoxy resin (X) in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. The epoxy resin that can be used in combination with the liquid epoxy resin (X) is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin Bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc., liquid epoxy resin, phenol novolac type epoxy Resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol Aralkyl epoxy resin, naphthol novolak epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin epoxy resin, Biphenyl modified novolac type epoxy resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolac type epoxy resin and the like can be mentioned. Also included are reactive diluent type epoxy resins such as butyl glycidyl ether, alkylphenol glycidyl ether, and aliphatic chain carboxylic acid glycidyl ester, and liquid epoxy resins such as alicyclic epoxy resins. Moreover, the said other epoxy resin may be used independently and may mix 2 or more types.

  When the one-part epoxy resin composition of the present invention, particularly a liquid composition, is desired, it is desirable to use a low-viscosity liquid epoxy resin, for example, bisphenol A type epoxy resin, bisphenol. F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, butyl glycidyl ether, alkylphenol glycidyl ether, fatty chain carboxylic A reactive diluent type epoxy resin such as acid glycidyl ester or a liquid epoxy resin such as alicyclic epoxy resin is preferred.

  Various curing agents (Y) can be used in the present invention, and are not particularly limited. However, aromatic polyamines and aromatic polyamides and N-alkylated products thereof, alicyclic polyamines and alicyclic polyamides are used. And N-alkylated compounds thereof, cyclic amines, nitrogen-containing heterocyclic compounds, amine compounds such as imidazoles, acid anhydride compounds, polyphenol compounds, and the like, and aromatic polyamines can be used. , N-alkylated products of aromatic polyamines, alicyclic polyamines, N-alkylated products of alicyclic polyamines, cyclic amines, nitrogen-containing heterocyclic compounds, imidazoles and acid anhydrides It is preferable that it is 1 or more types of compounds chosen from these.

  Examples of amine compounds include, for example, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, metaxylylenediamine, diaminodiphenylmethane, phenylenediamine, 1,3-bis (amino Methyl) cyclohexane, isophoronediamine, norbornanediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 2-ethyl-4- Dimer of methylimidazole, 2-methylimidazole, N, N-dimethyltrimethylenediamine and N, N, N ′, N′-tetramethyltrimethylenediamine, dicyandiamide, linolenic acid and ethylenedi Polyamide resin synthesized from min, Mannich type curing agent which is a polycondensation product of the above polyamines, phenols and formaldehyde, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. It is done.

  Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. And methyl hexahydrophthalic anhydride.

Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylol methane resins, tetraphenylol. Examples include ethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, aminotriazine-modified phenol resins, and modified products thereof. Examples of the latent catalyst include imidazole, BF ₃ -amine complex, and guanidine derivative.

  Further, these amine compounds, acid anhydride compounds, amide compounds, phenol compounds and the like curing agents may be used alone or in admixture of two or more.

  Among the various curing agents described above, an amine compound or an acid anhydride compound is preferable because an epoxy resin composition having excellent fluidity and adhesion can be obtained.

  In the one-pack type epoxy resin composition of the present invention, the amount of the curing agent (Y) used is that the curing proceeds smoothly and good cured properties are obtained, so that 1 equivalent of the epoxy group of the liquid epoxy resin (X) In contrast, the amount by which the active hydrogen group in the curing agent (Y) is 0.7 to 1.5 equivalents is preferable.

  Moreover, a hardening accelerator can also be suitably used for the one-component epoxy resin composition of the present invention. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. The above combination is also possible. For example, as a semiconductor encapsulating material application, triphenylphosphine for phosphorus and DBU for amine are preferable because cured products having excellent curability and excellent heat resistance, electrical characteristics, moisture resistance reliability, and the like can be obtained.

  An inorganic filler can be blended in the one-pack type epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by weight or more with respect to the total amount of the epoxy resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier, can be added to the one-component epoxy resin composition of the present invention as necessary.

  A flame retardant imparting agent may be added to the one-pack type epoxy resin composition of the present invention as necessary. Various flame retardants can be used, for example, halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A, phosphorus atom-containing compounds such as red phosphorus and various phosphoric acid ester compounds, melamine or derivatives thereof, etc. Examples thereof include inorganic flame retardant compounds such as nitrogen atom-containing compounds, aluminum hydroxide, magnesium hydroxide, zinc borate, and calcium borate.

  If necessary, an organic solvent can be used in the one-component epoxy resin composition of the present invention. The organic solvent is used to lower the viscosity and improve the fluidity and moldability, and the type is not particularly limited. Illustrative examples include methanol, toluene, xylene, diethyl ether, acetone, methyl ethyl ketone, dimethylformamide and the like. The amount used is preferably such that the solid content of the epoxy resin composition is in the range of 20 to 95% by weight.

  The one-pack type epoxy resin composition of the present invention comprises a liquid epoxy resin (X), a curing agent (Y), and, if necessary, other epoxy resins, curing accelerators and the like, according to the viscosity of the resulting composition. It can obtain by mixing uniformly using. The shape of the epoxy resin composition of the present invention is not limited at all. Even if the liquid epoxy resin (X) to be used is liquid, the epoxy resin to be used together, the curing agent (Y), the filler species and the use thereof Depending on the amount, the resulting epoxy resin composition may not become liquid at room temperature. What is necessary is just to select the shape of this composition suitably according to a use application, desired performance, etc.

  The use of the epoxy resin composition of the present invention is not particularly limited, and for example, for printed circuit boards, electronic component sealing materials, resist inks, conductive pastes, resin casting materials, adhesives, and insulation. Examples thereof include coating materials such as paints, and among these, it can be suitably used for resin compositions for printed circuit boards, resin compositions for encapsulants for electronic components, resist inks, and conductive pastes.

  As the printed circuit board, it can be suitably used particularly for prepregs, copper-clad laminates, and interlayer insulation materials for build-up printed circuit boards.

  In order to make the epoxy resin composition of the present invention into a resin composition for a prepreg for a printed circuit board, it can be used without a solvent depending on the viscosity of the resin composition, but for prepreg by varnishing with an organic solvent. A resin composition is preferred. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, non-alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethylformamide. Examples thereof include solvents having a boiling point of 160 ° C. or lower, such as a polar solvent, and can be appropriately used as a mixed solvent of two or more. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.

  In order to obtain a resin composition for a copper-clad laminate from the epoxy resin composition of the present invention, it is the same as the method for preparing the resin composition for prepreg, and the obtained prepreg is disclosed in, for example, JP-A-7-41543. A copper-clad laminate can be obtained by laminating as described, stacking copper foils as appropriate, and thermocompression bonding at 170-250 ° C. for 10 minutes to 3 hours under a pressure of 1-10 MPa.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  As the electronic component sealing material, it can be suitably used for a semiconductor chip sealing material, underfill, and semiconductor interlayer insulating film.

  In order to adjust the epoxy resin composition of the present invention for a semiconductor encapsulating material, epoxy resin (X), curing agent (Y), other epoxy resins blended as necessary, coupling agent, mold release Examples thereof include a method in which an additive such as an agent or an inorganic filler is premixed and then sufficiently mixed until uniform using an extruder, a kneader, a roll or the like. In the case of a melt mixed type (solvent-free) composition, the composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours. Thus, a cured product can be obtained, and semiconductor package molding corresponds to this.

  Moreover, when using as a tape-shaped sealing agent, after heating the resin composition obtained by the above-mentioned method and producing a semi-hardened sheet and using it as a sealing agent tape, this sealing agent tape is used as a semiconductor chip. Examples of the method include placing it on top, heating to 100 to 150 ° C, softening and molding, and completely curing at 170 to 250 ° C.

  Furthermore, when using as a potting type liquid sealing agent, the resin composition obtained by the above-mentioned method may be applied on a semiconductor chip or an electronic component and directly cured.

  The method of using the epoxy resin composition of the present invention as an underfill resin is not particularly limited. However, Japanese Patent Application Laid-Open No. 9-266221 and “Plastics in the Electronics Field” (published by Industrial Research Council, 1999, pages 27 to 34). Can be used. More specifically, the epoxy resin composition of the present invention is injected into the gap between the semiconductor element with electrodes and the printed wiring board with solder during flip-chip mounting by a capillary flow method using a capillary phenomenon and cured. And a compression flow method in which the epoxy resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance, and then the semiconductor element and the substrate are brought into close contact with each other to be completely cured. In this case, the epoxy resin composition of the present invention is preferably used in the form of a liquid epoxy resin composition containing no organic solvent. In particular, when the capillary flow method is used, the viscosity needs to be low, and the viscosity is preferably 5000 mPa · s or less. If the said resin composition is a viscosity exceeding this, it can also inject | pour after heating to room temperature-100 degrees C or less.

  When the epoxy resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, the method described in JP-A-6-85091 can be employed. When used as an interlayer insulating film, it will be in direct contact with the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment. The In addition, in order to cope with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for a technology for reducing the capacity of insulating materials. be able to. The resin composition is preferable because it has characteristics satisfying these requirements.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  When the epoxy resin composition of the present invention is used as a resin composition for coatings, for example, a pigment, a colorant, an additive, etc. are added to the epoxy resin (X) and other epoxy resins used in combination as necessary. If necessary, add an organic solvent, mix thoroughly using a device such as a paint shaker, mixing mixer, ball mill, etc., and disperse uniformly, and further add a curing agent (Y), a curing accelerator, etc. And preparing a desired viscosity with an organic solvent or the like.

  The resin composition prepared for the paint obtained by the above technique can be applied to various substrates by various coating methods, and the technique is not particularly limited. For example, a gravure coater, a knife Examples of the coating method include a coater, a roll coater, a comma coater, a spin coater, a bar coater, brush coating, dipping coating, spray coating, and electrostatic coating.

  Further, the curing method after coating the resin composition prepared for the paint is not particularly limited, and a cured coating film can be obtained by any of room temperature curing and heat curing.

  When the epoxy resin composition of the present invention is used as a resin composition for an adhesive, for example, epoxy resin (X), curing agent (Y), other epoxy resins used in combination as necessary, curing accelerator It can be obtained by mixing the additives, etc., uniformly at room temperature or under heating using a mixing mixer, etc., and after applying to various base materials, the base material can be adhered by leaving it at room temperature or under heating. It can be carried out.

  In order to obtain a composite material from the epoxy resin composition of the present invention, the epoxy resin composition of the present invention can be used in a solvent-free system depending on the viscosity, but it is difficult to handle in a solvent-free system. Varnished with an organic solvent, impregnating the varnish into a reinforcing base material, heating to obtain a prepreg, and then changing the fiber direction little by little to make it pseudo-isotropic The method of carrying out hardening shaping | molding by laminating | stacking and heating after that is mentioned. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and the like. Non-alcoholic polar solvents and the like have a boiling point of 160 ° C. or lower, and can be used as a mixed solvent of two or more as appropriate. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing substrate is not particularly limited, and examples thereof include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 60% by weight.

  The cured product of the present invention can be obtained by molding and curing the one-pack type epoxy resin composition of the present invention, and has forms such as a molded product, a laminate, a cast product, an adhesive, a coating film, and a film. For example, in the case of a melt-mixed type composition, the composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 80 to 200 ° C. for 2 to 10 hours. A cured product can be obtained, and semiconductor package molding corresponds to this. In the case of a varnish-like composition, a coating film can be obtained by coating it on a substrate and drying it by heating, and the paint corresponds to this. In addition, it can be obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating to obtain a prepreg, which can be obtained by hot press molding. This applies to the laminated material for CFRP and CFRP.

  Next, the present invention will be specifically described with reference to examples and comparative examples. The parts and% described below are based on weight unless otherwise specified.

  Synthesis Example 1 Synthesis of liquid epoxy resin (X-1) represented by the following structural formula (3)

温度計、撹拌機を取り付けたフラスコにビスフェノールＡ２２８ｇ（１．００モル）とトリエチレングリコールジビニルエーテル（ＩＳＰ社製：商品名Ｒａｐｉ−Ｃｕｒｅ ＤＶＥ−３）１７２ｇ（０．８５モル）を仕込み、１２０℃まで１時間要して昇温した後に、さらに１２０℃で６時間反応させて、透明半固形の原料樹脂（変性多価フェノール類）４００ｇを得た。これの水酸基当量は３６４ｇ／ｅｑ．であった。次いで、上記で得られた原料樹脂４００ｇ、エピクロルヒドリン９２５ｇ（１０モル）、ｎ−ブタノール１８５ｇを仕込み溶解させた。その後、窒素ガスパージを施しながら、６５℃に昇温した後に、共沸する圧力までに減圧して、４９％水酸化ナトリウム水溶液１２２ｇ（１．５モル）を５時間かけて滴下した、次いでこの条件下で０．５時間撹拌を続けた。この間、共沸で留出してきた留出分をディーンスタークトラップで分離して、水層を除去し、有機層を反応系内に戻しながら反応した。その後、未反応のエピクロルヒドリンを減圧蒸留して留去させた。それで得られた粗エポキシ樹脂にメチルイソブチルケトン１０００ｇとｎ−ブタノール１００ｇを加え溶解した。更にこの溶液に１０％水酸化ナトリウム水溶液２０ｇを添加して８０℃で２時間反応させた後に洗浄液のＰＨが中性となるまで水３００ｇで水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去して、液状エポキシ樹脂（Ｘ−１）を得た。これのエポキシ当量は４６２ｇ／ｅｑ．、粘度は１２，０００ｍＰａ・ｓ（２５℃、キャノンフェンスケ法）、エポキシ当量から算出される上記構造式中のｎの平均値は１．３５であることが確認された。

A flask equipped with a thermometer and a stirrer was charged with 228 g (1.00 mol) of bisphenol A and 172 g (0.85 mol) of triethylene glycol divinyl ether (manufactured by ISP: trade name Rapi-Cure DVE-3) at 120 ° C. It took 1 hour until the temperature was raised, and further reacted at 120 ° C. for 6 hours to obtain 400 g of a transparent semi-solid raw material resin (modified polyhydric phenols). Its hydroxyl equivalent is 364 g / eq. Met. Next, 400 g of the raw material resin obtained above, 925 g (10 mol) of epichlorohydrin, and 185 g of n-butanol were charged and dissolved. Then, after raising the temperature to 65 ° C. while purging with nitrogen gas, the pressure was reduced to the azeotropic pressure, and 122 g (1.5 mol) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was continued under 0.5 hours. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the organic layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 1000 g of methyl isobutyl ketone and 100 g of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 20 g of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 300 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain a liquid epoxy resin (X-1). Its epoxy equivalent weight is 462 g / eq. The viscosity was 12,000 mPa · s (25 ° C., Canon Fenske method), and the average value of n in the above structural formula calculated from the epoxy equivalent was 1.35.

Synthesis Example 2 Synthesis of Liquid Epoxy Resin (X-2) In Synthesis Example 1, a raw material resin was obtained in the same manner as in Synthesis Example 1 except that the amount of triethylene glycol divinyl ether (DVE-3) was changed to 192 g. . The raw material resin has a hydroxyl group equivalent of 423 g / eq. Met. Next, 688 g of a liquid epoxy resin (X-2) was obtained in the same manner as in Synthesis Example 1 except that 615 g of this raw material resin was used. Moreover, the epoxy equivalent of this is 526 g / eq. The viscosity was 4,700 mPa · s (25 ° C., Canon Fenske method), and the average value of n in the above structural formula calculated from the epoxy equivalent was 1.65.

Examples 1-2 and Comparative Example 1
The two types of liquid epoxy resins (X-1) and (X-2) synthesized as described above were compared and evaluated with general epoxy resins. The epoxy resin used for the comparison is a bisphenol A type liquid epoxy resin (Dainippon Ink & Chemicals, Inc .: trade name EPICLON 850S, epoxy equivalent 188 g / eq., Viscosity 15,000 mPa · s). These epoxy resins, a commercially available modified imidazole compound (manufactured by Ajinomoto Fine Techno Co., Ltd .: Amicure PN-23) as a curing agent, and Aerosil # 200 (manufactured by Nippon Aerosil Co., Ltd.) as an additive according to the blending ratios shown in Table 1. The mixture was mixed to obtain a one-pack type epoxy resin composition. Table 1 shows the results of evaluating the storage stability of this composition and the basic physical properties of a cured product test piece obtained by curing it at 100 ° C. for 1 hour.

Footnotes in Table 1:
* 1 Storage stability evaluation method: The formulation was stored at 40 ° C., and the number of days for thickening to 2 times the initial viscosity was evaluated.
* 2 Hardened product flexibility: Disk-shaped test pieces having a diameter of 5 cm and a thickness of 3 mm were prepared, and those that could be bent 180 ° were evaluated as “◯” and those that could not be bent were evaluated as “X”.
* 3 Hardened material toughness: The specimens of * 2 which were bent by 180 ° and were not broken were evaluated as ◯, and the specimens which were broken were evaluated as ×.
* 4 Hardened product adhesive strength: Evaluated by a tensile shear test using an aluminum plate according to JIS K-6850 as a base material.

Claims (13)

It is a one-pack type epoxy resin composition containing a liquid epoxy resin (X) and a curing agent (Y), and the liquid epoxy resin (X) acetalizes polyhydric phenol (a1) and polyhydric vinyl ethers (a2). A one-pack type epoxy resin composition, which is a liquid epoxy resin obtained by glycidyl etherification of a modified polyphenol (A) obtained by reaction. The one-pack type epoxy resin composition according to claim 1, wherein the polyhydric phenols (a1) are dihydric phenols and the polyhydric vinyl ethers (a2) are divinyl ethers. The aromatic hydroxyl group in the polyhydric phenol (a1) and the vinyl ether group in the polyvalent vinyl ether (a2) are [aromatic hydroxyl group of the polyhydric phenol] / [vinyl ether group of the polyvalent vinyl ether] = 80. The one-pack type epoxy resin composition according to claim 2, which is / 20 to 50/50 (molar ratio). The one-pack type epoxy resin composition according to claim 2, wherein the polyvalent vinyl ether (a2) contains a polyalkylene glycol skeleton and / or a cycloalkane skeleton. The epoxy equivalent of liquid epoxy resin (X) is 200-2,000 g / eq. The one-pack type epoxy resin composition according to claim 2. The one-pack type epoxy resin composition according to claim 5, wherein the viscosity of the liquid epoxy resin (X) at 25 ° C is 1,000 to 50,000 mPa · s. Curing agent (Y) is aromatic polyamines, N-alkylated products of aromatic polyamines, alicyclic polyamines, N-alkylated products of alicyclic polyamines, cyclic amines, nitrogen-containing heterocyclic compounds, The one-pack type epoxy resin composition according to claim 1, which is one or more compounds selected from the group consisting of imidazoles and acid anhydrides. The one-component epoxy resin composition according to any one of claims 1 to 7, which is a resin composition for printed circuit boards. The one-component epoxy resin composition according to any one of claims 1 to 7, which is a resin composition for a sealing material for electronic parts. The one-component epoxy resin composition according to any one of claims 1 to 7, which is used for resist ink. The one-pack type epoxy resin composition according to any one of claims 1 to 7, which is for a conductive paste. The one-component epoxy resin composition according to any one of claims 1 to 7, which is used for an interlayer insulating material. A cured product obtained by curing the one-component epoxy resin composition according to claim 1.