JP4636307B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention provides an epoxy resin composition that has a good flexibility, toughness, moisture resistance reliability, and high temperature storage reliability, and can be suitably used for coating materials, electronic materials, automotive materials, structural materials, and the like. It relates to a cured product obtained by curing this.

  Epoxy resins are cured with various curing agents, and generally have low shrinkage (dimensional stability) when cured, resulting in a cured product with excellent electrical insulation and chemical resistance. It has the essential problem of being inferior. Due to recent technological innovations in the fields of electronics, high-performance paints, automobiles, etc., the demand for solving these problems is increasing. As means for solving these problems, for example, (1) an aliphatic dicarboxylic acid such as dimer acid or sebacic acid is reacted with a low molecular weight epoxy resin (liquid bisphenol A type epoxy resin or the like) as a molecular chain extender. And a method of obtaining a high molecular weight epoxy resin having flexibility (see, for example, Patent Document 1). (2) A method of obtaining an epoxy resin by adding alkylene oxide to a low molecular weight phenol resin (such as bisphenol A) and epoxidizing the generated alcoholic hydroxyl group has been proposed.

  However, in the above-mentioned method (1), the cured product obtained cannot exhibit satisfactory flexibility due to the action of strong intermolecular cohesive force (hydrogen bonding) due to the ester group and the generated hydroxyl group at the joint. Furthermore, since ester groups are easily hydrolyzable, the moisture resistance reliability of the cured product is poor. In addition, in the method (2), a cured product having good flexibility can be obtained, but it cannot easily have toughness and is easily cracked. Furthermore, the cured product is thermally weak and lacks reliability at high temperature. Therefore, in the prior art, there has been no excellent epoxy resin composition having both flexibility and toughness, moisture resistance reliability, and high temperature storage reliability.

  In general, various compounds having a functional group capable of reacting with an epoxy group such as amines, phenols, and acid anhydrides are known as curing agents for epoxy resins. Among these, amine-based compounds have good curability, and it is possible to obtain a cured product without using a curing accelerator, and it is easy to prepare a resin composition, so that it is suitable for industrial production. There is a need for such convenience at the same time.

JP-A-8-53533 (pages 2-4)

  Therefore, the problem of the present invention is that it can be cured without using a curing accelerator, and the resulting cured product is excellent in flexibility and toughness, and has good moisture resistance reliability and high temperature storage reliability. The object is to provide an epoxy resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an epoxy resin and a Mannich type curing agent obtained by converting a modified polyphenols obtained by reacting polyhydric phenols with polyvalent vinyl ethers to glycidyl ether. The present invention has been completed by finding that an epoxy resin composition containing can solve the above-mentioned problems.

  That is, the present invention relates to an epoxy resin (X) obtained by glycidyl etherification of a modified polyhydric phenol (A) obtained by reacting a polyhydric phenol (a1) with a polyvalent vinyl ether (a2) and a Mannich type. An epoxy resin composition containing a curing agent (Y) and a cured product obtained by curing the epoxy resin composition are provided.

  The epoxy resin composition of the present invention can be cured without using a curing accelerator, and gives a cured product that is excellent in flexibility and toughness, and is excellent in moisture resistance reliability and high temperature storage reliability. Because of these physical properties, it can satisfy strict demands from the recent paint materials, electronic materials, automotive materials, structural materials fields, and high-quality paints, semiconductor encapsulants, printed wiring boards, automotive materials, composite materials. And so on.

Hereinafter, the present invention will be described in detail.
The epoxy tree composition of the present invention is an epoxy resin (X) obtained by glycidyl etherification of a modified polyhydric phenol (A) obtained by reacting a polyhydric phenol (a1) with a polyvalent vinyl ether (a2). And a Mannich type curing agent (Y).

  In the 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 chain extended by an acetal group. The resulting modified polyhydric phenols (A) have a chemical structure obtained by converting the hydroxyl group into glycidyl ether with epihalohydrin.

  The reaction between the hydroxyl group and the vinyl ether group is represented by the following chemical reaction formula:

で表され、アセタール基を生成する。

And produces an acetal group.

  The polyhydric phenol (a1) is not particularly limited as long as it is an aromatic compound containing more than one aromatic hydroxyl group in one molecule. For example, hydroquinone, resorcin, catechol, and substitution thereof Dihydroxybenzenes such as group-containing compounds; 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxy Dihydroxynaphthalenes such as naphthalene and substituents thereof; bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (3-Methyl-4-hydroxyphenyl) propane (bisph Nord C), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), bis (4-hydroxyphenyl) sulfone Bisphenols such as (bisphenol S) and these substituent-containing compounds; bisnaphthols such as bis (2-hydroxy-1-naphthyl) methane and bis (2-hydroxy-1-naphthyl) propane; phenol / formaldehyde polycondensation , Orthocresol / formaldehyde polycondensate, 1-naphthol / formaldehyde polycondensate, 2-naphthol / formaldehyde polycondensate, phenol / acetaldehyde polycondensate, orthocresol / acetaldehyde polycondensate, 1-naphthol / acetaldehyde polycondensate Compound, 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 these substituent-containing products; phenol / dicyclopentadiene polyadducts, phenol / tetrahydroindene polyadducts, phenol / 4-vinylcyclohexene polyadducts, phenols / 5-vinyl noborna-2-ene polyadduct, phenol / α-pinene polyadduct, phenol / β-pinene polyadduct, phenol / limonene polyadduct, orthocresol / dicyclopentadiene polyadduct, orthocresol / Tetrahydroindene weight , Orthocresol / 4-vinylcyclohexene polyadduct, orthocresol / 5-vinylnoborn-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 heavy adduct Phenols (naphthols) / dienes polyadducts such as adducts, orthocresol / β-pinene polyadducts, orthocresol / limonene polyadducts, etc., and substituents thereof; phenol / p-xylene dichloride Polycondensate, 1-naphthol / p-xylene dichloride polycondensate, 2-naphthol / p Xylene 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, and halogen atoms.

  Among these polyhydric phenols, dihydric phenols are preferred because a liquid low-viscosity epoxy resin can be obtained even if the vinyl ether modification rate is increased. Among dihydric phenols, bisphenols such as bisphenol A and bisphenol F are preferred because a cured product having excellent toughness and high temperature storage reliability can be obtained, and hydroquinone is considered in view of the fluidity of the resulting epoxy resin composition. Particularly preferred are dihydroxybenzenes such as resorcin and catechol, and dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene.

  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 diester Vinyl ether, Tetraethylene glycol divinyl ether, Polyethylene glycol divinyl ether, Propylene glycol divinyl ether, Dipropylene glycol divinyl ether, Tripropylene glycol divinyl ether, Tetrapropylene glycol divinyl ether, Polypropylene glycol divinyl ether, Polytetramethylene glycol di Divinyl ethers containing (poly) oxyalkylene groups such as vinyl ether; Divinyl 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- Divinyl ethers having an alkylene group such as decanediol divinyl ether, neopentyl glycol divinyl ether, and hydroxypivalate neopentyl glycol divinyl ether; 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclo Decanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclope Divinyl ethers containing a cycloalkane structure such as tadecanediol 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; trivalent vinyl ethers such as trimethylolpropane trivinyl ether, ethylene oxide modified trimethylolpropane trivinyl ether, propylene oxide modified trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether ; Pentaerythritol Examples thereof include tetravalent vinyl ethers such as tetravinyl ether, pentaerythritol ethoxytetravinyl ether and ditrimethylolpropane tetravinyl ether; and polyvalent vinyl ethers such as dipentaerythritol hexa (penta) vinyl ether.

  Among the polyvalent vinyl ethers, divinyl ethers are preferable because a low-viscosity liquid epoxy resin can be obtained even when the vinyl ether modification rate is increased. As the divinyl ethers, an appropriate one may be selected in consideration of the desired properties of the resulting epoxy resin. If low viscosity, flexibility, toughness, etc. are desired, it contains a polyoxyalkylene skeleton. Divinyl ethers are preferred. Also, divinyl ethers containing a cycloalkane skeleton are preferred if excellent moisture resistance reliability and high temperature storage reliability are desired.

  The modified polyphenols (A) can be obtained by subjecting the polyhydric phenol (a1) and the polyvalent vinyl ethers (a2) to an acetalization reaction.

  The acetalization reaction method 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, the polyhydric phenols (a1) and the polyvalent vinyl ethers ( and a method of heating while stirring and mixing. 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, for example, aromatic organic solvents such as benzene, toluene, xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Examples thereof include alcohol organic solvents such as ethanol, 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, and economics. The amount of the organic solvent used is preferably in the range of 5 to 500% by weight with respect to the raw material weight.

  The reaction usually proceeds sufficiently even without a catalyst, but depending on the type of raw material used, the desired properties of the resulting modified polyphenols (A), the desired reaction rate, etc., a catalyst may be used. Also good. The type of the catalyst is not particularly limited as long as it is usually a catalyst used for the reaction between a hydroxyl group and a vinyl ether group. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and 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, bromide Examples include Lewis acids such as gallium, boron trifluoride ether complex, and boron trifluoride phenol complex. The addition amount can be in the range of 10 ppm to 1% by weight 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. At this time, in order to prevent the self-polymerization of vinyl ethers, it is preferable to react in an oxygen-containing atmosphere. 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. Further, when an organic solvent is used, it can be removed by distillation or the like, and when a catalyst is used, it can be deactivated with a deactivator or the like, if necessary, and 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 not particularly limited as long as at least one aromatic hydroxyl group remains in one molecule of the reaction product. Without limitation, types and combinations of raw material polyhydric phenols (a1) and polyvalent vinyl ethers (a2), desired vinyl ether modification rate of the obtained modified polyhydric phenols (A), molecular weight, hydroxyl group equivalent, etc. It may be determined in accordance with the physical property value of and the acetal conversion rate depending on the reaction conditions. For example, when the effects such as flexibility, toughness, and moisture resistance reliability due to vinyl ether modification are to be remarkably enhanced, the amount of the polyvalent vinyl ethers (a2) may be increased. Specifically, the vinyl ether group in the polyvalent vinyl ether (a2) is [the aromatic hydroxyl group in the polyvalent phenol (a1)] / the aromatic hydroxyl group in the polyhydric phenol (a1) / [Vinyl ether group in the polyvalent vinyl ether (a2)] = 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 ratio [aromatic hydroxyl group in polyhydric phenol (a1)] / [polyhydric vinyl ether (a2) Of vinyl ether groups] = 50/50 (molar ratio), and the vinyl ether group excess charge condition may be used. On the other hand, when it is important to balance other physical properties such as curability and heat resistance, the aforementioned ratio [aromatic hydroxyl group in polyhydric phenols (a1)] / [vinyl ether group in polyhydric vinyl ethers (a2)] A range of = 95/5 to 80/20 (molar ratio) is preferable.

Next, the method for producing the epoxy resin (X) used in the present invention will be described in detail. The production method is not particularly limited. For example, sodium hydroxide or potassium hydroxide is added to a dissolved mixture of the modified polyhydric phenol (A) obtained above and epihalohydrin such as epichlorohydrin or 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. As the addition amount of the epihalohydrin, a range of 0.3 to 20 equivalents is usually used with respect to 1 equivalent of the hydroxyl group in the raw material modified polyphenol (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 in the raw material modified polyphenol (A) is substituted with a glycidyl group is increased. What is necessary is just to adjust the quantity of epihalohydrin suitably according to desired characteristics (viscosity, epoxy equivalent, etc. of an epoxy resin).

  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. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol obtained by the reaction and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) 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 the alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, with respect to 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 based on the crude epoxy resin.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the target epoxy resin (X) is 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 epoxy resin (X) obtained above has the following general formula (1)

（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。該エポキシ樹脂（Ｘ）の官能基濃度（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）に関しても、特に限定されるものではないが、なかでもエポキシ当量に関しては、２００〜２，０００ｇ／ｅｑ．の範囲が粘度、硬化性、靭性、柔軟性、耐湿信頼性、高温放置信頼性等のバランスに優れることから好ましく、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。

(In the formula, X represents a divalent organic group, and the oxygen atoms (*) at both ends are directly bonded to the 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) of the epoxy resin (X) are not particularly limited, but the epoxy equivalent is 200-2. , 000 g / eq. Is preferable because it has a good balance of viscosity, curability, toughness, flexibility, moisture resistance reliability, high temperature storage reliability, etc. Regarding the functional group concentration, the range of 1 <number of functional groups (pieces) ≦ 20 is the same. It is preferable because of its excellent property balance.

  In addition, the viscosity of the epoxy resin (X) at 25 ° C. is preferably in the range of 5,000 to 100,000 mPa · s from the viewpoint of fluidity, workability, freedom of composition blending, and the like.

  In the epoxy resin composition of the present invention, other epoxy resins other than the epoxy resin (X) can be used in combination as long as the effects of the present invention are not impaired. When used together, the proportion of the 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 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, phenolic Rukyle type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type 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.

  The Mannich type curing agent (Y) used in the present invention is not particularly limited as long as it is a compound obtained by reacting a polyamine compound (b1), formaldehydes (b2), and a phenol compound (b3). The Mannich type curing agent generally has good curability among amine curing agents and has an aromatic ring derived from the phenol compound (b3) in the molecule, so that the water resistance and mechanical properties of the resulting cured product are improved. When used in combination with the above-described epoxy resin (X), the curing reaction proceeds promptly without using a curing accelerator, and the moisture resistance reliability and high temperature storage reliability are excellent. It can give a cured product.

  The polyamine compound (b1) may be a compound having two or more primary or secondary amino groups in the molecule, and examples thereof include alkylene diamines such as ethylene diamine and hexamethylene diamine; diethylene triamine, triethylene tetramine, tetra Polyalkylene polyamines such as ethylenepentamine; alicyclic polyamines such as 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, isophoronediamine, 1,4-bis (3-aminopropyl) piperazine A polyamine having an aromatic ring such as m-xylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone;

  Furthermore, by using the so-called raw amine (unmodified) exemplified above, an amine adduct obtained by reacting a part of the amino group with the various epoxy resins exemplified above, or a part of the amino group Further, there may be mentioned modified products such as polyamide polyamines obtained by polycondensation of amides with aliphatic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid that can be used at this time include dimer acid composed of tall oil fatty acid, linolenic acid, linoleic acid, and the like. Moreover, you may use the adduct thing of the polyamidoamine obtained by making the above-mentioned epoxy resin react further with a part of amino group of polyamidoamines. These polyamine compounds (b1) may be used alone or in combination of two or more.

  The polyamine compound (b1) may be selected appropriately in consideration of the desired properties of the cured product to be obtained. If excellent flexibility, toughness, etc. are desired, the polyalkylene polyamine and its modification It is preferable to use a product. Moreover, if excellent moisture resistance reliability and high temperature storage reliability are desired, amines having an aromatic ring are preferably used.

  Examples of the formaldehydes (b2) include formaldehyde releasing substances such as formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and acetone. Among these, formaldehyde is preferable because of excellent reactivity.

  Examples of the phenol compound (b3) include phenol, alkyl-substituted phenol, cresol, halogen-substituted phenol, anisole, bisphenol A, bisphenol F and the like, and these may be used alone or in combination of two or more. Among these, phenol is preferred because of excellent curability and excellent moisture resistance reliability of the cured product.

  A method for obtaining the Mannich type curing agent (Y) by reacting these polyamine compounds (b1), formaldehydes (b2), and phenol compounds (b3) is not particularly limited. For example, polyamine compounds (b1) ) And a phenol compound (b3) are added formaldehydes (b2) at 80 ° C. or less, preferably 60 ° C. or less, and then heated to 80 to 180 ° C., preferably 90 to 150, and the distillate is added. The method obtained by making it react for 1 to 10 hours, removing from a reaction system, etc. are mentioned. The obtained Mannich type curing agent (Y) may be used alone or in combination of two or more.

  As the use amount of the Mannich type curing agent (Y), since the curing proceeds smoothly and good cured properties are obtained, the Mannich type curing agent (Y) is used with respect to 1 equivalent of the epoxy group of the epoxy resin to be used. The amount in which the active hydrogen group in the amount becomes 0.7 to 1.5 equivalents is preferable.

  Since the epoxy resin composition of the present invention has good curability without using a curing accelerator, it is not necessary to use a curing accelerator, but it further increases the reaction rate and imparts workability, etc. For this purpose, a curing accelerator may be used. 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, phosphorous-based triphenylphosphine and amine-based 1,8-diazabicyclo- [5,4,0] -undecene (DBU) are excellent in curability, heat resistance, electricity It is preferable from the point that the hardened | cured material which is excellent in a characteristic, moisture resistance reliability, etc. is obtained.

  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, 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, an emulsifier, can be added to the epoxy resin composition of this invention as needed.

  A flame retardant imparting agent can be added to the 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.

  An organic solvent can be used for the epoxy resin composition of this invention as needed. 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.

  In the epoxy resin composition of the present invention, the epoxy resin (X), the Mannich type curing agent (Y), and other epoxy resins used in combination as necessary, additives, etc., are mixed according to the viscosity of the resulting composition. And can be obtained by mixing uniformly. The shape of the epoxy resin composition of the present invention is not limited at all. Even if the epoxy resin (X) used is liquid, the epoxy resin to be used together, the Mannich type curing agent (Y), the filler species and the type thereof are used. Depending on the amount used, 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 used as a mixed solvent of two kinds or more as appropriate. 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 sealing material, an epoxy resin (X), a Mannich type curing agent (Y), other epoxy resins blended as necessary, a coupling agent, An example is a method in which an additive such as a release agent or an inorganic filler is premixed and then sufficiently mixed until uniform using an extruder, kneader, 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 deal with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for technology for reducing the capacity of insulating materials, and this problem can be solved by reducing the dielectric 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 is mentioned after apply | coating.

  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 it uniformly, and then mix it with Mannich type curing agent (Y) to make it uniform. And a method of 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, an epoxy resin (X), a Mannich type curing agent (Y), other epoxy resins used in combination as necessary, addition It can be obtained by uniformly mixing agents etc. at room temperature or under heating using a mixing mixer, etc., and after applying to various base materials, the base material is adhered by leaving it to stand at room temperature or under heating Can do.

  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. A solvent having a boiling point of 160 ° C. or lower such as a non-alcoholic polar solvent can be used, and two or more mixed solvents can be used 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 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 epoxy resin (X-1) represented by the following structural formula

  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. 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. Thereafter, the temperature was raised to 65 ° C. while purging with nitrogen gas, and then the pressure was reduced to an azeotropic pressure, and 122 g (1.5 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under these conditions for 0.5 hour. During this time, the distillate distilled azeotropically was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was conducted 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 the desired epoxy resin (X-1). The epoxy equivalent of the obtained epoxy resin (X-1) was 462 g / eq. The viscosity was 12,000 mPa · s (25 ° C., Canon Fenske method), and the average value of n in the formula calculated from the epoxy equivalent was 1.35.

Synthesis Example 2 Synthesis of Epoxy Resin (X-2) 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 101 g. The raw material resin has a hydroxyl equivalent of 262 g / eq. Met.

  Next, 395 g of the target epoxy resin (X-2) was obtained in the same manner as in Synthesis Example 1 except that the raw material resin was changed to 329 g. The epoxy equivalent of the obtained epoxy resin (X-2) was 350 g / eq. The viscosity was 90,000 mPa · s (25 ° C., E-type viscometer), and the average value of n in the formula calculated from the epoxy equivalent was confirmed to be 0.84.

Synthesis Example 3 Synthesis of Dimer Acid-Modified Epoxy Resin (X′-1) A flask equipped with a thermometer, a condenser tube, and a stirrer was charged with a bisphenol A liquid epoxy resin (Dainippon Ink Chemical Co., Ltd .: trade name EPICLON 850S, epoxy equivalent 185 g / eq.) 457 g and dimer acid (Tsuno Food Industries, trade name: Tsunodyme 216) 243 g were charged and heated to 80 ° C. while purging with nitrogen gas, and 0.14 g of triphenylphosphine (catalyst) Was added and reacted at 140 ° C. for 2 hours to obtain 700 g of a semisolid epoxy resin. This epoxy resin is an epoxy resin (X′-1) having a structure in which a molecular chain is extended by an ester bond by reacting a carboxylic acid of a dimer acid with an epoxy group, and an epoxy equivalent is 451 g / eq. The viscosity was 170 mPa · s (150 ° C., ICI viscometer).

Examples 1-4 and Comparative Examples 1-8
As epoxy resins, the two types of epoxy resins (X-1) and (X-2) obtained in Synthesis Examples 1 and 2 and the dimer acid-modified epoxy resin (X′- ) obtained in Synthesis Example 3 for comparison are used. 1) 6EO-modified bisphenol A type epoxy resin ( X'-2 , manufactured by Shin Nippon Rika Co., Ltd.), which is a glycidyl ether of an ethylene oxide adduct (6 mol addition) of bisphenol A, trade name “Rikaresin BEO-60E”, Epoxy equivalent 358 g / eq.) Was used. In addition, as a curing agent, Mannich type curing agent Rakkamide WH-614 (manufactured by Dainippon Ink & Chemicals, Inc .: Mannich type curing agent using triethylenetetramine, active hydrogen equivalent 51 g / eq.), Mannich type curing agent Rakkamide F4 (Dainippon Ink & Chemicals, Inc .: Mannich type curing agent using m-xylenediamine, active hydrogen equivalent 80 g / eq.), Triaminetetramine (active hydrogen equivalent 24 g / eq.) As an aliphatic amine curing agent. ).

Flexibility of cured product In the formulation according to Table 1, the epoxy resin and the curing agent were uniformly mixed at room temperature, poured into an iron petri dish (diameter 65 mm, height 12 mm), 2 hours at 80 ° C., 2 hours at 125 ° C. Heating was performed for 2 hours at 150 ° C. for 2 hours to obtain a test piece having a thickness of 2 mm. A flexibility confirmation test was performed using the cured product. In the flexibility confirmation test, a specimen that can be bent at about 180 degrees at room temperature was judged as ◯, and a specimen that could not be folded was judged as x.

Hardened material toughness A test piece produced in the same manner as in the flexibility confirmation test was bent by about 180 degrees, and a test piece that was not broken was judged as ◯, and a test piece that was broken was judged as x.

High temperature storage reliability Test pieces prepared in the same manner as the flexibility confirmation test are left in a dryer at 150 ° C for 500 hours. If the test pieces show deformation, cracks, cracks, etc. Was judged as ○.

Moisture resistance reliability A pressure cooker test was performed using a test piece prepared in the same manner as the flexibility confirmation test, and the moisture resistance reliability was evaluated. The pressure cooker test was performed under the conditions of 121 ° C., 100% RH, 2 atm × 2 hours. The cured product was visually checked for defects such as cracks, cracks, discoloration, and cloudiness. Further, the water absorption was calculated from the rate of weight increase after the pressure cooker test.

Claims (11)

An epoxy resin (X) obtained by glycidyl etherification of a modified polyphenol (A) obtained by reacting a polyhydric phenol (a1) with a polyvalent vinyl ether (a2), and a Mannich type curing agent (Y); An epoxy resin composition comprising: The 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 in the polyhydric phenol (a1)] / [polyvalent vinyl ether (a2 3) The epoxy resin composition according to claim 2, wherein the vinyl ether group in) is 80/20 to 50/50 (molar ratio). The epoxy equivalent of the epoxy resin (X) is 200 to 2,000 g / eq. The epoxy resin composition according to claim 2. The epoxy resin composition according to claim 2, wherein the polyvalent vinyl ether (a2) contains a polyoxyalkylene skeleton and / or a cycloalkane skeleton. The epoxy resin composition according to claim 1, wherein the Mannich type curing agent (Y) is obtained using an amine having an aromatic ring. It is a resin composition for printed circuit boards, The epoxy resin composition of any one of Claims 1-6 . The epoxy resin composition according to any one of claims 1 to 6 , which is a resin composition for a sealing material for electronic parts. The epoxy resin composition of any one of claims 1 to 6 is a resist ink. The epoxy resin composition according to any one of claims 1 to 6 , which is a conductive paste. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 10 .