JP2007308642A - Epoxy resin, curable resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin that is useful for an insulating material for electric/electronic components (such as a highly reliable semiconductor-sealing material), various composite materials including laminates (printed wiring boards, build-up substrates or the like) and CFRP, adhesives, coatings and the like, exhibits excellent flame retardancy and gives a cured product exhibiting excellent heat resistance and flexibility. <P>SOLUTION: The epoxy resin is obtained by causing a mixture of at least two selected from among 4,4'-dihydroxybiphenylmethane, 2,4'-dihydroxybiphenylmethane and 2,2'-dihydroxybiphenylmethane, biphenol and an epihalohydrin to react. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to insulating materials for electrical and electronic parts (such as highly reliable semiconductor encapsulating materials) and laminates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, etc. Useful for applications such as laminates, metal foil-clad laminates, insulating materials for build-up substrates, flexible substrate materials, etc. More specifically, the present invention is a resin for producing copper-clad laminates used for electronic circuit boards The present invention relates to an epoxy resin that provides a curable resin composition useful as a composition and a cured product of the composition.

  Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.

  However, in recent years, with the development in the electric and electronic fields, the resin composition is highly purified, moisture resistance, adhesion, dielectric properties, low viscosity for high filler filling, and shortening the molding cycle. There is a need for further improvements in various properties such as increased reactivity. Further, as a structural material, there is a demand for a material that is lightweight and has excellent mechanical properties in applications such as aerospace materials and leisure / sports equipment. Especially in the field of semiconductor encapsulation and substrates (substrate itself or its peripheral materials), thinning is becoming more and more sophisticated year by year, and heat resistance as well as flexibility is required as a characteristic required for materials. . In addition, due to environmental problems, halogen-based epoxy resins and antimony trioxide are recently widely used as flame retardants, especially as flame retardants for electric and electronic parts. It has been pointed out that it contributes to the generation of toxic substances such as As one method for solving the above problem, an epoxy resin having a phosphorus atom in the skeleton has been proposed. In particular, since a normal phosphate ester type compound has low stability, a cyclic phosphate compound having good stability is used. Even if a phosphoric acid ester compound is not used, those having excellent flame retardancy compared to conventional epoxy resins have been developed by selecting a resin skeleton. At present, there is a demand for flame retardancy generally called “halogen-free, phosphorus-free”. Examples of such an epoxy resin include a phenol-biphenyl aralkyl type epoxy resin (specifically, NC-3000 series manufactured by Nippon Kayaku Co., Ltd.) and the like, but the manufacturing process is complicated, and it is simpler and excellent in flame retardancy. Development of epoxy resin is desired.

JP 2006-45261 A

  The object of the present invention is to provide insulating materials (such as highly reliable semiconductor encapsulating materials) for electrical and electronic parts, laminated plates (printed wiring boards, build-up substrates, etc.), various composite materials including CFRP, adhesives, paints, etc. It is an epoxy resin that is useful for the above, and provides an epoxy resin that gives a cured product excellent in flame retardancy, and a curable resin composition using the epoxy resin.

（式中ｎは下記平均分子量にみあった繰り返し数を表す。複数あるＡｒは下記式（１ａ）または（１ｂ）を表し、それぞれ互いに同一であっても異なっていてもよいが、全てのＡｒが式（１ａ）または式（１ｂ）であることはない。）

で表されるエポキシ樹脂であって、酸素原子に対するメチレン結合の結合位置において下記式（２）、（３）、（４）

で表される結合の含有量（モル）をそれぞれβ、γ、δとしたとき、０＜β／（β＋γ＋δ）≦０．５であり、かつその平均分子量が５００〜１００００である事を特徴とするエポキシ樹脂、
（３）エポキシ当量が２５０〜２０００ｇ／ｅｑ．であり、かつ軟化点（もしくは融点）が４５〜１５０℃であることを特徴とする（１）または（２）に記載のエポキシ樹脂、
（４）（１）〜（３）のいずれか１項に記載のエポキシ樹脂、および硬化剤を含有してなるエポキシ樹脂組成物、
（５）無機充填剤を組成物の総重量の２０重量％以上含有することを特徴とするエポキシ樹脂組成物、
（６）（４）または（５）に記載の硬化性樹脂組成物を硬化してなる硬化物、
（７）（ａ）下記式（１’）

（式中ｎ'は平均分子量１５０〜５００にみあった繰り返し数を表す。複数あるＡｒは下記式（１ａ）または（１ｂ）を表し、それぞれ互いに同一であっても異なっていてもよい。）

で表されるエポキシ樹脂に
（ｂ）４，４’−ジヒドロキシビフェニルメタン、２，４’−ジヒドロキシビフェニルメタン及び２，２’−ジヒドロキシビフェニルメタンから選ばれる２種以上の混合物
及び／または
（ｃ）ビフェノール
を反応させることを特徴とする下記式（１）

（式中ｎは平均分子量５００〜１００００にみあった繰り返し数を表す。複数あるＡｒは前記式（１ａ）または（１ｂ）を表し、それぞれ互いに同一であっても異なっていてもよいが、全てのＡｒが式（１ａ）または式（１ｂ）であることはない。また、酸素原子に対するメチレン結合の結合位置において下記式（２）、（３）、（４）

で表される結合の含有量（モル）をそれぞれβ、γ、δとしたとき、０＜β／（β＋γ＋δ）≦０．５である。）
で表されるエポキシ樹脂の製造方法
（８）（ａ）のエポキシ樹脂がビスフェノールＦ型エポキシ樹脂であり、（ｂ）がビフェノールである（７）記載の製造方法
に関する。 The present inventors have completed the present invention as a result of intensive studies in order to solve the above problems. That is, the present invention
(1) Average molecular weight obtained by reacting a mixture of two or more selected from 4,4′-dihydroxybiphenylmethane, 2,4′-dihydroxybiphenylmethane and 2,2′-dihydroxybiphenylmethane, biphenol and epihalohydrin An epoxy resin of 500 to 10000,
(2) The following formula (1)

(In the formula, n represents the number of repetitions according to the following average molecular weight. Plural Ars represent the following formula (1a) or (1b), which may be the same or different from each other, but all Ar Is not formula (1a) or formula (1b).)

The following formulas (2), (3), (4) at the bonding position of the methylene bond to the oxygen atom

When the content (moles) of the bond represented by β is β, γ, and δ, respectively, 0 <β / (β + γ + δ) ≦ 0.5 and the average molecular weight is 500 to 10,000. Epoxy resin,
(3) Epoxy equivalent is 250-2000 g / eq. And the softening point (or melting point) is 45 to 150 ° C., the epoxy resin according to (1) or (2),
(4) An epoxy resin composition comprising the epoxy resin according to any one of (1) to (3) and a curing agent,
(5) An epoxy resin composition comprising an inorganic filler at 20% by weight or more of the total weight of the composition,
(6) A cured product obtained by curing the curable resin composition according to (4) or (5),
(7) (a) The following formula (1 ′)

(In the formula, n ′ represents the number of repetitions with an average molecular weight of 150 to 500. A plurality of Ars represents the following formula (1a) or (1b), which may be the same as or different from each other.)

(B) a mixture of two or more selected from 4,4′-dihydroxybiphenylmethane, 2,4′-dihydroxybiphenylmethane and 2,2′-dihydroxybiphenylmethane and / or (c) The following formula (1) characterized by reacting biphenol

(In the formula, n represents the number of repetitions with an average molecular weight of 500 to 10000. A plurality of Ars represents the above formula (1a) or (1b), which may be the same as or different from each other. Ar in formula (1a) or formula (1b) is not limited to the following formula (2), (3), (4) at the bonding position of the methylene bond to the oxygen atom.

And 0 <β / (β + γ + δ) ≦ 0.5, where β, γ, and δ are the content (moles) of bonds represented by: )
(8) It relates to the production method according to (7), wherein the epoxy resin of (a) is a bisphenol F type epoxy resin and (b) is biphenol.

  The epoxy resin composition using the epoxy resin of the present invention is an epoxy resin that exhibits flame retardancy without using a flame retardant and a phosphorus compound and contributes to the reduction of the flame retardant and phosphorus compound in the composition. Yes, it is useful for insulating materials for electrical and electronic parts (highly reliable semiconductor encapsulating materials, etc.), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, etc. .

  The epoxy resin of the present invention is an epoxy resin having a bisphenol skeleton and a biphenol skeleton. The reaction method is not particularly limited, but it can be obtained by reacting bisphenol F and biphenol with epihalohydrin all at once or stepwise.

市販されているビスフェノールＦはこれに相当する。なお、たとえば、４，４’−ビスフェノールＦのみを原料として本発明のエポキシ樹脂を製造した場合、結晶性が非常に高くなり、融点が１５０℃を超えてしまうことから製造時のハンドリングを考えてもあまり好ましくはない。
好ましい位置異性体の含有量（モル）としては前記式（２ａ）、（３ａ）、（４ａ）の位置異性体の含有量をそれぞれ（β’）、（γ’）、（δ’）とすると、０＜β’／（β’＋γ’＋δ’）≦０．５を満たすことが好ましく、さらにβ’×γ’×δ’≠０を満たすことが好ましい。
また本発明のエポキシ樹脂を得る反応において使用できる’エピハロヒドリンとしてはエピクロロヒドリン、エピブロモヒドリン、エピヨウ化ヒドリン等の化合物が挙げられ、市場からの入手の簡便さからエピクロロヒドリンが好ましい。 Bisphenol F that can be used in the present invention refers to a reaction product of phenol and formalin (or a derivative thereof). Such bisphenol F has several positional isomers, and bisphenol F containing two or more positional isomers selected from the following (2a) to (4a) is used.

Commercially available bisphenol F corresponds to this. For example, when the epoxy resin of the present invention is produced using only 4,4′-bisphenol F as a raw material, the crystallinity becomes very high and the melting point exceeds 150 ° C. Is also not preferred.
The preferred positional isomer content (mole) is that the content of the positional isomers of the formulas (2a), (3a), and (4a) is (β ′), (γ ′), and (δ ′), respectively. 0 <β ′ / (β ′ + γ ′ + δ ′) ≦ 0.5 is preferably satisfied, and β ′ × γ ′ × δ ′ ≠ 0 is preferably satisfied.
Examples of the 'epihalohydrin that can be used in the reaction for obtaining the epoxy resin of the present invention include compounds such as epichlorohydrin, epibromohydrin, epiiodinated hydrin and the like, and epichlorohydrin is preferable because it is easily available from the market. .

The specific synthesis method of the epoxy resin of the present invention will be described below. The synthesis method of the epoxy resin of the present invention is not limited to the following synthesis method.
The epoxy resin of the present invention can be synthesized by the one-step method or the fusion method (also called the Advanced method or the two-step method. New epoxy resin edited by Hiroshi Kakiuchi, pages 24-25 and 30-31). Hereinafter, both will be described in detail.

(One-stage method)
In this method, the epoxy resin of the present invention is obtained by mixing bisphenol F, biphenol and epihalohydrin and reacting them in the presence of an alkali metal hydroxide.

The amount of bisphenol F and biphenol used is 0.1 ≦ (F / P) where the number of moles of the bisphenol F-derived fragment of the resulting epoxy resin is (F) and the number of moles of the biphenol-derived fragment is (P). ) It is preferable to charge to satisfy ≦ 10. More preferably, 0.4 ≦ (F / P) ≦ 5, and further preferably 0.6 ≦ (F / P) ≦ 4. In the case of (F / P)> 0.1, the crystallinity is too high, so that the handling becomes worse. In the case of (F / P) <10, the contribution to flame retardancy is reduced.
The amount of epihalohydrin used is usually 1.0 to 5.0 moles, preferably 1.0 to 4.0 moles, more preferably 1.5 to 3.0 moles per mole of total hydroxyl groups of bisphenol F and biphenol. It is.

  Examples of the alkali metal hydroxide that can be used in this reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.3-2.5 mol normally with respect to 1 mol of total hydroxyl groups of bisphenol F and biphenol, Preferably it is 0.5-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mol of the total hydroxyl groups of bisphenol F and biphenol.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-200 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-150 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2, based on 1 mol of the total hydroxyl groups of bisphenol F and biphenol used for epoxidation. Is a mole. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

(Fusion method)
This method is a method in which bisphenol F and / or biphenol are reacted with an epoxy resin obtained by glycidylating bisphenol F and / or biphenol. That is, a phenol compound is further reacted with the intermediate epoxy resin. The intermediate epoxy resin and phenol compound to be used may be a combination in which the obtained epoxy resin has a bisphenol F skeleton and a biphenol skeleton. The epoxy resin obtained by glycidylating bisphenol F and / or biphenol as a raw material may be a commercially available compound (described later) or may be used after glycidylating bisphenol F and / or biphenol.

  Examples of commercially available bisphenol F include RE-304S, RE-303S-L, RE-404S, and RE-403S manufactured by Nippon Kayaku Co., Ltd., such as jER-806, jER-806L, and jER manufactured by Japan Epoxy Resin Co., Ltd. -807, etc., Toto Kasei Kogyo Co., Ltd. YDF-170, YDF-175S etc. are mentioned.

  When synthesizing the intermediate epoxy resin, for example, bisphenol F and / or biphenol and epihalohydrin are reacted in the presence of an alkali metal hydroxide. The amount of epihalohydrin used is usually 3.0 to 20.0 mol, preferably 3.5 to 10.0 mol, based on 1 mol of the total hydroxyl group of bisphenol F and / or biphenol. Examples of the bisphenol F that can be used here include the bisphenol F and the like.

  Examples of the alkali metal hydroxide that can be used in the above reaction include sodium hydroxide, potassium hydroxide, and the like, and a solid substance may be used or an aqueous solution thereof may be used. When using an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and further separated to remove water. Alternatively, the epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of hydroxyl groups of bisphenol F and / or biphenol, Preferably it is 0.95-2.0 mol.

  In order to accelerate the reaction, it is preferable to add a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, relative to 1 mol of the total hydroxyl group of C-BP.

  At this time, it is preferable for the reaction to proceed by adding an aprotic polar solvent such as alcohols such as methanol, ethanol and isopropyl alcohol, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran and dioxane.

  When using alcohol, the amount of its use is 2-50 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 4-20 weight%. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the usage-amount of epihalohydrin, Preferably it is 10-80 weight%.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent and the like are removed under heating and reduced pressure. In order to make the epoxy resin less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. The reaction can be carried out to ensure the ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2, based on 1 mol of the total hydroxyl group of bisphenol F and / or biphenol used for glycidylation. Is a mole. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain an intermediate epoxy resin. The intermediate epoxy resin thus obtained generally has an average molecular weight of preferably 150 to 500, more preferably 155 to 400. In the present invention, the “average molecular weight” is a value calculated from the epoxy equivalent.
The epoxy resin of the present invention can be obtained by reacting the obtained intermediate epoxy resin with bisphenol F and / or biphenol.

  This reaction uses a catalyst if necessary. Specific examples of catalysts that can be used include quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride; quaternary phosphonium salts such as triphenylethiphosphonium chloride and triphenylphosphonium bromide; sodium hydroxide Alkali metal salts such as potassium hydroxide, potassium carbonate, cesium carbonate; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) ) Tertiary amines such as phenol, triethylenediamine, triethanolamine, 1,8-diazabicyclo (5,4,0) undecene-7 ;, triphenylphosphine, diphenyl Organic phosphines such as sphin and tributylphosphine; metal compounds such as tin octylate; tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4- Examples thereof include tetraphenylboron salts such as methylimidazole / tetraphenylborate and N-methylmorpholine / tetraphenylborate. These catalysts are generally used in an amount of 10 ppm to 30000 ppm, preferably 100 ppm to 5000 ppm, if necessary, based on the total weight of the intermediate epoxy resin and bisphenol F and / or biphenol, depending on the type of the catalyst. In this reaction, since the reaction proceeds without adding a catalyst, the catalyst is appropriately used in consideration of the reaction temperature and the amount of the reaction solvent.

In this fusion method, a solvent may or may not be used. When a solvent is used, any solvent can be used as long as it does not affect the reaction. For example, the following solvents can be used.
Polar solvents, ethers; dimethyl sulfoxide, N, N′-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, diglyme, triglyme, propylene glycol monomethyl ether, etc.
Ester-based organic solvents; ethyl acetate, butyl acetate, butyl lactate, γ-butyrolactone, etc.
Ketone organic solvents; aromatic organic solvents such as methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; toluene, xylene, etc. The amount of solvent used is 0 with respect to the total weight of the intermediate epoxy resin and bisphenol F and / or biphenol. It is -300 weight%, Preferably it is 0-100 weight%.

  In the fusion method, an intermediate epoxy resin is reacted with bisphenol F and / or biphenol (hereinafter, both referred to as a chain extender) in the presence of a catalyst as necessary. The chain extender is selected so that the obtained epoxy resin always has a bisphenol fragment and a biphenol fragment, but a combination in which the intermediate epoxy resin is a bisphenol F type epoxy resin and the chain extender is biphenol is preferable. It is preferable to prepare the ratio of the intermediate epoxy resin and the chain extender used in the fusion method so that F / P of the resulting epoxy resin satisfies 0.1 ≦ (F / P) ≦ 10. More preferably, 0.4 ≦ (F / P) ≦ 5, and further preferably 0.6 ≦ (F / P) ≦ 4. In addition, F / P of the obtained epoxy resin can be confirmed by NMR. The reaction temperature and reaction time in the fusion method need to be appropriately selected depending on the amount of solvent used and the type and amount of the catalyst, and cannot be generally specified, but the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours. It is. In view of productivity, it is preferable that the reaction time is short. The reaction temperature is 0 to 250 ° C, preferably 30 to 200 ° C.

  After completion of the reaction, the epoxy resin of the present invention can be obtained by removing the catalyst or the like by washing with water or the like, if necessary, or by further distilling off the solvent under heating and reduced pressure.

で表される結合の含有量（モル）をそれぞれ（β）、（γ）、（δ）としたとき、０＜β／（β＋γ＋δ）≦０．５であるものが好ましく、β×γ×δ≠０であるものが特に好ましい。
このような関係を満たすには、一段法では、原料のビスフェノールＦ中の各結合異性体の含有割合が上記範囲を満たすようにすればよいし、フュージョン法では中間体エポキシ樹脂及びこれと反応させるビスフェノールＦの各結合異性体のトータルの含有割合が上記範囲を満たせばよい。 The epoxy resin of the present invention thus obtained has the following formulas (2), (3), (4)

Is preferably 0 <β / (β + γ + δ) ≦ 0.5 when the content (moles) of the bond represented by (β) is (β), (γ), and (δ), respectively, and β × γ × δ Those in which ≠ 0 are particularly preferred.
In order to satisfy such a relationship, in the one-step method, the content ratio of each bond isomer in the raw material bisphenol F may be set to satisfy the above range, and in the fusion method, the intermediate epoxy resin and this are reacted. It is only necessary that the total content ratio of each linking isomer of bisphenol F satisfies the above range.

  Moreover, it is preferable that the average molecular weight of this invention epoxy resin is 500-10000. More preferably, it is 500-5000. When the average molecular weight exceeds 10,000, the softening point becomes very high and handling becomes difficult. The epoxy resin of the present invention has an epoxy equivalent of 250 to 5000 g / eq. But 250 to 2500 g / eq. Are preferred. The softening point (or melting point) is preferably 40 to 160 ° C., particularly 45 to 150 ° C., from the viewpoint of easy handling. More preferably, it is 50-130 degreeC.

  The epoxy resin of the present invention thus obtained can be used as a main component of the epoxy resin composition described below, and can be derived into epoxy acrylate and derivatives thereof, carbonate resin, oxazolidone resin and the like.

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent. In the curable resin composition of the present invention, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the epoxy resin is preferably 5% by weight or more, particularly preferably 10% by weight or more.

  Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic substitution). Phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, croton Polycondensates with aldehydes, cinnamaldehyde, etc., phenols and various diene compounds (disi Polymers with lopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl) Ketones, acetophenones, benzophenones, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α, α ' -Polycondensates with dichloroxylene, bischloromethylbiphenyl, etc.), phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxyme) Glycidyl ether epoxy resin, alicyclic epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin obtained by glycidylation of alcohols, etc. However, the epoxy resin is not limited thereto as long as it is a commonly used epoxy resin. These may be used alone or in combination of two or more.

  Examples of the curing agent in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, triethylene anhydride. Mellitic acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, di Droxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polycondensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) , Phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone) , Acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α, α ' -Polycondensates with dichloroxylene, bischloromethylbiphenyl, etc.) Polycondensates with phenols and aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), bisphenols And polycondensates of aldehydes, and modified products thereof, imidazoles, trifluoroborane-amine complexes, guanidine derivatives, and the like, but are not limited thereto.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, particularly preferably 0.6 to 1.2 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

  Moreover, when using the said hardening | curing agent, a hardening accelerator may be used together. Examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, triethylenediamine, Triethanolamine, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine, metal compounds such as tin octylate, Tetraphenylphosphonium / tetraphenylborate, tetrasubstituted phosphonium / tetrasubstituted borate such as tetraphenylphosphonium / ethyltriphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmol Such as tetraphenyl boron salts such as phosphorus-tetraphenylborate and the like. When the curing accelerator is used, the amount used is 0.01 to 15 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

  Furthermore, an inorganic filler, a silane coupling material, a release agent, various compounding agents such as a pigment, and various thermosetting resins can be added to the epoxy resin composition of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. These inorganic fillers may be used in different amounts depending on the application. For example, when used for semiconductor encapsulants, the heat resistance, moisture resistance, mechanical properties, flame retardancy, etc. of the cured epoxy resin composition From the aspect, it is preferably used in a proportion of 20% by weight or more in the epoxy resin composition, more preferably 30% by weight or more, and more preferably 40 to 95% by weight.

  Furthermore, a known additive can be blended in the epoxy resin composition of the present invention as necessary. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluorine resin, maleimide compound, cyanate resin (or its prepolymer), silicone Gel, silicone oil, silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, glass fiber, glass nonwoven fabric or carbon fiber Inorganic fillers such as, surface treatment agents for fillers such as silane coupling agents, release agents, colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. And the epoxy resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. For example, an epoxy resin and a curing agent and, if necessary, a curing accelerator and an inorganic filler, a compounding agent, and various thermosetting resins are mixed thoroughly using an extruder, kneader, roll, etc. as necessary until uniform. Thus, the curable resin composition of the present invention is obtained, and the curable resin composition is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like, and further at 80 to 200 ° C. A cured product can be obtained by heating for 10 hours.

  Moreover, the epoxy resin composition of the present invention may optionally contain a solvent. An epoxy resin composition (epoxy resin varnish) containing a solvent is formed by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. By this, it can be set as the hardened | cured material of the epoxy resin composition of this invention. The solvent content of the epoxy resin composition is usually about 10 to 70% by weight, preferably about 15 to 70% by weight, based on the total amount of the epoxy resin composition of the present invention and the solvent. Moreover, the curable resin composition containing this solvent can be used also as the following varnish. Examples of the solvent include amide solvents such as γ-butyrolactone, N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-dimethylimidazolidinone, tetra Sulfones such as methylene sulfone, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower alkylene glycol mono or di-lower alkyl ether, methyl ethyl ketone, Ketone-based solvents such as methyl isobutyl ketone, preferably di-lower alkyl ketones in which two alkyl groups may be the same or different; Emissions, and aromatic solvents such as xylene. These may be used alone or in combination of two or more.

  Moreover, a sheet-like adhesive can be obtained by applying the varnish on a release film, removing the solvent under heating, and performing B-stage. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  The cured product obtained in the present invention can be used for various applications. Specifically, general applications in which a thermosetting resin such as an epoxy resin is used can be mentioned. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRPs, etc.), insulating materials (printed boards, In addition to sealing agents, etc., additives to other resins and the like can be mentioned.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. Moreover, in the Example, the epoxy equivalent was measured by the method according to JIS K-7236, and the softening point according to JIS K-7234.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while bisphenol F type epoxy resin (Nippon Kayaku Co., Ltd. RE-304S epoxy equivalent 171 g / eq.) 171 parts, 4, 4′- Add 93 parts of biphenol (p, p'-biphenol, manufactured by Honshu Chemical Industry Co., Ltd.), 70 parts of methyl isobutyl ketone, and 0.25 part of triphenylphosphine, add 1 hour at 100 ° C, 3 hours at 120 ° C, 5 parts at 130 ° C. Time reaction was performed. After completion of the reaction, 264 parts of the epoxy resin of the present invention was obtained by distilling off the solvent under heating and reduced pressure. The epoxy equivalent of the obtained epoxy resin was 438 g / eq. The softening point was 54 ° C. The average molecular weight was 876. Β / (β + γ + δ) ≈0.24 and F / P = 2.

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, and 100 parts of bisphenol F (BisF-ST, Mitsui Chemicals Fine Co., Ltd.), 4,4'-biphenol (Popular Honshu Chemical Co., Ltd. p) , P'-biphenol), 564 parts of epichlorohydrin, and 141 parts of dimethyl sulfoxide were added, and the temperature was raised to 40 ° C. Next, 50 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further performed at 40 ° C. for 2 hours, at 60 ° C. for 1 hour, and at 70 ° C. for 1 hour. After completion of the reaction, washing was performed, and excess solvent such as epichlorohydrin was distilled off from the oil layer under reduced pressure at 140 ° C. using a rotary evaporator. 380 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 80 ° C. Under stirring, 12 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water until the washing water became neutral, and the resulting solution was obtained at 180 ° C. using a rotary evaporator. By distilling off methyl isobutyl ketone and the like under reduced pressure, 182 parts of intermediate epoxy resin (NEP1) was obtained. The epoxy equivalent of the obtained epoxy resin is 164 g / eq. The average molecular weight was 328.
Furthermore, in a flask equipped with a stirrer, a reflux condenser, and a stirrer, 164 parts of an intermediate epoxy resin (NEP1) obtained while performing a nitrogen purge, 4,4′-biphenol (p. p'-biphenol) (46.5 parts), triphenylphosphine (0.2 parts) and cyclopentanone (30 parts) were added, and the reaction was carried out at 100 ° C for 1 hour, at 120 ° C for 3 hours, and at 130 ° C for 5 hours. After completion of the reaction, 210 parts of the epoxy resin (EP2) of the present invention was obtained by distilling off the solvent under heating and reduced pressure. The epoxy equivalent of the obtained epoxy resin is 440 g / eq. The softening point was 61 ° C. The average molecular weight was 880. Further, β / (β + γ + δ) ≈0.24 and F / P≈1.4.

Examples 3 and 4 and Comparative Example 1
Epoxy resins (EP1) and (EP2) of the present invention obtained in Examples 1 and 2, commercially available solid bisphenol F type epoxy resin (EP3) as a comparative example (YDF-2004 epoxy equivalent 471 g / eq, manufactured by Toto Kasei Co., Ltd.) Β / (β + γ + δ) ≈0.25) KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., phenol aralkyl resin, hydroxyl group equivalent 199 g / eq.) As a curing agent, and triphenylphosphine (TPP) as a curing accelerator The blending ratio (parts by weight) shown in Table 1 was blended. In addition, the following components were added as other components. MSR-2212 as a filler is 83% by weight relative to the total weight of the composition, Carnauba No. 1 as a wax is 0.3% by weight relative to the filler amount, and KBM-303 (Shin-Etsu Chemical Co., Ltd.) is used as a coupling agent. A composition is prepared by adding 0.4% by weight to the amount of filler, and a resin molded body is obtained by transfer molding (175 ° C. 60 seconds), which is further heated at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours. And cured.

Table 1
Example 3 Example 4 Comparative Example 1
Epoxy resin EP1 43.8
EP2 44.0
EP3 47.1
Hardener HD1 19.9 19.9 19.9
Curing accelerator TPP 0.44 0.44 0.47

The results of measuring the physical properties of the obtained cured product are shown in Table 2. The physical property values were measured by the following methods.
Glass transition point:
TMA thermomechanical measuring device: TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature increase rate: 2 ° C./min.
Flame retardancy: Conforms to UL-94 (Evaluation value is described in total combustion time, V-0 within 50 seconds)

Table 2
Example 3 Example 4 Comparative Example 1
Glass transition temperature (℃)
TMA 105 112 76
Flame resistance (thickness 0.8mm)
UL-94 V-0 V-0 V-1
Total burning time (seconds) 48 42 95

Examples 5 and 6, Comparative Example 2
Epoxy resins (EP1) and (EP2) of the present invention obtained in Examples 1 and 2, commercially available solid bisphenol F type epoxy resin (EP3) as a comparative example (YDF-2004 epoxy equivalent 471 g / eq, manufactured by Toto Kasei Co., Ltd.) Β / (β + γ + δ) ≈0.25) KAYAHARD GPH-65 (manufactured by Nippon Kayaku Co., Ltd., phenol aralkyl resin, hydroxyl group equivalent 199 g / eq.) As a curing agent, and triphenylphosphine (TPP) as a curing accelerator The blending ratio (parts by weight) shown in Table 3 was blended. A resin molding was obtained by transfer molding (175 ° C. 60 seconds), and further cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 3
Example 5 Example 6 Comparative Example 2
Epoxy resin EP1 87.6
EP2 88.0
EP3 94.2
Hardener HD1 39.8 39.8 39.8
Curing accelerator TPP 0.88 0.88 0.94

The results of measuring the physical properties of the obtained cured product are shown in Table 2. The physical property values were measured by the following methods.
HDT (thermal deformation temperature): JIS K-6911
Fracture toughness (K1C): JIS K-6911
Water absorption rate: Weight increase (%) when left in water at 100 ° C for 24 hours
Curing shrinkage; JIS K-6911 (mold shrinkage)

Table 4
Example 5 Example 6 Comparative Example 2
Thermal deformation temperature HDT (° C) 95 96 83
Fracture toughness K1C (MPa) 41 40 34
Water absorption rate 100 ° C. 24 hr, 2.2 2.1 2.6
Curing shrinkage (%) 1.1 1.1 1.5

  The modified epoxy resin of the present invention is not only excellent in flame retardancy (Table 2), but also retains heat resistance and gives a cured epoxy resin product excellent in toughness (Table 4). In addition, the curing shrinkage during curing is small (Table 4). Therefore, it is useful for insulating materials for electrical and electronic parts (such as highly reliable semiconductor encapsulating materials), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials including CFRP, adhesives, paints, and the like.

Claims (8)

The average molecular weight obtained by reacting a mixture of two or more selected from 4,4′-dihydroxybiphenylmethane, 2,4′-dihydroxybiphenylmethane and 2,2′-dihydroxybiphenylmethane, biphenol and epihalohydrin is 500 to 10,000. Epoxy resin. Following formula (1)

(In the formula, n represents the number of repetitions according to the following average molecular weight. Plural Ars represent the following formula (1a) or (1b), which may be the same or different from each other, but all Ar Is not formula (1a) or formula (1b).)

The following formulas (2), (3), (4) at the bonding position of the methylene bond to the oxygen atom

When the content (moles) of the bond represented by β is β, γ, and δ, respectively, 0 <β / (β + γ + δ) ≦ 0.5 and the average molecular weight is 500 to 10,000. Epoxy resin. Epoxy equivalent is 250-2000 g / eq. The epoxy resin according to claim 1 or 2, which has a softening point (or melting point) of 45 to 150 ° C. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and a curing agent. The epoxy resin composition according to claim 4, wherein the inorganic filler is contained in an amount of 20% by weight or more of the total weight of the composition. Hardened | cured material formed by hardening | curing the curable resin composition of Claim 4 or 5. (A) Formula (1 ′) below

(In the formula, n ′ represents the number of repetitions with an average molecular weight of 150 to 500. A plurality of Ars represents the following formula (1a) or (1b), which may be the same as or different from each other.)

(B) a mixture of two or more selected from 4,4′-dihydroxybiphenylmethane, 2,4′-dihydroxybiphenylmethane and 2,2′-dihydroxybiphenylmethane and / or (c) The following formula (1) characterized by reacting biphenol

(In the formula, n represents the number of repetitions with an average molecular weight of 500 to 10000. A plurality of Ars represents the above formula (1a) or (1b), which may be the same as or different from each other. Ar in formula (1a) or formula (1b) is not limited to the following formula (2), (3), (4) at the bonding position of the methylene bond to the oxygen atom.

And 0 <β / (β + γ + δ) ≦ 0.5, where β, γ, and δ are the content (moles) of bonds represented by: )
The manufacturing method of the epoxy resin represented by these. The method according to claim 7, wherein the epoxy resin of (a) is a bisphenol F type epoxy resin, and (b) is biphenol.