JP2005200544A - Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin giving a cured product excellent in moisture resistance, toughness and adhesivity. <P>SOLUTION: A phenol resin expressed by formula (2) is produced by reacting phenols with tricyclopentadiene under heating conditions in the presence of a Lewis acid, where the phenols are expressed by formula (1) and the heating conditions include heating at 100-130°C for 1-3 h followed by further heating at 130-180°C for 3-12 h. Provided that, in formula (1), Rs are each independently represents a hydrogen atom, a halogen atom, a 1-10C alkyl group or an aryl group; and m is an integer of 1-3, and in formula (2), R's are each independently represents a hydrogen atom, a halogen atom, a 1-10C alkyl group or an aryl group; Q represents a tricyclopentanyl group; m is an integer of 1-3; and n is a repeating number of 1-15 on average. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a phenol resin, an epoxy resin, and an epoxy resin composition containing these, which provide a cured product having low water absorption and high toughness and adhesion.

  Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as aviation / space industry and automobile industry.

  Epoxy resin is also a useful material as a matrix material for various composite materials because it is easy to mold and has a balanced performance in adhesion, electrical insulation, water resistance and chemical resistance. is there. Conventionally, as an epoxy resin most used industrially, a compound obtained by reacting bisphenol A with epichlorohydrin is known. In applications such as semiconductor encapsulants, cresol novolac epoxy resins are widely used because heat resistance is required.

  Numerous reports have been made on epoxy resins having a skeleton obtained by crosslinking phenols with dicyclopentadiene, and a well-balanced resin material that provides a cured product with excellent water resistance, adhesion, heat resistance, and low dielectric constant. It has been reported that. (Patent Documents 1, 2, and 3)

  In addition, in the field of optoelectronics, especially in recent years, advanced information technology, in order to smoothly transmit and process a huge amount of information, technology that utilizes optical signals will be developed instead of conventional signal transmission using electrical wiring. In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, it is desired to develop resins having excellent transparency and high heat resistance, low water absorption, adhesion, and low stress. .

JP 11-60688 JP-A-11-1544 JP 2003-277475 A

  An object of the present invention is to provide a phenol resin, an epoxy resin, and an epoxy resin composition that give a cured product having low water absorption, physical properties with high toughness and adhesion, and good dielectric properties. .

  As a result of diligent research to develop a cured product of an epoxy resin having the above-mentioned characteristics, the present inventors have completed the present invention.

（式（１）中、Ｒはそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、又はアリール基を表す。ｍは１〜３の整数である。）で示され、加熱条件が１００℃〜１３０℃にて１〜３時間加熱した後、さらに１３０℃〜１８０℃にて３〜１２時間加熱する条件である下記式（２）

（式（２）中、Ｒ’はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、又はアリール基を表す。Ｑはトリシクロペンタニル基を表す。ｍ’は１〜３の整数を、又ｎは１〜１５の繰り返し数であり、平均値である。）で示されるフェノール樹脂の製造法、
（２）式（１）及び式（２）においてＲ及びＲ’がメチル基であり、ｍが１である（１）に記載のフェノール樹脂の製造法、
（３）式（２）記載のフェノール樹脂が軟化点８０〜１４０℃、水酸基当量１９０〜２５０ｇ／ｅｑであることを特徴とする（１）又は（２）のいずれか一項に記載のフェノール樹脂の製造法、 That is, the present invention is (1) a process for producing a phenol resin characterized in that phenols and tricyclopentadiene are reacted under heating conditions in the presence of a Lewis acid, wherein the phenols are represented by the following formula (1):

(In formula (1), each R independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. M is an integer of 1 to 3) and heated. After heating for 1 to 3 hours at 100 ° C. to 130 ° C., the condition is further heated for 3 to 12 hours at 130 ° C. to 180 ° C.

(In Formula (2), R ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Q represents a tricyclopentanyl group. An integer of 3, and n is a repeating number of 1 to 15 and is an average value.)
(2) The method for producing a phenol resin according to (1), wherein R and R ′ are methyl groups and m is 1 in formula (1) and formula (2),
(3) The phenol resin according to any one of (1) and (2), wherein the phenol resin described in formula (2) has a softening point of 80 to 140 ° C. and a hydroxyl group equivalent of 190 to 250 g / eq. Manufacturing method,

(4) An epoxy resin obtained by reacting an epihalohydrin with a phenol resin obtained by the production method according to any one of (1) to (3) in the presence of a metal hydroxide,
(5) An epoxy resin composition comprising the epoxy resin according to (4) and a curing agent or a photopolymerization initiator,
(6) Hardened | cured material formed by hardening | curing the epoxy resin composition as described in (5),
(7) A semiconductor device having a cured product obtained by curing the epoxy resin composition according to (5),
About.

  The epoxy resin of the present invention is less colored and its cured product has excellent moisture resistance, toughness, and adhesion. Therefore, the epoxy resin composition of the present invention is extremely useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, optical materials and the like.

  The phenol resin represented by the formula (2) is obtained by adding a Lewis acid to phenols kept at a constant temperature in advance and adding tricyclopentadiene to a mixture of the phenols and Lewis acid. Formula (1) is a preferable aspect, R represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, or an aryl group each independently. Q represents a tricyclopentanyl group. m represents an integer of 1 to 3, and n represents an average value of 1 to 15 repetitions.

ｍ”は１〜３の整数であり、好ましくはｍ”＝１である。Ｒ”は水素原子又はハロゲン原子若しくは炭素数１〜１０のアルキル基、若しくはアリール基である。ハロゲン原子の具体例は、フッ素原子、塩素原子、臭素原子、ヨウ素原子などである。アルキル基の具体例は、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などの直鎖又は分岐のアルキル基、又はシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基などの環状アルキル基である。アリール基の具体例は、フェニル基、ナフチル基などである。Ｒ”はこれらのうち水素原子とメチル基が好ましい。Ｒ”の置換位置はフェノール性水酸基に対してオルト、メタ、パラ位があるが、好ましくはオルト位である。フェノール類の具体例としては、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、エチルフェノール、ｎ−プロピルフェノール、イソプロピルフェノール、ｓｅｃ−ブチルフェノール、ｔｅｒｔ−ブチルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、シクロヘキシルフェノール、キシレノール、メチルプロピルフェノール、メチルブチルフェノール、クロルフェノール、ブロムフェノール、ヨードフェノール等のフェノール類が挙げられ、本発明においては、これらのうちフェノールまたはクレゾールが好ましい。又、クレゾールの内、ｏ−クレゾールが更に好ましい。また、これらフェノール類は単独でまたは２種以上を混合して使用することができる。 The phenols used in the present invention are compounds having one phenolic hydroxyl group on the benzene ring. In the following formula (3),

m ″ is an integer of 1 to 3, and preferably m ″ = 1. R ″ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Specific examples of the alkyl group Examples are methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl A linear or branched alkyl group such as octyl group, nonyl group, decyl group, or cyclic alkyl such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc. Specific examples of the aryl group include a phenyl group and a naphtho group. Le group is such .R "is preferably a hydrogen atom and a methyl group of these. The substitution position of R ″ is ortho, meta, and para with respect to the phenolic hydroxyl group, but is preferably ortho. Specific examples of phenols include phenol, o-cresol, m-cresol, and p-cresol. Phenols such as ethylphenol, n-propylphenol, isopropylphenol, sec-butylphenol, tert-butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, xylenol, methylpropylphenol, methylbutylphenol, chlorophenol, bromophenol, iodophenol In the present invention, phenol or cresol is preferable, and o-cresol is more preferable among cresols. Phenol compounds may be used alone or in admixture of two or more.

  Specific examples of the Lewis acid in the present invention include boron trifluoride; boron trifluoride complexes such as boron trifluoride ether complexes, alkyl ether complexes, water complexes, amine complexes, phenol complexes, and alcohol complexes; aluminum trichloride, Any aluminum compound such as diethylaluminum monochloride; iron chloride; titanium tetrachloride; sulfuric acid; hydrogen fluoride; trifluoromethanesulfonic acid can be used. In particular, boron trifluoride and boron trifluoride complexes are preferred from the viewpoint of activity and ease of catalyst removal. The amount of the catalyst used is not particularly limited and can be appropriately selected depending on the catalyst used. For example, in the case of boron trifluoride-ether complex, 0.1 to 20% by weight based on tricyclopentadiene. Preferably, the content is 0.1 to 10% by weight.

に示される構造を有するものである。本発明においてはいずれの異性体を用いてもよい。また、これらは単体で用いても、混合体を用いてもかまわない。トリシクロペンタジエンに対するフェノール類の使用量はトリシクロペンタジエン１モルに対して通常１〜５０モルであるが、好ましくは２〜１０モルである。 Tricyclopentadiene used in the production method of the present invention is commercially available. There are various optical isomers and structural isomers in tricyclopentadiene, but typical ones are represented by formula (4) or formula (5).

It has the structure shown in FIG. Any isomer may be used in the present invention. These may be used alone or in a mixture. Although the usage-amount of the phenols with respect to tricyclopentadiene is 1-50 mol normally with respect to 1 mol of tricyclopentadiene, Preferably it is 2-10 mol.

  In the production method of the present invention, the mixed solution of the phenols and the Lewis acid is kept at a constant temperature in advance, and tricyclopentadiene is added thereto, but the tricyclopentadiene at this time is used as it is as a solution dissolved in a solvent. However, any of them may be used, but it is preferable to add dropwise as a solution dissolved in a solvent. The dropping temperature is preferably 50 ° C to 200 ° C, particularly preferably 80 ° C to 130 ° C.

  Solvents that can be used to prepare the tricyclopentadiene solution include aromatic hydrocarbons such as toluene and chlorobenzene, ketones such as methyl isobutyl ketone, cyclohexanone, and cyclopentanone, and ethers such as tetrahydrofuran and dioxane. Further, when the phenol used is liquid, the compound itself may be used as a solvent. The solvent is used as necessary in a proportion of 500% by weight or less based on tricyclopentadiene, but it is preferable to reduce the amount of the solvent as much as possible.

  The reaction temperature after dropping tricyclopentadiene or a solution thereof is usually 40 to 200 ° C, preferably 100 to 150 ° C. The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours. The reaction temperature is preferably raised stepwise, for example, it is preferably first heated at 100 to 130 ° C. for 1 to 3 hours, and then further continuously heated at 130 to 180 ° C. for 3 to 12 hours. . In order to obtain the phenol resin of the formula (2), the heating in the previous stage is carried out in two stages of 100 to 120 ° C. for 1 to 2 hours and slightly raised in temperature to 110 to 130 ° C. for 1 to 2 hours. preferable.

  In the production method of the present invention, it is preferable to sufficiently dry each compound to be used, or to perform a gas purge with an inert gas such as nitrogen or argon gas.

  After completion of the reaction, impurities such as an acid catalyst are neutralized and removed by washing with water. Then, the target phenol resin can be obtained by collect | recovering unreacted phenols and a solvent. At this time, various organic solvents can be used to facilitate separation from water. Examples of the organic solvent that can be used include aromatic organic solvents such as toluene, xylene, and cresol, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone. The amount of these organic solvents to be used is usually 50 to 400% by weight, preferably 50 to 200% by weight, based on the weight of the reaction product. The recovery of unreacted phenols and solvent is preferably distilled off under normal pressure or reduced pressure. It is also possible to blow off water vapor and distill it off with water vapor distillation. The softening point of the phenol resin obtained by the production method of the present invention is 80 to 140 ° C., and the hydroxyl equivalent is 190 to 300 g / eq, preferably 190 to 250 g / eq.

  The epoxy resin of the present invention can be obtained by reacting the phenol resin obtained by the production method of the present invention with epihalohydrin in the presence of an alkali metal hydroxide.

  In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, epibromohydrin or the like can be used as the epihalohydrin, and epichlorohydrin is preferred in the present invention. The usage-amount of epihalohydrin is 0.8-20 mol normally with respect to 1 mol of hydroxyl groups of the phenol resin obtained by the manufacturing method of this invention, Preferably it is 0.9-15 mol.

  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 thereof 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 amount of the alkali metal hydroxide used is usually 0.9 to 2.5 mol, preferably 0.95 to 2.0 mol, based on 1 mol of the hydroxyl group of the phenol resin obtained by the production method of the present invention. is there.

  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 based on 1 equivalent of the hydroxyl group of the phenol resin represented by the formula (2).

  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 1 mol of hydroxyl group of the phenol resin obtained by the production method of the present invention used for epoxidation. 0.2 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.

  The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent or a photopolymerization initiator as essential components. In this case, 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 total epoxy resin is preferably 30% by weight or more, particularly preferably 50% by weight or more.

  The epoxy resin composition of the present invention can be cured by an epoxy curing agent or a method using light, and the components contained in the epoxy resin composition differ depending on the curing method. Curing methods can be roughly classified into two types, one is curing by reaction of an epoxy curing agent and an epoxy resin, and the other is curing (polymerization) that gives a homopolymer of an epoxy resin by a polymerization initiator. In the latter method, cationic polymerization or anionic polymerization can be selected depending on the kind of the polymerization initiator.

  Hereinafter, the epoxy resin composition of the present invention containing a curing agent is referred to as a thermosetting epoxy resin composition. Specific examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention in the thermosetting epoxy resin cured product of the present invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4 ′ -Biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4 -Hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, Benz Rudehydr, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4 ' Polycondensates with bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, etc., and modified products thereof, tetra Examples include halogenated bisphenols such as bromobisphenol A, glycidyl etherified products derived from alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, and other solid or liquid epoxy resins. Not limited toThese may be used alone or in combination of two or more.

  Examples of the curing agent that can be used in preparing the thermosetting epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. 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, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic resin of the present invention, bisphenol A, bisphenol F Bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-bi Enyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl) Substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4 , 4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chlorome E) polycondensates with benzene, 1,4′-bis (methoxymethyl) benzene, etc., and modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, Although the condensate of a terpene and phenols is mentioned, it is not limited to these. These may be used alone or in combination of two or more.

  In the thermosetting epoxy resin composition of the present invention, the content of the curing agent is preferably 0.7 to 1.2 equivalents with respect to 1 equivalent of epoxy groups in the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the thermosetting epoxy resin composition of the present invention, a curing accelerator may be used. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo ( And tertiary amines such as 5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The curing accelerator is used as necessary in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

   Furthermore, an inorganic filler can be added to the thermosetting 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 are used in an amount of 0 to 95% by weight in the epoxy resin composition of the present invention. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the epoxy resin composition of the present invention. be able to.

  The thermosetting epoxy resin composition of the present invention can be obtained by uniformly mixing the above components. For example, the epoxy resin composition of the present invention is thoroughly mixed with a curing accelerator, an inorganic filler and a compounding agent as necessary using an extruder, kneader, roll, etc. You can get things. Moreover, 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. The cured product can be obtained by molding the epoxy resin composition using a cast or transfer molding machine after melting, and further heating at 80 to 200 ° C. for 2 to 10 hours.

  Further, the thermosetting epoxy resin composition is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and glass fiber, carbon fiber, polyester fiber, polyamide It is also possible to obtain a cured product by hot press molding a prepreg obtained by impregnating a substrate such as fiber, alumina fiber or paper and heating and semi-drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  Hereinafter, the epoxy resin composition of the present invention containing a photopolymerization initiator is referred to as a photocurable epoxy resin composition. When ion-polymerizing the photocurable epoxy resin composition of the present invention, the epoxy resin of the present invention and a photopolymerization initiator are contained. The present composition may further contain various known compounds such as diluents, polymerizable monomers, polymerizable oligomers, polymerization initiation assistants, photosensitizers, and the like. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

  Among the ionic polymerizations, cationic polymerization is preferable, and photocationic polymerization is particularly preferable. Examples of the cationic photopolymerization initiator include onium salts such as iodonium salts, sulfonium salts, and diazonium salts, and these can be used alone or in combination of two or more. The amount of the cationic photopolymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Furthermore, it is possible to simultaneously use one or more of these photocationic polymerization initiators, known polymerization initiation assistants and photosensitizers. Examples of polymerization initiators that can be used include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl. Phenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1-chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, aceto E Non dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone. The usage-amount of polymerization initiation adjuvants, such as radical photopolymerization initiator, is 0.01-30 weight part with respect to 100 weight part of resin components, Preferably it is 0.1-10 weight part.

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of epoxy resin components, Preferably it is 0.1-10 weight part.

  The photocurable epoxy resin composition of this invention is obtained by mixing each component uniformly. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the photocurable epoxy resin composition of the present invention and the solvent. Although the photocurable epoxy resin composition of the present invention can be cured by irradiating with ultraviolet rays, the amount of ultraviolet irradiation varies depending on the epoxy resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable epoxy resin composition hardens | cures, and should just satisfy | fill the hardening conditions with which the adhesive strength of hardened | cured material is favorable. However, it is difficult to cure these photo-curable epoxy resins by light irradiation alone, and in applications where heat resistance is required, it is necessary to complete the reaction by heating after light irradiation. Since it is necessary for light to be transmitted through the details during the curing, the photocurable epoxy resin and the photocurable epoxy resin composition of the present invention are highly transparent.

  The heating after the light irradiation of the photocurable epoxy resin composition may be performed in the normal curing temperature range of the epoxy resin composition. For example, the range of 30 minutes to 7 days at normal temperature to 150 ° C. is suitable. Although it changes depending on the composition of the photocurable epoxy resin composition, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By such heat after-curing, the effect of aging treatment of moisture and organic substances to be deposited is also obtained.

  In addition, even if it mix | blends a photocationic polymerization initiator, if there is no light irradiation, superposition | polymerization will not start easily, a pot life is long, and workability | operativity is good. In addition, the application method of these photocurable epoxy resin compositions will be described depending on each part and member, but may be a generally used uniform coating method, for example, screen printing method, spin coating method, spray method, Examples thereof include a transfer method and a dispenser method, but are not limited thereto.

  Further, when the photocurable epoxy resin composition of the present invention is used for, for example, a cationic curable resist, the photocurable type of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone. The epoxy resin composition is applied to a substrate such as a copper-clad laminate, a ceramic substrate, or a glass substrate with a film thickness of 5 to 160 μm by a method such as screen printing or spin coating, and the coating film is applied at 60 to 110 ° C. After pre-drying, the film is irradiated with ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film on which a desired pattern is drawn. Process. Then, after dissolving and removing (development) the unexposed portion with a solvent such as polyethylene glycol monoacetate, if necessary, sufficient curing is performed by irradiation with ultraviolet rays and heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). To obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The semiconductor device of the present invention is sealed with the thermosetting or photocurable epoxy resin composition of the present invention, and has a cured product of the epoxy resin composition of the present invention. As semiconductor devices, for example, DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), TSOP (Thin Small Outline Package), TQFP (Sink Quad Flat Package). In the optical semiconductor field, a light-emitting diode (LED), a phototransistor, a CCD (charge coupled device), an optical semiconductor device (semiconductor chip) such as an EPROM such as a UV-EPROM, and the like are particularly preferable. .

  The semiconductor device of the present invention, particularly the optical semiconductor device, can be manufactured by sealing an optical semiconductor element (optical semiconductor chip) with the thermosetting or photocurable epoxy resin composition of the present invention. As the sealing method, a method of molding (casting and curing) a sealing resin for sealing the optical semiconductor element by a method such as casting, potting or printing can be employed. As the molding conditions, the molding conditions in the sealing molding of a semiconductor element using a conventional epoxy resin composition can be employed as they are, and may be appropriately set depending on the composition of the epoxy resin composition of the present invention. For example, the molding conditions in the transfer molding are preferably in the range of a curing time of 60 to 120 seconds at a mold temperature of 150 to 160 ° C.

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 softening point, melt viscosity, and epoxy equivalent were measured under the following conditions.
-Softening point It measured by the method according to JIS K-7234.
Melt viscosity Melt viscosity in cone plate method at 150 ° C Measuring instrument: Cone plate (ICI) high temperature viscometer
(RESEACH EQUIPMENT (LONDON) LTD. Made)
Corn No. : 3 (measurement range 0 to 2.00 Pa · s)
Sample amount: 0.155 ± 0.01 g
-Epoxy equivalent It measures by the method according to JIS K-7236, and a unit is g / eq.

Example 1
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 151 parts of phenol and 0.3 part of trifluoroborane diethyl ether complex, and heated to 100 ° C. with stirring. A solution prepared by dissolving 79 parts of tricyclopentadiene (manufactured by TCPD Maruzen Petroleum Co., Ltd.) with 50 parts of toluene was dropped over 30 minutes while purging with nitrogen gas. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 1 hour and at 150 ° C. for 10 hours, and it was confirmed by gel permeation chromatography (GPC) (UV254 nm) that the reaction did not proceed any further. When the solution became 50 ° C. or lower, 500 parts of toluene was added to dissolve the reaction solution, and the solution was washed and separated three times with 100 parts of water. Excess phenol and solvent were distilled off under heating and reduced pressure to obtain 138 parts of phenol resin (A). The softening point was 122 ° C. and the hydroxyl equivalent was 213 g / eq. By GPC, the phenol resin (A) was estimated to have an average value of 1.49 in formula (1).

Example 2
50 parts of phenol resin (A), 89 parts of epichlorohydrin, and 22 parts of dimethyl sulfoxide were charged, heated to 35 ° C. with stirring, and dissolved. Subsequently, 9.5 parts of flaky sodium hydroxide was added in portions over 60 minutes, and then further reacted at 40 ° C. for 3 hours, 55 ° C. for 2 hours, and 70 ° C. for 0.5 hour. Subsequently, excess epichlorohydrin was distilled off under reduced pressure under heating, and 200 parts of methyl isobutyl ketone was added to the residue and dissolved. To this methyl isobutyl ketone, 100 parts of water was added and washed with water to remove the deposited salt.

  This methyl isobutyl ketone solution was heated to 70 ° C., 2 parts of a 30 wt% aqueous sodium hydroxide solution was added, reacted for 1 hour, and then washed with water until the washing solution became neutral. Further, the aqueous layer was separated and removed to obtain 57 parts of a yellow transparent epoxy resin (B) of the present invention.

  The obtained epoxy resin had a viscosity at 150 ° C. of 1.26 Pa · s, an epoxy equivalent of 285 g / eq, a softening point of 93 ° C., and a hue (Gardner) of 2.

Comparative Example 1
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 188 parts of phenol and 0.4 part of trifluoroborane diethyl ether complex, and the temperature was raised to 100 ° C. with stirring. While performing nitrogen gas purging, a solution in which 79 parts of tricyclopentadiene (TCPD manufactured by Maruzen Petroleum Corporation) was dissolved in 40 parts of toluene was dropped over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at 110 ° C. for 20 hours, and then the system was allowed to cool, and it was confirmed by GPC that the reaction did not proceed further. When the solution reached 50 ° C. or lower, 800 parts of toluene was added to dissolve the reaction solution, and the mixture was washed and separated three times with 150 parts of water. Excess phenol and solvent were distilled off under heating and reduced pressure to obtain 119 parts of phenol resin (X). From the amount of excess phenol, the amount of added phenol was 1.075 mol per 1 mol of tricyclopentadiene. When the product was confirmed by GPC, 76 area% of the phenol resin (X) was a mono-substituted product of phenol of tricyclopentadiene, and this reaction requires reaction conditions at a temperature higher than 110 ° C. all right.

Example 3
The same operation as in Example 1 was carried out except that 151 parts of phenol in Example 1 was changed to 215 parts of orthocresol and 0.2 part of trifluoroborane diethyl ether complex was changed. The obtained phenol resin (C) was 152 parts, the softening point was 105 ° C., and the hydroxyl group equivalent was 225 g / eq. By GPC, the phenol resin (C) was estimated to be a compound having an average value of n of 1.17 in the formula (1).

Example 4
50 parts of phenol resin (C), 124 parts of epichlorohydrin, 24 parts of methanol and 5 parts of water were charged, and the temperature was raised to 70 ° C. with stirring to dissolve. Subsequently, 9.0 parts of flaky sodium hydroxide was added in portions over 60 minutes, and then further reacted at 70 ° C. for 1 hour. Subsequently, washing with water was repeated to return to neutrality, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 200 parts of methyl isobutyl ketone was added to the residue and dissolved.

  This methyl isobutyl ketone solution was heated to 70 ° C., 2 parts of a 30 wt% aqueous sodium hydroxide solution was added, reacted for 1 hour, and then washed with water until the washing solution became neutral. Further, 59 parts of yellowish transparent epoxy resin (D) of the present invention was obtained by separating and removing the aqueous layer.

  The resulting epoxy resin had a viscosity at 150 ° C. of 0.34 Pa · s, an epoxy equivalent of 312 g / eq, a softening point of 81 ° C., and a hue (Gardner) of 2.

Example 5
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was charged with 141 parts of phenol and 0.3 part of trifluoroborane diethyl ether complex, and the temperature was raised to 100 ° C. with stirring. A solution prepared by dissolving 60 parts of tricyclopentadiene (TCPD, Maruzen Petroleum Co., Ltd.) with 30 parts of toluene was dropped over 30 minutes while purging with nitrogen gas. After completion of the dropwise addition, the mixture was further stirred at 120 ° C. for 1 hour, 130 ° C. for 1 hour, and 145 ° C. for 4 hours. After confirming that the reaction did not proceed further by GPC, the system was allowed to cool. When the solution became 50 ° C. or lower, 500 parts of toluene was added to dissolve the reaction solution, and the mixture was washed and separated three times with 120 parts of water. Excess phenol and solvent were distilled off under heating and reduced pressure to obtain 108 parts of phenol resin (E). The softening point was 117 ° C. and the hydroxyl equivalent was 212 g / eq. By GPC, the phenol resin (E) was estimated to be a compound having an average value of 1.46 in formula (1).

Example 6
A phenol resin (E) (160 parts), epichlorohydrin (312 parts), and dimethyl sulfoxide (80 parts) were charged, and the mixture was heated to 35 ° C. with stirring and dissolved. Next, 12 parts of flaky sodium hydroxide was added in portions over 60 minutes, and then further reacted at 40 ° C. for 3 hours, 55 ° C. for 2 hours, and 70 ° C. for 0.5 hour. Subsequently, washing with water was repeated to return to neutrality, and then excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 200 parts of methyl isobutyl ketone was added to the residue and dissolved.

  This methyl isobutyl ketone solution was heated to 70 ° C., 3 parts of a 30% by weight aqueous sodium hydroxide solution was added, reacted for 1 hour, and then washed repeatedly with water until the washing solution became neutral. Furthermore, 68 parts of light yellow transparent epoxy resin (F) of the present invention was obtained by separating and removing the aqueous layer.

  The resulting epoxy resin had a viscosity at 150 ° C. of 0.26 Pa · s, an epoxy equivalent of 323 g / eq, a softening point of 80 ° C., and a hue (Gardner) of 1.

Example 7, Comparative Example 2
The epoxy resin (F) obtained in Example 6 as an epoxy resin, a dicyclopentadiene phenol condensation type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., XD-1000, epoxy equivalent 253 g / eq), and a terpene phenol as a curing agent Resin (manufactured by Yasuhara Chemical Co., Ltd., YP90, hydroxyl group equivalent 162 g / eq, melting point 85 ° C.), triphenylphosphine (TPP) as a curing accelerator in the proportion (parts by weight) shown in Table 1, and resin molding by transfer molding The body was prepared and cured at 160 ° C. for 2 hours and further at 180 ° C. for 8 hours.

Table 1
Example 7 Comparative Example 2
Epoxy resin F 64
XD-1000 50
Hardener YP90 32 32
Curing accelerator TPP 0.6 0.5

Table 2 shows the results of measuring the physical properties of the obtained invention and comparative cured products. The physical property values were measured by the following methods.
Glass transition temperature (TMA): TM-7000 manufactured by Vacuum Riko Co., Ltd.
Temperature rising rate 2 ° C./min.
-Water absorption: Rate of weight increase (%) after boiling a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm in water at 100 ° C for 24 hours
-Fracture toughness (K1C): Conforms to JIS K-6911.
・ Peel strength: Conforms to JIS K-6911.

Table 2
Example 7 Comparative Example 2
Glass transition temperature (° C) 147 150
Water absorption rate (%) 0.8 0.9
Fracture toughness (K1C) (MPa) 27.1 23.9
Peel strength (Cu, kN / m) 2.6 2.3

  From Table 2, the cured product of the present invention has excellent toughness and copper adhesion as compared with the cured product of dicyclopentadiene phenol condensation type epoxy resin. Moreover, it is clear that it is excellent in moisture resistance from the low water absorption.

Claims (7)

A method for producing a phenol resin, comprising reacting a phenol with tricyclopentadiene in the presence of a Lewis acid, wherein the phenol is represented by the following formula (1):

(In formula (1), each R independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. M is an integer of 1 to 3) and heated. After heating for 1 to 3 hours at 100 ° C. to 130 ° C., the condition is further heated for 3 to 12 hours at 130 ° C. to 180 ° C.

(In Formula (2), R ′ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group. Q represents a tricyclopentanyl group. 3 is an integer of 3 and n is a repeating number of 1 to 15, which is an average value.) The method for producing a phenol resin according to claim 1, wherein R and R 'in the formulas (1) and (2) are methyl groups and m is 1. 3. The method for producing a phenol resin according to claim 1, wherein the phenol resin represented by the formula (2) has a softening point of 80 to 140 ° C. and a hydroxyl group equivalent of 190 to 250 g / eq. . The epoxy resin obtained by making an epihalohydrin react with the phenol resin obtained by the manufacturing method as described in any one of Claims 1 thru | or 3 in presence of a metal hydroxide. An epoxy resin composition comprising the epoxy resin according to claim 4 and a curing agent or a photopolymerization initiator. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 5. A semiconductor device having a cured product obtained by curing the epoxy resin composition according to claim 5.