JP4698586B2 - Novel phenolic compound and novel epoxy resin derivable from the phenolic compound - Google Patents
Novel phenolic compound and novel epoxy resin derivable from the phenolic compound Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
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- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
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Description
本発明は新規フェノール化合物及び該フェノール化合物から誘導し得る新規エポキシ樹脂に関し、詳しくは、合成樹脂原料等として好適に用いられるフェノール化合物、及び塗料、接着剤、成型品等に用いる材料として有用で、該フェノール化合物から誘導し得るエポキシ樹脂に関するものである。 The present invention relates to a novel phenol compound and a novel epoxy resin that can be derived from the phenol compound. Specifically, the phenol compound is preferably used as a synthetic resin raw material and the like, and is useful as a material used for paints, adhesives, molded articles, The present invention relates to an epoxy resin that can be derived from the phenol compound.
ポリフェノール化合物は、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂等の合成樹脂用原料、エポキシ硬化剤、感熱記録に用いられる顕色剤や退色防止剤、電子材料の原料等として有用であり、また、酸化防止剤、殺菌剤、防菌防カビ剤等の添加剤としても有用である。 Polyphenol compounds are useful as raw materials for synthetic resins such as phenol resins, epoxy resins, polycarbonate resins, and polyester resins, epoxy curing agents, developers and anti-fading agents used in thermal recording, and raw materials for electronic materials. It is also useful as an additive for antioxidants, bactericides, fungicides and fungicides.
また、エポキシ樹脂は、接着性、耐熱性、耐薬品性、電気特性、機械特性等に優れるため、塗料、接着剤、成型品等に用いる材料として広く使用されており、ＩＣ封止材料、積層材料、電気絶縁材料等の電気電子分野においても広く活用されている。 Epoxy resins are widely used as materials for paints, adhesives, molded products, etc. because of their excellent adhesiveness, heat resistance, chemical resistance, electrical properties, mechanical properties, etc. It is also widely used in electrical and electronic fields such as materials and electrical insulating materials.
近年、特に、電気電子分野において、機器の小型化、高性能化に伴って、用いられる樹脂に対しても、機械的特性や熱的特性の向上のみならず、耐湿性、電気絶縁性、低誘電性等の向上がますます強く要求されるに至っており、それに伴って、かかる要求を満足する樹脂を提供し得る新たなビスフェノール化合物が求められている。 In recent years, especially in the field of electrical and electronic equipment, along with the downsizing and high performance of equipment, not only improved mechanical and thermal properties, but also moisture resistance, electrical insulation, Improvements in dielectric properties and the like have been increasingly demanded, and accordingly, new bisphenol compounds capable of providing a resin that satisfies such requirements have been demanded.
新規のフェノール化合物の開発は多く行われており、例えば、特許文献１には、テルペンジフェノール化合物が提案されており、特許文献２には、４−置換シクロヘキシリデンビスフェノール類が提案されているが、これらの化合物は上記の要求を未だ満足できるものではない。 Many new phenol compounds have been developed. For example, Patent Document 1 proposes terpene diphenol compounds, and Patent Document 2 proposes 4-substituted cyclohexylidene bisphenols. However, these compounds still cannot satisfy the above requirements.
また、例えば、特許文献３には、４−〔１，１−ビス（４−ヒドロキシフェニル）エチル〕ビフェニル等のビスフェノール化合物を電子受容性化合物として使用してなる記録材料が提案されており、特許文献４には、ビフェニルアルキリデン−４，４’−ビスフェノール化合物より誘導されるポリカーボネート系共重合体が提案されており、特許文献５には、メチル−フェニル−メチリデンビスフェノールを顕色剤として使用してなる感熱記録体が提案されており、特許文献６には、シクロヘキシルメチレン−４，４’−ビスフェノール化合物等を電子受容性化合物として使用してなる感熱記録材料が提案されている。しかし、これらも上記の要求を未だ満足できるものではない。 For example, Patent Document 3 proposes a recording material using a bisphenol compound such as 4- [1,1-bis (4-hydroxyphenyl) ethyl] biphenyl as an electron-accepting compound. Document 4 proposes a polycarbonate copolymer derived from a biphenylalkylidene-4,4′-bisphenol compound, and Patent Document 5 uses methyl-phenyl-methylidenebisphenol as a developer. A thermal recording material using a cyclohexylmethylene-4,4′-bisphenol compound or the like as an electron-accepting compound is proposed in Patent Document 6. However, these still cannot satisfy the above requirements.
従って、本発明の目的は、合成樹脂原料等として好適に用いられるフェノール化合物を提供すること、ならびに、塗料、接着剤、成型品等に用いる材料として有用なエポキシ樹脂を提供することにある。 Accordingly, an object of the present invention is to provide a phenol compound that is suitably used as a synthetic resin raw material and the like, and to provide an epoxy resin that is useful as a material for use in paints, adhesives, molded articles, and the like.
本発明者等は、鋭意検討を重ねた結果、新規フェノール化合物及び該フェノール化合物から誘導し得るエポキシ樹脂が、上記目的を満足し得ることを見出し、本発明に到達した。 As a result of intensive studies, the present inventors have found that a novel phenol compound and an epoxy resin that can be derived from the phenol compound can satisfy the above object, and have reached the present invention.
即ち、本発明は、下記一般式（Ｉ）で表されるフェノール化合物を提供するものである。 That is, the present invention provides a phenol compound represented by the following general formula (I).
また、本発明は、下記一般式（ＩＩ）で表されるエポキシ樹脂を提供するものである。 The present invention also provides an epoxy resin represented by the following general formula (II).
以下、本発明のフェノール化合物及びエポキシ樹脂について詳細に説明する。 Hereinafter, the phenolic compound and the epoxy resin of the present invention will be described in detail.
上記一般式（Ｉ）中、Ｃｙで表される炭素原子数３〜１０のシクロアルキル基としては、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、メチルシクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等の基が挙げられる。また、Ｙ及びＺで表される炭素原子数１〜１０のアルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、イソオクチル、第三オクチル、２−エチルヘキシル、ノニル、イソノニル、デシル、イソデシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル等の直鎖、分岐及び環状のアルキル基が挙げられる。また、Ｘで表わされる炭素原子数３〜１０のシクロアルキル基としては、Ｃｙとして例示したものと同様のものが挙げられ、また、Ｘで表わされるフェニル基を置換し得る炭素原子数１〜１０のアルキル基としては、Ｙ及びＺとして例示したものと同様のものが挙げられる。 In the above general formula (I), the cycloalkyl group having 3 to 10 carbon atoms represented by Cy is a group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. Is mentioned. Examples of the alkyl group having 1 to 10 carbon atoms represented by Y and Z include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl and isooctyl. , Tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. Examples of the cycloalkyl group having 3 to 10 carbon atoms represented by X include those exemplified as Cy, and also has 1 to 10 carbon atoms capable of substituting the phenyl group represented by X. Examples of the alkyl group include those similar to those exemplified as Y and Z.
本発明のフェノール化合物としては、例えば、下記の化合物等が挙げられる。 Examples of the phenol compound of the present invention include the following compounds.
本発明のフェノール化合物の製造方法は特に限定されるものではないが、例えば、下記〔化１１〕に示すように、ケトン化合物（１）とフェノール化合物（２）の混合物を、酸性触媒の存在下に反応させることによって容易に製造することができる。 The method for producing the phenolic compound of the present invention is not particularly limited. For example, as shown in the following [Chemical Formula 11], a mixture of the ketone compound (1) and the phenolic compound (2) is added in the presence of an acidic catalyst. It can be easily produced by reacting with.
上記反応に使用される酸性触媒としては、例えば、メタンスルホン酸、ベンゼンスルホン酸、ｍ−キシレンスルホン酸、ｐ−トルエンスルホン酸、ヒドロキシメチルスルホン酸、２−ヒドロキシエチルスルホン酸、ヒドロキシプロピルスルホン酸、トリフルオロメタンスルホン酸、スルホサリチル酸、スルホフタル酸等のスルホン酸類；硫酸、無水硫酸、発煙硫酸、クロロ硫酸、フルオロ硫酸、塩酸、塩化水素ガス、シュウ酸、ギ酸、リン酸、トリクロロ酢酸、トリフルオロ酢酸、ケイタングステン酸、リンタングステン酸等のヘテロポリ酸、強酸性のイオン交換樹脂等が挙げられる。 Examples of the acidic catalyst used in the above reaction include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, Sulfonic acids such as trifluoromethanesulfonic acid, sulfosalicylic acid, sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, Examples include heteropolyacids such as silicotungstic acid and phosphotungstic acid, and strongly acidic ion exchange resins.
さらに、上記反応においては、反応を促進するためにメルカプタン触媒を使用することができ、該メルカプタン触媒としては、例えば、メチルメルカプタン、エチルメルカプタン、プロピルメルカプタン、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、１，６−ヘキサンジチオール等のアルキルメルカプタン類；チオフェノール、チオクレゾール等の芳香族メルカプタン類；メルカプト酢酸（チオグリコール酸）、３−メルカプトプロピオン酸、メルカプトウンデカン酸、チオ安息香酸等のメルカプト有機酸類；２−メルカプトベンゾチアゾール等の複素環族メルカプタン類；硫化水素等が挙げられる。 Furthermore, in the above reaction, a mercaptan catalyst can be used to promote the reaction. Examples of the mercaptan catalyst include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 1, Alkyl mercaptans such as 6-hexanedithiol; aromatic mercaptans such as thiophenol and thiocresol; mercapto organic acids such as mercaptoacetic acid (thioglycolic acid), 3-mercaptopropionic acid, mercaptoundecanoic acid, and thiobenzoic acid; 2 -Heterocyclic mercaptans such as mercaptobenzothiazole; hydrogen sulfide and the like.
本反応において、フェノール化合物（２）は、ケトン化合物（１）の１モルに対して、１モル以上、特に２〜１０モルの範囲で使用することが好ましく、酸性触媒はケトン化合物（１）１モルに対し、０．００１〜２．０モル、特に０．０１〜１．５モル使用することが好ましく、メルカプト触媒は、ケトン化合物（１）１モルに対し、特に０．００１〜１．０モル使用することが好ましい。 In this reaction, the phenol compound (2) is preferably used in an amount of 1 mol or more, particularly 2 to 10 mol, per 1 mol of the ketone compound (1), and the acidic catalyst is the ketone compound (1) 1 It is preferable to use 0.001 to 2.0 mol, particularly 0.01 to 1.5 mol, based on mol, and the mercapto catalyst is particularly 0.001 to 1.0 mol per mol of the ketone compound (1). It is preferable to use molar.
また、上記反応には、汎用溶媒を使用することができ、該溶媒としては、例えば、トルエン、キシレン、クメン等の芳香族炭化水素系溶媒；テレピン油、Ｄ−リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶剤；メタノール、エタノール等のアルコール系溶媒；酢酸エチル等のエステル溶媒；ジクロロエタン、四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、クロロベンゼン等のハロゲン系溶媒；テトラヒドロフラン、ジオキサン等の環状エーテル系溶媒；アニリン、トリエチルアミン、ピリジン、ジオキサン、酢酸、アセトニトリル、二硫化炭素等が挙げられる。 In addition, a general-purpose solvent can be used for the above reaction, and examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene and cumene; terpene carbonization such as terpine oil, D-limonene and pinene. Hydrogen oil; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcohol solvents such as methanol and ethanol; ester solvents such as ethyl acetate; Examples include halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; aniline, triethylamine, pyridine, dioxane, acetic acid, acetonitrile, and carbon disulfide.
本反応は０〜２００℃、特に１０〜１００℃の範囲で行なうのが好ましい。０℃未満であると反応が遅くなり長時間の反応が必要となり、２００℃を越えると副反応が多く起こり好ましくない。反応時間は、反応温度が０〜２００℃の場合、通常、数分〜数十時間の範囲から選択される。 This reaction is preferably carried out in the range of 0 to 200 ° C, particularly 10 to 100 ° C. If it is less than 0 ° C., the reaction is slow, and a long reaction time is required. When the reaction temperature is 0 to 200 ° C., the reaction time is usually selected from the range of several minutes to several tens of hours.
本発明のフェノール化合物は、フェノール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリスルホン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリビスマレイミド樹脂、ポリアリレート樹脂、ポリアセタール樹脂等の合成樹脂用原料；エポキシ硬化剤；顕色剤、退色防止剤等の感熱記録材料；電子材料原料；酸化防止剤、紫外線吸収剤、難燃剤、殺菌剤、防菌防カビ剤等の添加剤、及びそれらの原料としても有用である。 The phenol compound of the present invention is used for synthetic resins such as phenol resin, epoxy resin, polycarbonate resin, polyester resin, polysulfone resin, polyimide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polyarylate resin, polyacetal resin, etc. Raw materials; Epoxy curing agents; Heat sensitive recording materials such as developers and anti-fading agents; Electronic material raw materials; Additives such as antioxidants, ultraviolet absorbers, flame retardants, bactericides, fungicides and fungicides, and their It is also useful as a raw material.
上記一般式（ＩＩ）で表わされる本発明のエポキシ樹脂としては、例えば、下記の化合物等が挙げられる。 As an epoxy resin of this invention represented by the said general formula (II), the following compound etc. are mentioned, for example.
本発明のエポキシ樹脂の製造方法は特に限定されるものではないが、例えば、上記一般式（ＩＩ）におけるｎが０であるエポキシ樹脂は、下記〔化２０〕に示すように、本発明のフェノール化合物（Ｉ）とエピクロルヒドリン（３）とを、アルカリ及びルイス酸又は層間移動触媒の存在下に反応させることによって容易に製造することができる。 The method for producing the epoxy resin of the present invention is not particularly limited. For example, the epoxy resin in which n in the general formula (II) is 0 is represented by the following formula [20]. It can be easily produced by reacting compound (I) with epichlorohydrin (3) in the presence of an alkali and a Lewis acid or an intercalation catalyst.
上記反応で使用されるアルカリとしては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等が挙げられる。また、ルイス酸としては、上記で例示した如き酸性触媒、四塩化スズ、三フッ化ホウ素、四塩化チタン、活性白土、塩化アルミニウム、塩化マグネシウム、渦マンガン酸カリウム、クロム酸カリウム等が挙げられる。また、層間移動触媒としては、例えば、テトラメチルアンモニウムクロリド、テトラブチルアンモニウムブロミド、メチルトリオクチルアンモニウムクロリド、メチルトリデシルアンモニウムクロリド、ベンジルトリエチルアンモニウムクロリド、Ｎ，Ｎ−ジメチルピロリジニウムクロリド、Ｎ−エチル−Ｎ−メチルピロリジニウムヨージド、Ｎ−ブチル−Ｎ−メチルピロリジニウムブロミド、Ｎ−ベンジル−Ｎ−メチルピロリジニウムクロリド、Ｎ−エチル−Ｎ−メチルピロリジニウムブロミド、Ｎ−ブチル−Ｎ−メチルモルホリニウムブロミド、Ｎ−ブチル−Ｎ−メチルモルホリニウムヨージド、Ｎ−アリル−Ｎ−メチルモルホリニウムブロミド、Ｎ−メチル−Ｎ−ベンジルピペリジニウムクロリド、Ｎ−メチル−Ｎ−ベンジルピペリジニウムブロミド、Ｎ，Ｎ−ジメチルピペリジニウムヨージド、Ｎ−メチル−Ｎ−エチルピペリジニウムアセテート、Ｎ−メチル−Ｎ−エチルピペリジニウムヨージド等が挙げられるが、テトラメチルアンモニウムクロリド、ベンジルトリエチルアンモニウムクロリドが好ましい。 Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Examples of the Lewis acid include acidic catalysts as exemplified above, tin tetrachloride, boron trifluoride, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium vortex manganate, and potassium chromate. Examples of the interlayer transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl. -N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl- N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N -Benzylpiperidi Umbromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide, and the like include tetramethylammonium chloride, benzyltriethyl Ammonium chloride is preferred.
上記反応において、エピクロルヒドリンは、本発明のフェノール化合物（Ｉ）の水酸基１当量に対し、１当量以上、特に２〜１０当量の範囲で使用することが好ましく、アルカリは、上記水酸基１当量に対し、０．１〜２．０モル、特に０．３〜１．５モル使用するのが好ましく、層間移動触媒は、本発明のフェノール化合物（Ｉ）の水酸基１当量に対し、０．０１〜１０モル％、特に０．２〜５モル％使用するのが好ましい。また、上記一般式（ＩＩ）におけるｎが１〜１０のエポキシ樹脂も、ｎが０の場合の上記反応に準じて製造することができ、その際にはエピクロルヒドリンの使用量を適宜選択すればよい。また、上記一般式（ＩＩ）におけるｎが１〜１０のエポキシ樹脂は、上記一般式（ＩＩ）におけるｎが０のエポキシ樹脂及び上記一般式（Ｉ）で表わされる本発明のフェノール化合物を反応させることによっても製造することができる。 In the above reaction, epichlorohydrin is preferably used in an amount of 1 equivalent or more, particularly 2 to 10 equivalents, based on 1 equivalent of the hydroxyl group of the phenol compound (I) of the present invention. It is preferable to use 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol, and the interlayer transfer catalyst is 0.01 to 10 mol with respect to 1 equivalent of the hydroxyl group of the phenol compound (I) of the present invention. %, Particularly 0.2 to 5 mol% is preferred. Moreover, the epoxy resin whose n in the said general formula (II) is 1-10 can also be manufactured according to the said reaction in case n is 0, and should just select the usage-amount of epichlorohydrin suitably in that case . The epoxy resin having n of 1 to 10 in the general formula (II) is reacted with the epoxy resin having n of 0 in the general formula (II) and the phenol compound of the present invention represented by the general formula (I). Can also be manufactured.
上記〔化２０〕に示す反応においては、本発明のフェノール化合物（Ｉ）の製造に用い得る溶媒として例示した如き溶媒を使用することができる。また、過剰のエピクロルヒドリンを溶媒として使用することもできる。 In the reaction shown in the above [Chemical Formula 20], a solvent as exemplified as a solvent that can be used in the production of the phenol compound (I) of the present invention can be used. Excess epichlorohydrin can also be used as a solvent.
本反応は２０〜１００℃、特に３０〜６０℃の範囲で行なうのが好ましい。２０℃未満であると反応が遅くなり長時間の反応が必要となり、１００℃を越えると副反応が多く起こり好ましくない。反応時間は、反応温度が２０〜１００℃の場合、通常、数分〜数十時間の範囲から選択される。 This reaction is preferably carried out in the range of 20 to 100 ° C, particularly 30 to 60 ° C. If it is less than 20 ° C., the reaction is delayed and a long reaction time is required. When the reaction temperature is 20 to 100 ° C., the reaction time is usually selected from the range of several minutes to several tens of hours.
本発明のエポキシ樹脂は、通常、エポキシ樹脂用の硬化剤と組み合わせて使用され、該硬化剤としては、例えば、ジエチレントリアミン、トリエチレントリアミン、テトラエチレンペンタミン等のポリアルキルポリアミン類；１，２−ジアミノシクロヘキサン、１，４−ジアミノ−３，６−ジエチルシクロヘキサン、イソホロンジアミン等の脂環式ポリアミン類；ｍ−キシリレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の芳香族ポリアミン類等のポリアミン類が挙げられる。また、これらのポリアミン類と、フェニルグリシジルエーテル、ブチルグリシジルエーテル、ビスフェノールＡ−ジグリシジルエーテル、ビスフェノールＦ−ジグリシジルエーテル等のグリシジルエーテル類又はカルボン酸のグリシジルエステル類等の各種エポキシ樹脂とを常法によって反応させることによって製造されるポリエポキシ付加変性物；これらのポリアミン類と、フタル酸、イソフタル酸、ダイマー酸等のカルボン酸類とを常法によって反応させることによって製造されるアミド化変性物；これらのポリアミン類とホルムアルデヒド等のアルデヒド類及びフェノール、クレゾール、キシレノール、第三ブチルフェノール、レゾルシン等の核に少なくとも一個のアルデヒド化反応性場所を有するフェノール類とを常法によって反応させることによって製造されるマンニッヒ化変性物等が挙げられる。さらに、ジシアンジアミド、酸無水物、イミダゾール類等の潜在性硬化剤も使用できる。 The epoxy resin of the present invention is usually used in combination with a curing agent for epoxy resin. Examples of the curing agent include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,2- Alicyclic polyamines such as diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane and isophoronediamine; polyamines such as aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone It is done. In addition, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acid are used in a conventional manner. Polyepoxy addition-modified products produced by reacting them with these; amidation-modified products produced by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; Reaction of aldehydes such as formaldehyde with phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, tert-butylphenol, resorcin, etc. Mannich-modified products and the like that are prepared by. Furthermore, latent curing agents such as dicyandiamide, acid anhydrides, and imidazoles can also be used.
また、本発明のエポキシ樹脂を使用する際には、必要に応じて、硬化触媒；モノグリシジルエーテル類、ジオクチルフタレート、ジブチルフタレート、ベンジルアルコール、コールタール等の反応性又は非反応性の希釈剤（可塑剤）；ガラス繊維、炭素繊維、セルロース、ケイ砂、セメント、カオリン、クレー、水酸化アルミニウム、ベントナイト、タルク、シリカ、微粉末シリカ、二酸化チタン、カーボンブラック、グラファイト、酸化鉄、瀝青物質等の充填剤もしくは顔料；γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、Ｎ−β−（アミノエチル）−Ｎ’−β−（アミノエチル）−γ−アミノプロピルトリエトキシシラン、γ−アニリノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、ビニルトリエトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン等のシランカップリング剤；キャンデリラワックス、カルナウバワックス、木ろう、イボタロウ、みつろう、ラノリン、鯨ろう、モンタンワックス、石油ワックス、脂肪酸ワックス、脂肪酸エステル、脂肪酸エーテル、芳香族エステル、芳香族エーテル等の潤滑剤；増粘剤；チキソトロピック剤；酸化防止剤；光安定剤；紫外線吸収剤；難燃剤；消泡剤；防錆剤；コロイダルシリカ、コロイダルアルミナ等の常用の添加物を添加してもよく、さらに、キシレン樹脂、石油樹脂等の粘着性の樹脂類を併用することもできる。 In addition, when using the epoxy resin of the present invention, if necessary, a curing catalyst; a reactive or non-reactive diluent such as monoglycidyl ethers, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, coal tar, etc. Plasticizer); glass fiber, carbon fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, talc, silica, fine powder silica, titanium dioxide, carbon black, graphite, iron oxide, bituminous substances, etc. Filler or pigment: γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N′-β- (aminoethyl) -γ -Aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycol Sidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ- Silane coupling agents such as methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, ibotarou, beeswax, lanolin, spermaceti, montan Lubricants such as waxes, petroleum waxes, fatty acid waxes, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; Foaming agent; rust preventive; colloidal Ca may be added additives conventional such colloidal alumina, further xylene resins, may be used in combination tacky resin such as petroleum resin.
さらに、本発明のエポキシ樹脂は、ウレタン変性、シリカ変性、リン酸変性、アミン変性、（メタ）アクリル酸変性等の各種の変性品の原料としても使用することができる。 Furthermore, the epoxy resin of the present invention can also be used as a raw material for various modified products such as urethane modification, silica modification, phosphoric acid modification, amine modification, and (meth) acrylic acid modification.
本発明のエポキシ樹脂あるいはその変性品は、例えば、コンクリート、セメントモルタル、各種金属、皮革、ガラス、ゴム、プラスチック、木、布、紙等に対する塗料あるいは接着剤；包装用粘着テープ、粘着ラベル、冷凍食品ラベル、リムーバルラベル、ＰＯＳラベル、粘着壁紙、粘着床材の粘着剤；アート紙、軽量コート紙、キャストコート紙、塗工板紙、カーボンレス複写機、含浸紙等の加工紙；天然繊維、合成繊維、ガラス繊維、炭素繊維、金属繊維等の収束剤、ほつれ防止剤、加工剤等の繊維処理剤；シーリング材、セメント混和剤、防水材等の建築材料；電子・電気機器用封止剤等の広範な用途に使用することができる。 The epoxy resin of the present invention or a modified product thereof includes, for example, paints or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc .; adhesive tape for packaging, adhesive label, frozen Food labels, removable labels, POS labels, adhesive wallpaper, adhesives for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copiers, impregnated paper and other processed paper; natural fiber, synthetic Fiber treatment agents such as fibers, glass fibers, carbon fibers, metal fibers, etc., fiber treatment agents such as fraying prevention agents and processing agents; building materials such as sealing materials, cement admixtures and waterproofing materials; sealants for electronic and electrical equipment, etc. It can be used for a wide range of applications.
以下、実施例等を示して本発明のフェノール化合物及びエポキシ樹脂を更に詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example etc. are shown and a phenol compound and an epoxy resin of the present invention are explained still in detail, the present invention is not limited to these.
〔参考例１〕ビフェニルシクロヘキシルケトン（ケトン化合物Ｋ−１）の製造
攪拌装置、冷却管、温度計を付した５Ｌ四つ口フラスコに塩化アルミニウム４５４．７ｇ、クロロベンゼン２６３０ｇを仕込み、氷浴下で攪拌しながらビフェニル４３８．３ｇを添加し、溶解させた。その後、シクロヘキサンカルボン酸クロライド５００．０ｇを０〜８℃で２．５時間かけて滴下し、その後ゆっくりと２０℃まで昇温し、２時間さらに反応させた。
反応液を、氷水４ｋｇ中に攪拌下、発熱に注意しながら注ぎ、油水分離して得た有機層を希塩酸３ｋｇで洗浄後、さらに水３ｋｇで３回洗浄した。無水硫酸ナトリウムで脱水後、溶媒を留去し、ヘキサンから再結晶して白色結晶５６３．５ｇ（収率７５％）を得た。
得られた白色結晶は、１Ｈ−ＮＭＲ及びＩＲによる分析を行なったところ、以下の１Ｈ−ＮＭＲのケミカルシフト及びＩＲの吸収を示し、目的物であるケトン化合物Ｋ−１であることが確認された。また、該白色結晶は、融点が８６．９℃（示差熱ピークトップ）であった。[Reference Example 1] Production of biphenyl cyclohexyl ketone (ketone compound K-1) Into a 5 L four-necked flask equipped with a stirrer, a condenser tube and a thermometer were charged 454.7 g of aluminum chloride and 2630 g of chlorobenzene and stirred in an ice bath. While adding 438.3 g of biphenyl, it was dissolved. Thereafter, 500.0 g of cyclohexanecarboxylic acid chloride was added dropwise at 0-8 ° C. over 2.5 hours, and then the temperature was slowly raised to 20 ° C. and further reacted for 2 hours.
The reaction solution was poured into 4 kg of ice water with stirring while paying attention to heat generation, and the organic layer obtained by oil-water separation was washed with 3 kg of dilute hydrochloric acid and further washed with 3 kg of water three times. After dehydration with anhydrous sodium sulfate, the solvent was distilled off, and recrystallization from hexane gave 563.5 g (yield 75%) of white crystals.
When the obtained white crystals were analyzed by 1 H-NMR and IR, they showed the following 1 H-NMR chemical shift and IR absorption, and were confirmed to be the target ketone compound K-1. It was done. The white crystals had a melting point of 86.9 ° C. (differential heat peak top).
（１Ｈ−ＮＭＲのケミカルシフト）
［実施例１］１，１−ビス（４’−ヒドロキシフェニル）−１−（１”−ビフェニル）−１−シクロヘキシルメタン（化合物Ｐ−１）の製造
攪拌装置、冷却管、温度計を付した１Ｌ四つ口フラスコに、参考例１で得られたケトン化合物Ｋ−１の７０．５ｇ、フェノール２００．７ｇ、チオ酢酸１０．１５ｇを仕込み、水冷下、攪拌しながらトリフルオロメタンスルホン酸４０．０ｇを１８℃で２０分かけて滴下した。水冷１７〜１９℃で１８時間反応後、水冷したまま水５００ｇを加えて反応をクエンチし、トルエン５００ｇで抽出した。有機層をｐＨ３〜４になるまで水で洗浄し、減圧下でトルエン、水及び過剰のフェノールを留去し、さらにトルエンを加えて析出した結晶をろ取し、トルエンで分散洗浄し、淡黄色結晶５９．２ｇ（収率５１．２％）を得た。
得られた淡黄色結晶は、１Ｈ−ＮＭＲ及びＩＲによる分析を行なったところ、以下の１Ｈ−ＮＭＲのケミカルシフト及びＩＲの吸収を示し、目的物である化合物Ｐ−１であることが確認された。また、該淡黄色結晶は、融点が２３９．５℃（示差熱ピークトップ）であった。Example 1 Production of 1,1-bis (4′-hydroxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (Compound P-1) A stirrer, a condenser, and a thermometer were attached. A 1 L four-necked flask was charged with 70.5 g of the ketone compound K-1 obtained in Reference Example 1, 200.7 g of phenol, and 10.15 g of thioacetic acid, and 40.0 g of trifluoromethanesulfonic acid with stirring under water cooling. Was added dropwise over 20 minutes at 18 ° C. After reaction for 18 hours at 17 to 19 ° C. with water cooling, 500 g of water was added while cooling with water to quench the reaction, and extraction was performed with 500 g of toluene. After washing with water, toluene, water and excess phenol were distilled off under reduced pressure. Further, toluene was added and the precipitated crystals were collected by filtration, dispersed and washed with toluene, and 59.2 g of light yellow crystals (yield) It was obtained 1.2%).
When the obtained pale yellow crystal was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was confirmed to be the target compound P-1. It was done. The pale yellow crystals had a melting point of 239.5 ° C. (differential heat peak top).
（１Ｈ−ＮＭＲのケミカルシフト）
［実施例２］１，１−ビス（４’−エポキシプロパニルオキシフェニル）−１−（１”−ビフェニル）−１−シクロヘキシルメタン（化合物Ｅ−１）の製造
攪拌装置、冷却管、温度計を付した５００ｍＬ四つ口フラスコに、実施例１で得られたフェノール化合物（化合物Ｐ−１）５７．５ｇ、エピクロルヒドリン１９５．８ｇを仕込み、ベンジルトリエチルアンモニムクロライド０．６０２ｇを加え、６４℃まで昇温し、１８時間攪拌した。その後５４℃まで降温し、２４質量％水酸化ナトリウム水溶液４３．０ｇを滴下、３０分攪拌した。その後、エピクロルヒドリンと水を共沸により留去し、さらに１２１℃まで昇温してエピクロルヒドリンを完全に留去した。続いてメチルイソブチルケトン２１６ｇを加えて３回水洗し、２４質量％水酸化ナトリウム２．２ｇを滴下した。８０℃で２時間攪拌、室温に戻し、３質量％モノリン酸ナトリウム水溶液で中和後、３回水洗した。溶媒を減圧留去し、黄色固形エポキシ樹脂５７ｇ（収率７８．８％）を得た。
得られた黄色固形エポキシ樹脂は、１Ｈ−ＮＭＲ及びＩＲによる分析を行なったところ、以下の１Ｈ−ＮＭＲのケミカルシフト及びＩＲの吸収を示し、目的物である化合物Ｅ−１であることが確認された。また、該黄色固形エポキシ樹脂は、融点が６４．２℃（示差熱ピークトップ）であった。Example 2 Production of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-cyclohexylmethane (Compound E-1) Stirrer, condenser, thermometer Is charged with 57.5 g of the phenolic compound (Compound P-1) obtained in Example 1 and 195.8 g of epichlorohydrin, and 0.602 g of benzyltriethylammonium chloride is added to 64 ° C. The temperature was raised and the mixture was stirred for 18 hours, then the temperature was lowered to 54 ° C., 43.0 g of a 24% by mass aqueous sodium hydroxide solution was added dropwise and stirred for 30 minutes, and then epichlorohydrin and water were distilled off azeotropically, and further 121 ° C. The epichlorohydrin was completely distilled off by heating to 216 g, followed by adding 216 g of methyl isobutyl ketone and washing with water three times. 2.2 g of sodium chloride was added dropwise, and the mixture was stirred at 80 ° C. for 2 hours, returned to room temperature, neutralized with a 3% by mass aqueous sodium monophosphate solution, and washed with water three times. Yield 78.8%) was obtained.
When the obtained yellow solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was the target compound E-1. confirmed. The yellow solid epoxy resin had a melting point of 64.2 ° C. (differential heat peak top).
（１Ｈ−ＮＭＲのケミカルシフト）
＜使用例１＞
化合物Ｅ−１の１００ｇ、アデカハードナーＥＨ−３３２６（旭電化工業製；メチルテトラヒドロ無水フタル酸）５８．８ｇ、トリフェニルフォスフィン１．５９ｇを混合し、１００℃で１時間、１３０℃で２時間、１６０℃で２時間ずつ加熱し、硬化物を得た。
この硬化物のガラス転移温度（Ｔｇ）を測定したところ、１５５℃であった。<Use Example 1>
Compound E-1 (100 g), Adeka Hardener EH-3326 (Asahi Denka Kogyo; methyltetrahydrophthalic anhydride) (58.8 g) and triphenylphosphine (1.59 g) were mixed and mixed at 100 ° C. for 1 hour and at 130 ° C. for 2 hours. And heated at 160 ° C. for 2 hours to obtain a cured product.
It was 155 degreeC when the glass transition temperature (Tg) of this hardened | cured material was measured.
＜比較使用例１＞
エピコート８３４（ジャパンエポキシレジン製；ビスフェノールＡ型エポキシ樹脂）１００ｇ、アデカハードナーＥＨ−３３２６の６６．４ｇ、トリフェニルフォスフィン１．６６ｇを混合し、１００℃で１時間、１３０℃で２時間、１６０℃で２時間ずつ加熱し、硬化物を得た。
この硬化物のガラス転移温度（Ｔｇ）を測定したところ、１３０℃であった。<Comparative use example 1>
Epicoat 834 (manufactured by Japan Epoxy Resin; bisphenol A type epoxy resin) 100 g, 66.4 g of Adeka Hardener EH-3326, and 1.66 g of triphenylphosphine were mixed, and 100 ° C. for 1 hour, 130 ° C. for 2 hours, 160 Heated at 2 ° C. for 2 hours to obtain a cured product.
It was 130 degreeC when the glass transition temperature (Tg) of this hardened | cured material was measured.
〔比較例１〕１，１−ビス（４’−エポキシプロパニルオキシフェニル）−１−（１”−ビフェニル）−１−エタン（化合物ＨＥ−１）の製造
４−〔１，１−ビス（４−ヒドロキシフェニル）エチル〕ビフェニル２１．９ｇ及びエピクロルヒドリン９９．７ｇを仕込み、ベンジルトリエチルアンモニムクロライド０．２７２ｇを加え、７５℃まで昇温し、１５時間反応させた。水とエピクロルヒドリンを共沸して還流脱水させながら４８質量％水酸化ナトリウム水溶液１０．０１ｇを滴下し、さらに還流脱水を行った後、１３０℃まで昇温してエピクロルヒドリンを留去した。トルエン５９．９ｇを加えて８０℃で１時間攪拌し、水２３ｇを加えて水洗した。
その後、４８質量％水酸化ナトリウム水溶液０．７２ｇ、水０．２９ｇ及びベンジルトリエチルアンモニムクロライド０．２７３ｇを加えて、８０℃で３時間反応させた後、水洗した。次いで、１質量％モノリン酸ナトリウム水溶液で中和し、さらに３回水洗した後、ろ渦し、１３０℃減圧下で脱溶媒して、黄色固形エポキシ樹脂２３．９ｇ（収率８３％）を得た。
得られた黄色固形エポキシ樹脂は、１Ｈ−ＮＭＲ及びＩＲによる分析を行なったところ、以下の１Ｈ−ＮＭＲのケミカルシフト及びＩＲの吸収を示し、目的物である化合物ＨＥ−１であることが確認された。Comparative Example 1 Preparation of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-ethane (Compound HE-1) 4- [1,1-bis ( 4-hydroxyphenyl) ethyl] biphenyl (21.9 g) and epichlorohydrin (99.7 g) were added, benzyltriethylammonium chloride (0.272 g) was added, and the mixture was heated to 75 ° C. and allowed to react for 15 hours. Then, 10.01 g of a 48 mass% sodium hydroxide aqueous solution was added dropwise while refluxing and dehydrating, and then the temperature was raised to 130 ° C. to distill off epichlorohydrin, and 59.9 g of toluene was added at 80 ° C. The mixture was stirred for 1 hour, and 23 g of water was added and washed with water.
Thereafter, 0.72 g of a 48% by mass aqueous sodium hydroxide solution, 0.29 g of water and 0.273 g of benzyltriethylammonium chloride were added and reacted at 80 ° C. for 3 hours, followed by washing with water. Next, the solution was neutralized with a 1% by mass sodium monophosphate aqueous solution, further washed with water three times, filtered and vortexed, and desolvated at 130 ° C. under reduced pressure to obtain 23.9 g of a yellow solid epoxy resin (yield 83%). It was.
When the obtained yellow solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, and was the target compound HE-1. confirmed.
（１Ｈ−ＮＭＲのケミカルシフト）
〔比較例２〕１，１−ビス（４’−エポキシプロパニルオキシフェニル）−１−（１”−ビフェニル）−１−プロパン（化合物ＨＥ−２）の製造
４−〔１，１−ビス（４−ヒドロキシフェニル）プロピル〕ビフェニル１３．５ｇ及びエピクロルヒドリン５９．７ｇを仕込み、ベンジルトリエチルアンモニムクロライド０．１６３ｇを加え、７５℃まで昇温し、１４時間攪拌した。水とエピクロルヒドリンを共沸して還流脱水させながら４８質量％水酸化ナトリウム水溶液５．４３ｇを滴下し、さらに還流脱水を行った後、１３０℃まで昇温してエピクロルヒドリンを留去した。トルエン３２．６ｇを加えて８０℃で１時間攪拌し、水１２．４ｇを加えて水洗した。
その後、４８質量％水酸化ナトリウム水溶液０．７２ｇ、水０．２９ｇ及びベンジルトリエチルアンモニムクロライド０．１５２ｇを加えて、８０℃で３時間反応させた後、水洗した。次いで、１質量％モノリン酸ナトリウム水溶液を加えて中和し、さらに３回水洗した後、ろ過し、１３０℃減圧下で脱溶媒して、橙色固形エポキシ樹脂１３．８ｇ（収率７９％）を得た。
得られた橙色固形エポキシ樹脂は、１Ｈ−ＮＭＲ及びＩＲによる分析を行なったところ、以下の１Ｈ−ＮＭＲのケミカルシフト及びＩＲの吸収を示し、目的物である化合物ＨＥ−２であることが確認された。Comparative Example 2 Production of 1,1-bis (4′-epoxypropanyloxyphenyl) -1- (1 ″ -biphenyl) -1-propane (Compound HE-2) 4- [1,1-bis ( 4-hydroxyphenyl) propyl] biphenyl 13.5 g and epichlorohydrin 59.7 g were added, 0.163 g of benzyltriethylammonium chloride was added, the temperature was raised to 75 ° C., and the mixture was stirred for 14 hours. While refluxing dehydration, 5.43 g of a 48% by mass aqueous sodium hydroxide solution was added dropwise, followed by further refluxing and dehydration, and then the temperature was raised to 130 ° C. to distill off epichlorohydrin. The mixture was stirred for an hour, and 12.4 g of water was added and washed with water.
Thereafter, 0.72 g of a 48% by mass aqueous sodium hydroxide solution, 0.29 g of water and 0.152 g of benzyltriethylammonium chloride were added and reacted at 80 ° C. for 3 hours, followed by washing with water. Next, the mixture was neutralized by adding a 1% by mass sodium monophosphate aqueous solution, further washed with water three times, filtered, and desolvated under reduced pressure at 130 ° C. to obtain 13.8 g of an orange solid epoxy resin (yield 79%). Obtained.
When the obtained orange solid epoxy resin was analyzed by 1 H-NMR and IR, it showed the following 1 H-NMR chemical shift and IR absorption, indicating that it was the target compound HE-2. confirmed.
（１Ｈ−ＮＭＲのケミカルシフト）
＜使用例２及び比較使用例２〜４＞
エポキシ樹脂（〔表１〕に記載）３．５ｇ、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭ−Ａｃ）１．５ｇ、アデカハードナーＥＨ−３３２６（配合量は〔表１〕に記載）及びキュアゾール２Ｅ４ＭＺ（四国化成工業（株）製；２−エチル−４−メチルイミダゾール）の０．０６ｇを混合し、硬化性組成物を作成した。該硬化性組成物３ｇをガラス板上に直径７ｃｍに均一に塗布し、８０℃で６０分、さらに１５０℃で１２０分加熱して硬化させて硬化物を得た。得られた硬化物を８０℃の湯浴中に６０分浸漬し、質量増加率（％）を求めた〔吸水率〕。それらの結果を表１に示す。<Use Example 2 and Comparative Use Examples 2-4>
Epoxy resin (described in [Table 1]) 3.5 g, propylene glycol monomethyl ether acetate (PGM-Ac) 1.5 g, Adeka Hardener EH-3326 (the amount is described in [Table 1]) and Curesol 2E4MZ (Shikoku Chemicals) 0.06 g of Kogyo Co., Ltd .; 2-ethyl-4-methylimidazole) was mixed to prepare a curable composition. 3 g of the curable composition was uniformly applied to a diameter of 7 cm on a glass plate and cured by heating at 80 ° C. for 60 minutes and further at 150 ° C. for 120 minutes to obtain a cured product. The obtained cured product was immersed in a hot water bath at 80 ° C. for 60 minutes, and the mass increase rate (%) was determined [water absorption rate]. The results are shown in Table 1.
本発明によるフェノール化合物は、エポキシ樹脂用の原料等として有用である。また、該フェノール化合物より誘導し得るエポキシ樹脂は、硬化物性及び耐水性に優れた硬化物を提供し得るものである。 The phenol compound according to the present invention is useful as a raw material for epoxy resins. Moreover, the epoxy resin which can be induced | guided | derived from this phenol compound can provide the hardened | cured material excellent in hardened | cured material property and water resistance.
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| JP4198173B2 (en) | 2004-09-17 | 2008-12-17 | 凸版印刷株式会社 | Colored alkali-developable photosensitive resin composition and color filter using the colored alkali-developable photosensitive resin composition |
| JP4916224B2 (en) * | 2005-06-20 | 2012-04-11 | 株式会社Ａｄｅｋａ | Alkali-developable photosensitive resin composition |
| KR101317223B1 (en) * | 2005-06-20 | 2013-10-15 | 가부시키가이샤 아데카 | Colored alkali-developable photosensitive resin composition and color filters made by using the same |
| JP4878845B2 (en) * | 2006-01-10 | 2012-02-15 | 凸版印刷株式会社 | SUBSTRATE WITH PROJECT FOR CONTROLLING LIQUID CRYSTAL ORIENTATION CONTROL FORMED USING ALKALINE DEVELOPING PHOTOSENSITIVE RESIN COMPOSITION |
| JP4667261B2 (en) * | 2006-02-01 | 2011-04-06 | 株式会社Ａｄｅｋａ | Alkali-developable photosensitive resin composition |
| JP4738190B2 (en) * | 2006-02-01 | 2011-08-03 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP4878876B2 (en) * | 2006-03-15 | 2012-02-15 | 株式会社Ａｄｅｋａ | Epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| JP5546093B2 (en) * | 2006-12-26 | 2014-07-09 | 株式会社Ａｄｅｋａ | Polymerizable compound and polymerizable composition |
| JP5311750B2 (en) * | 2007-02-28 | 2013-10-09 | 株式会社Ａｄｅｋａ | Phenol resin, epoxy resin, alkali-developable resin composition, and alkali-developable photosensitive resin composition |
| EP2507283B1 (en) | 2009-12-02 | 2013-10-23 | Dow Global Technologies LLC | Epoxy resin compositions |
| EP2507285A2 (en) * | 2009-12-02 | 2012-10-10 | Dow Global Technologies LLC | Composite compositions |
| EP2507325B1 (en) | 2009-12-02 | 2014-05-21 | Dow Global Technologies LLC | Coating compositions |
| JP7465673B2 (en) | 2020-02-25 | 2024-04-11 | 株式会社Adeka | Polymers, molded articles and optical materials |
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| JP2000239206A (en) * | 1998-12-25 | 2000-09-05 | Honshu Chem Ind Co Ltd | Asymmetric alkylidene polyhydric phenols and production thereof |
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| JP3173629B2 (en) * | 1992-02-12 | 2001-06-04 | 日本化薬株式会社 | Epoxy resin composition and cured product thereof |
| JPH05295089A (en) * | 1992-04-21 | 1993-11-09 | Daihachi Chem Ind Co Ltd | Curable resin composition |
| TW343990B (en) * | 1996-02-09 | 1998-11-01 | Nippon Kayaku Kk | Epoxy resin, epoxy resin composition and hardened product thereof |
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| JP2000239206A (en) * | 1998-12-25 | 2000-09-05 | Honshu Chem Ind Co Ltd | Asymmetric alkylidene polyhydric phenols and production thereof |
| JP2002316963A (en) * | 2001-02-15 | 2002-10-31 | Osaka Gas Co Ltd | Bisphenol with low activity as endocrine disruptor |
| JP2003064121A (en) * | 2001-08-23 | 2003-03-05 | Tosoh Corp | Method of producing polyolefin |
| JP2003306461A (en) * | 2002-02-15 | 2003-10-28 | Honshu Chem Ind Co Ltd | 1,3,5-tris(4-hydroxyphenyl)adamantane and method for producing the same |
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