JPH09194575A - Epoxy resin curing agent and epoxy resin composition - Google Patents
Epoxy resin curing agent and epoxy resin compositionInfo
- Publication number
- JPH09194575A JPH09194575A JP742396A JP742396A JPH09194575A JP H09194575 A JPH09194575 A JP H09194575A JP 742396 A JP742396 A JP 742396A JP 742396 A JP742396 A JP 742396A JP H09194575 A JPH09194575 A JP H09194575A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing agent
- aromatic hydrocarbon
- phenolic hydroxyl
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、積層用、成型用、
接着用、塗料用、特にガラスエポキシ樹脂積層板用に適
するエポキシ樹脂硬化剤及びエポキシ樹脂組成物に関す
るものである。TECHNICAL FIELD The present invention relates to lamination, molding,
The present invention relates to an epoxy resin curing agent and an epoxy resin composition suitable for adhesives, paints, particularly glass epoxy resin laminates.
【０００２】[0002]
【従来の技術】一般にエポキシ樹脂は成型性、接着性、
電気特性に優れており、その用途としてはプリント配線
板、ＩＣ封止剤といった電気電子材用途が大きな割合を
占めている。2. Description of the Related Art Generally, epoxy resin has excellent moldability, adhesiveness,
It has excellent electrical properties, and its use is dominated by electrical and electronic materials such as printed wiring boards and IC sealants.
【０００３】これらの用途では、従来のエポキシ樹脂の
性能に対しさらに高耐熱性、低吸水性、低誘電率等の性
能付与が求められている。特開平５−７８４５７号公報
には、従来のエポキシ樹脂硬化剤に対し、極めて優れた
低吸水性を示す硬化剤として、フェノール性水酸基を含
有する芳香族炭化水素に、エチレン性不飽和二重結合を
少なくとも２個有する化合物が付加した構造のノボラッ
ク型合成樹脂が記載されている。In these applications, it is required to impart performance such as high heat resistance, low water absorption, low dielectric constant, etc. to the performance of conventional epoxy resins. Japanese Unexamined Patent Publication (Kokai) No. 5-78457 discloses an ethylenically unsaturated double bond to an aromatic hydrocarbon containing a phenolic hydroxyl group as a curing agent showing extremely low water absorption as compared with a conventional epoxy resin curing agent. A novolac type synthetic resin having a structure in which a compound having at least two is added is described.
【０００４】[0004]
【化４】 Embedded image
【０００５】（式中、Ａは２価の原子団、Ｒは同一でも
異なっていても良い水素原子、アルキル基、水酸基また
はハロゲン原子である。）(In the formula, A is a divalent atomic group, and R is a hydrogen atom, an alkyl group, a hydroxyl group or a halogen atom, which may be the same or different.)
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、特開平
５−７８４５７号公報に記載されているエポキシ樹脂硬
化剤は極めて低い吸水性能を付与したものの、耐熱性に
ついては他の硬化剤と同等のレベルであり、電気電子材
料における要求性能をすべて満たすものではないという
問題がある。However, although the epoxy resin curing agent described in Japanese Patent Application Laid-Open No. 5-78457 imparts extremely low water absorption performance, it has the same heat resistance as other curing agents. However, there is a problem that it does not meet all the required performances in electric and electronic materials.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記課題
について鋭意検討した結果、特開平５−７８４５７号公
報記載のエポキシ樹脂硬化剤において、数平均分子量を
１５００以上まで高分子量化したノボラック樹脂をエポ
キシ樹脂硬化剤として用いることにより、一般的なポリ
イミドと同程度の高耐熱性エポキシ樹脂が得られことを
見いだした。この発明は、特開平５−７８４５７号公報
記載のエポキシ樹脂硬化剤が、数平均分子量１５００以
上にする際の反応制御が容易であるという新たな知見に
基づくものである。本発明によるノボラックを用いたエ
ポキシ樹脂硬化物は一般的なエポキシ樹脂硬化物に対
し、単に耐熱性が著しく高いばかりでなく、低吸水性、
低誘電率、耐衝撃性の性能も付与されており、電気電子
材料として複合的な効果を併せ持っているという特徴を
有する。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that the epoxy resin curing agent described in JP-A-5-78457 has a high molecular weight novolak of up to 1500 or more. It was found that by using the resin as an epoxy resin curing agent, a high heat resistant epoxy resin comparable to general polyimide can be obtained. This invention is based on the new finding that the epoxy resin curing agent described in JP-A-5-78457 can easily control the reaction when the number average molecular weight is 1500 or more. The epoxy resin cured product using the novolac according to the present invention is not only extremely high in heat resistance as compared with a general epoxy resin cured product, but also has low water absorption,
It has low dielectric constant and impact resistance, and has the characteristic that it has a composite effect as an electric / electronic material.
【０００８】本発明は、フェノール性水酸基を含有する
芳香族炭化水素（Ａ）と一般式（I）で示される化合物
（Ｂ）とを付加してなり、１５００以上の数平均分子量
を有する合成樹脂からなるエポキシ樹脂硬化剤及びエポ
キシ樹脂組成物であり、好ましくは二価の電子供与性官
能基がフェニレン基であることを特徴とするエポキシ樹
脂硬化剤及びエポキシ樹脂組成物を提供するものであ
る。The present invention is a synthetic resin obtained by adding an aromatic hydrocarbon (A) containing a phenolic hydroxyl group and a compound (B) represented by the general formula (I) and having a number average molecular weight of 1500 or more. The present invention provides an epoxy resin curing agent and an epoxy resin composition, wherein the divalent electron donating functional group is preferably a phenylene group.
【０００９】[0009]
【化５】 Ｈ2Ｃ＝ＣＨ−Ｘ−ＣＨ＝ＣＨ2 （I） （式中、Ｘは二価の電子供与性官能基を示す。）Embedded image H 2 C═CH—X—CH═CH 2 (I) (In the formula, X represents a divalent electron-donating functional group.)
【００１０】[0010]
【発明の実施の形態】フェノール性水酸基を有する芳香
族炭化水素（Ａ）としては、特に限定されるものではな
いが、例えばフェノール、クレゾール、キシレノール、
ｐ−タ−シャリ−ブチルフェノ−ル等のアルキル置換フ
ェノール、クロロフェノール、ブロモフェノール等のハ
ロゲノフェノール、レゾルシン、カテコール、ハイドロ
キノン等のフェノール性水酸基を２個以上有する芳香族
化合物、ビスフェノールＡ、ビスフェノールＦ、ビスフ
ェノールＡＦ、ビスフェノールＳ等のビスフェノール
類、ナフトール、ジヒドロキシナフタレン等のナフトー
ル類、ヒドロキシアントラセン等、またさらにこれらの
単量体の単独または２種以上の混合物をホルムアルデヒ
ド、パラホルムアルデヒド、ヘキサメチレンテトラミ
ン、１，３−ジオキソラン、ジシクロペンタジエン等で
縮合し高分子化した芳香族高分子類が挙げられる。これ
らの芳香族炭化水素の単量体および縮重合体は単独のみ
ならず、２種以上を混合して使用することができる。中
でもクレゾールノボラック樹脂を用いるのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The aromatic hydrocarbon (A) having a phenolic hydroxyl group is not particularly limited, and examples thereof include phenol, cresol, xylenol,
Alkyl-substituted phenols such as p-tert-butylphenol, halogenophenols such as chlorophenol and bromophenol, aromatic compounds having two or more phenolic hydroxyl groups such as resorcin, catechol and hydroquinone, bisphenol A, bisphenol F, Bisphenols such as bisphenol AF and bisphenol S, naphthols such as naphthol and dihydroxynaphthalene, hydroxyanthracene and the like, and further, these monomers alone or in a mixture of two or more kinds thereof with formaldehyde, paraformaldehyde, hexamethylenetetramine, 1, Aromatic polymers that are polymerized by condensation with 3-dioxolane, dicyclopentadiene and the like can be mentioned. These aromatic hydrocarbon monomers and polycondensates may be used alone or in combination of two or more. Above all, it is preferable to use cresol novolac resin.
【００１１】縮重合体として用いる場合には、耐衝撃性
の点から二官能性フェノールとホルムアルデヒドとの縮
重合体が好ましい。二官能性フェノールとしては、オル
ソクレゾール、パラクレゾール、パラｔブチルフェノー
ル等フェノール核の水酸基に対しオルソまたはパラ位の
水素が１つ他の置換基で置換されたものが挙げられる。
この場合、オルソ置換フェノール、パラ置換フェノール
をそれぞれ単独で用いるより、併用する方が、ケトンな
どの溶液にした場合の相溶性、粘度の低さ、エポキシと
の反応性，耐熱性の点で好ましい結果が得られる。When used as a condensation polymer, a condensation polymer of a bifunctional phenol and formaldehyde is preferable from the viewpoint of impact resistance. Examples of the bifunctional phenol include orthocresol, para-cresol, para-t-butylphenol, and the like in which one ortho or para-position hydrogen is substituted with another substituent for the hydroxyl group of the phenol nucleus.
In this case, it is preferable to use the ortho-substituted phenol and the para-substituted phenol individually, in combination, in view of compatibility, low viscosity, reactivity with epoxy, and heat resistance when a solution such as a ketone is used. The result is obtained.
【００１２】一般式（I）で表わされる化合物（Ｂ）の
Ｘについては、フェニレン基、ヒドロキシフェニレン
基、ナフタレン環またはヒドロキシナフタレン環骨格の
もの等の二価の電子供与性官能基が挙げられるが、Ｘが
フェニレン基であるジビニルベンゼンを用いるのが好ま
しい。Examples of X in the compound (B) represented by the general formula (I) include divalent electron-donating functional groups such as those having a phenylene group, a hydroxyphenylene group, a naphthalene ring or a hydroxynaphthalene ring skeleton. , X is a phenylene group, divinylbenzene is preferably used.
【００１３】また化合物（Ｂ）には、必要に応じて他の
反応性第三成分も併用することができる。この第３成分
としては、スチレン、メチルスチレン、エチルスチレ
ン、モノブロモスチレン等の芳香族モノビニル化合物、
（メタ）アクリル酸メチルエステル、（メタ）アクリル
酸ステアリルエステル、（メタ）アクリル酸、Ｎ−メチ
ロ−ル（メタ）アクリルアミド、γ−メルカプトプロピ
ルトリメトキシシラン等の脂肪族モノビニル化合物が挙
げられる。これらの第３成分も単独のみならず、２種類
以上混合して使用することもできる。If desired, the compound (B) may also be used in combination with another reactive third component. As the third component, aromatic monovinyl compounds such as styrene, methylstyrene, ethylstyrene and monobromostyrene,
Aliphatic monovinyl compounds such as (meth) acrylic acid methyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid, N-methylol (meth) acrylamide, and γ-mercaptopropyltrimethoxysilane may be mentioned. These third components may be used alone or in combination of two or more.
【００１４】化合物（Ｂ）の使用量は、特に制限される
ものではなく、フェノール性水酸基を有する芳香族炭化
水素（Ａ）の種類と目的とする分子量によって適宜選択
して最適値を決定すべきであるが、本発明の１５００以
上の数平均分子量を有する合成樹脂を得るためには、フ
ェノール性水酸基を含有する芳香族炭化水素（Ａ）が、
フェノール、クレゾール等の単量体である場合には、芳
香族炭化水素（Ａ）と一般式（I）で示される化合物
（Ｂ）とを、重量比で５０〜４０：５０〜６０であるこ
とが好ましく、４３〜４８：５７〜５２がより好まし
い。またフェノール性水酸基を含有する芳香族炭化水素
（Ａ）が、ホルムアルデヒドなどによる縮重合体である
場合には、フェノール性水酸基を有する芳香族炭化水素
（Ａ）と一般式（I）で示される化合物（Ｂ）とを、重
量比で９５〜５０：５〜５０が好ましく、９５〜７０：
５〜３０がより好ましい。The amount of the compound (B) used is not particularly limited and should be appropriately selected depending on the kind of the aromatic hydrocarbon (A) having a phenolic hydroxyl group and the desired molecular weight to determine the optimum value. However, in order to obtain the synthetic resin of the present invention having a number average molecular weight of 1500 or more, the aromatic hydrocarbon (A) containing a phenolic hydroxyl group is
When it is a monomer such as phenol or cresol, the aromatic hydrocarbon (A) and the compound (B) represented by the general formula (I) are in a weight ratio of 50 to 40:50 to 60. Is preferred, and 43-48: 57-52 is more preferred. When the aromatic hydrocarbon (A) having a phenolic hydroxyl group is a condensation polymer of formaldehyde or the like, the aromatic hydrocarbon (A) having a phenolic hydroxyl group and the compound represented by the general formula (I) With (B), the weight ratio is preferably 95 to 50: 5 to 50, and 95 to 70:
5-30 are more preferable.
【００１５】本発明に係わる樹脂を製造する際の反応温
度は特に限定するものではないが、合理的に短時間とす
るには８０℃以上にするのがよい。この際用いられる触
媒としては、例えば塩化アルミニウム、塩化第一鉄のご
とき金属塩化物や、硫酸、塩酸、リン酸などの無機酸、
ベンゼンスルホン酸、パラトルエンスルホン酸のごとき
有機スルホン類、酢酸、蓚酸、マレイン酸のごとき有機
カルボン酸などが使用できる。これらの触媒は２種以上
混合して使用することも可能である。このなかでも蓚酸
を用いるのが好ましい。The reaction temperature for producing the resin according to the present invention is not particularly limited, but it is preferably 80 ° C. or higher for a reasonably short time. Examples of the catalyst used at this time include metal chlorides such as aluminum chloride and ferrous chloride, and inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid.
Organic sulfones such as benzenesulfonic acid and paratoluenesulfonic acid, and organic carboxylic acids such as acetic acid, oxalic acid and maleic acid can be used. These catalysts can also be used as a mixture of two or more kinds. Of these, oxalic acid is preferably used.
【００１６】触媒の使用量は、特に制限されものではな
く、その種類によっても異なるが、短時間で反応が完了
でき、しかもその反応が穏和で反応制御が容易な点で、
芳香族炭化水素の１００重量部当たり０．１〜５．０重
量部用いるのが好ましい。The amount of the catalyst used is not particularly limited and varies depending on the kind thereof, but the reaction can be completed in a short time, the reaction is mild, and the reaction control is easy.
It is preferable to use 0.1 to 5.0 parts by weight per 100 parts by weight of the aromatic hydrocarbon.
【００１７】上記反応は無溶媒下で行ってもよいが、有
機溶媒の存在下で行ってもよい。有機溶媒としては、公
知慣用のものがいずれも使用できるが、例えばトルエ
ン、キシレン、ジメチルホルムアミド、ジメチルスルホ
キシド、ソルベッソ等が挙げられる。有機溶媒として
は、芳香族炭化水素を溶解できるものが好適である。The above reaction may be carried out in the absence of a solvent, or may be carried out in the presence of an organic solvent. As the organic solvent, any conventionally known organic solvent can be used, and examples thereof include toluene, xylene, dimethylformamide, dimethylsulfoxide, and Solvesso. As the organic solvent, those capable of dissolving aromatic hydrocarbons are suitable.
【００１８】本発明のエポキシ樹脂硬化剤を得るために
は、フェノール性水酸基を含有する化合物（Ａ）とし
て、その単量体とホルムアルデヒド等が重縮合した縮重
合体を使用し（Ｂ）を反応させる場合と、先にフェノー
ル性水酸基を有する単量体に化合物（Ｂ）を反応させて
からホルムアルデヒド等で重縮合する場合とでは同じ性
能の物ができるが、効率的に合成するには前者の方法が
望ましい。To obtain the epoxy resin curing agent of the present invention, a condensation polymer obtained by polycondensing the monomer and formaldehyde etc. is used as the compound (A) containing a phenolic hydroxyl group, and (B) is reacted. The same performance can be obtained when the compound (B) is first reacted with the monomer having a phenolic hydroxyl group and then polycondensed with formaldehyde or the like, but in the case of efficient synthesis, Method is preferred.
【００１９】本発明に係るエポキシ樹脂用硬化剤は、単
独でエポキシ樹脂硬化剤として用いることによりエポキ
シ樹脂組成物を得ることができるが、必要に応じて公知
慣用のエポキシ樹脂硬化剤を併用することができる。The epoxy resin curing agent according to the present invention can be used alone as an epoxy resin curing agent to obtain an epoxy resin composition. If necessary, a known and commonly used epoxy resin curing agent may be used in combination. You can
【００２０】公知慣用のエポキシ樹脂硬化剤としては、
例えばジシアンジアミド、ポリアルキレンポリアミン、
ポリアミドポリアミン、マンニッヒ生成物、フェノール
ノボラック樹脂、オルソクレゾールノボラック樹脂、ナ
フトールノボラック樹脂、臭素化フェノールノボラック
樹脂、ポリビニルフェノール、ジシクロペンタジエン・
フェノール付加物等が挙げられる。Known and commonly used epoxy resin curing agents include
For example, dicyandiamide, polyalkylene polyamine,
Polyamide polyamine, Mannich product, phenol novolac resin, orthocresol novolac resin, naphthol novolac resin, brominated phenol novolac resin, polyvinylphenol, dicyclopentadiene
Examples thereof include phenol adducts.
【００２１】本発明に係るエポキシ樹脂組成物を調製す
るに当たり用いるエポキシ樹脂は、特に制限されるもの
ではないが、例えばビスフェノールＦやビスフェノール
Ａ等のビスフェノール類を出発原料とするビスフェノー
ルジグリシジルエーテル型エポキシ樹脂およびそのハロ
ゲン化物、通常のフェノールノボラック樹脂、オルソク
レゾールノボラック樹脂、臭素化フェノールノボラック
樹脂を出発原料とするノボラック型多官能エポキシ樹脂
およびそのハロゲン化物、ジフェニルメタンジアミンテ
トラグリシジルエーテル、シクロヘキサンジアミンテト
ラグリシジルエーテル等のグリシジルアミン型多官能エ
ポキシ樹脂を始め、ポリエチレングリコールジグリシジ
ルエーテル、エポキシ化ＳＢＲ、エポキシ化大豆油等の
脂肪族エポキシ樹脂等が挙げられる。The epoxy resin used for preparing the epoxy resin composition according to the present invention is not particularly limited, but for example, a bisphenol diglycidyl ether type epoxy starting from bisphenols such as bisphenol F and bisphenol A is used as a starting material. Resins and their halides, ordinary phenol novolac resins, orthocresol novolac resins, novolak-type polyfunctional epoxy resins starting from brominated phenol novolac resins and their halides, diphenylmethanediamine tetraglycidyl ether, cyclohexanediamine tetraglycidyl ether, etc. Glycidyl amine type polyfunctional epoxy resin, polyethylene glycol diglycidyl ether, epoxidized SBR, epoxidized soybean oil and other aliphatic epoxy resin Etc. The.
【００２２】エポキシ樹脂組成物の配合割合は、組成配
合物によって異なるが、一般的に硬化剤たるフェノール
樹脂のフェノール性水酸基と、エポキシ樹脂のエポキシ
基の割合を当量比にて配合すべきものである。The mixing ratio of the epoxy resin composition varies depending on the composition mixing, but generally, the ratio of the phenolic hydroxyl group of the phenol resin as the curing agent and the epoxy group of the epoxy resin should be mixed in an equivalent ratio. .
【００２３】尚、エポキシ樹脂組成物を硬化架橋させる
際の硬化促進剤としては、一般的に用いられているもの
が使用することができるが、例えばＮーメチルイミダゾ
ールのごときイミダゾール類、トリエチルアミンのよう
な３級アミン類、トリフェニルフォスフィンのようなリ
ン系化合物等が挙げられる。As the curing accelerator for curing and crosslinking the epoxy resin composition, generally used ones can be used. For example, imidazoles such as N-methylimidazole and triethylamine can be used. And tertiary amines, phosphorus compounds such as triphenylphosphine, and the like.
【００２４】硬化物として高度物性が要求される場合に
は、本発明に係るエポキシ樹脂硬化剤と、それにエピハ
ロヒドリンを反応せしめて得られるエポキシ樹脂とを組
み合わせることも可能である。この組み合わせは、電気
絶縁積層板を製造するのに特に適した組成である。When the cured product is required to have a high degree of physical properties, the epoxy resin curing agent according to the present invention can be combined with an epoxy resin obtained by reacting it with epihalohydrin. This combination is a composition that is particularly suitable for making electrically insulating laminates.
【００２５】また本発明のエポキシ樹脂組成物には、分
子中にビニル基、（メタ）アクリロイル基等を有する化
合物、並びに必要に応じてこれらを重合しうる熱重合開
始剤や光重合開始剤を添加して、活性化エネルギーと熱
とを併用して組成物の硬化を行うこともできる。Further, the epoxy resin composition of the present invention contains a compound having a vinyl group, a (meth) acryloyl group, etc. in the molecule, and a thermal polymerization initiator or a photopolymerization initiator capable of polymerizing these, if necessary. In addition, the composition can be cured by using activation energy and heat in combination.
【００２６】分子中にビニル基、（メタ）アクリロイル
基等を有する化合物としては、例えばエポキシ樹脂に
（メタ）アクリル酸を付加させた構造のいわゆるエポキ
シアクリレートや、ジビニルベンゼン、アルキルジビニ
ルベンゼン、ジアリルフタレート等の芳香族ジビニル化
合物、グリセロールジアリルエーテルやトリメチロール
プロパントリアクリレート等の脂肪族ジビニル化合物、
スチレン、メチルスチレン、エチルスチレン、モノブロ
モスチレン等の芳香族モノビニル化合物、（メタ）アク
リル酸メチルエステル、（メタ）アクリル酸ステアリル
エステル、（メタ）アクリル酸、Ｎ−メチロール（メ
タ）アクリルアミド、γ−メルカプトプロピルトリメト
キシシラン等の脂肪族モノビニル化合物等を挙げること
ができる。Examples of the compound having a vinyl group, a (meth) acryloyl group or the like in the molecule include a so-called epoxy acrylate having a structure obtained by adding (meth) acrylic acid to an epoxy resin, divinylbenzene, alkyldivinylbenzene, diallyl phthalate. Such as aromatic divinyl compounds, glycerol diallyl ether and trimethylolpropane triacrylate, etc., aliphatic divinyl compounds,
Aromatic monovinyl compounds such as styrene, methylstyrene, ethylstyrene and monobromostyrene, (meth) acrylic acid methyl ester, (meth) acrylic acid stearyl ester, (meth) acrylic acid, N-methylol (meth) acrylamide, γ- Examples thereof include aliphatic monovinyl compounds such as mercaptopropyltrimethoxysilane.
【００２７】本発明のエポキシ樹脂組成物には、必要に
応じて充填剤、カップリング剤、難燃剤、滑剤、離型
剤、可塑剤、着色剤、増粘剤等の各種添加剤を添加して
用いてもよい。If desired, various additives such as a filler, a coupling agent, a flame retardant, a lubricant, a release agent, a plasticizer, a colorant, a thickener, etc. are added to the epoxy resin composition of the present invention. You may use it.
【００２８】本発明に係る合成樹脂をエポキシ樹脂硬化
剤として使用すると、その硬化物は吸水性、低誘電率
性、耐衝撃性、耐熱性能等が向上する。本発明に係るエ
ポキシ樹脂組成物は、例えば銅張り電絶積層板及びその
前駆体たるプリプレグ、被覆材、コーティング剤、成形
材料、ＩＣ封止材等、従来通常のノボラック系樹脂をエ
ポキシ樹脂硬化剤として使用してきた用途分野において
性能を向上させることが期待できるものである。When the synthetic resin according to the present invention is used as an epoxy resin curing agent, the cured product has improved water absorption, low dielectric constant, impact resistance, heat resistance and the like. The epoxy resin composition according to the present invention is a conventional epoxy resin hardener containing a conventional novolac resin such as a copper-clad laminated plate and its precursor prepreg, a coating material, a coating agent, a molding material, and an IC sealing material. It is expected that the performance will be improved in the field of application that has been used as.
【００２９】一方本発明に係るエポキシ樹脂用硬化剤
は、例えばヘキサメチレンテトラミン等の硬化剤と組み
合わせて鋳物用結合剤、研削砥石用結合剤、ガラス繊維
や炭素繊維用結合材、耐火物用結合剤、ブレーキライニ
ング用結合剤、クラッチフェーシング用結合剤、家庭用
航空機用壁装材、断熱材、フェノールフォーム用原料、
浴槽、防水パン、流し台、波板、貯水漕、プレジャーボ
ート用材料としても使用できる。On the other hand, the curing agent for epoxy resin according to the present invention is combined with a curing agent such as hexamethylenetetramine, for example, a binder for castings, a binder for grinding wheels, a binder for glass fibers and carbon fibers, a binder for refractories. Agents, binders for brake linings, binders for clutch facings, wall materials for household aircraft, heat insulating materials, raw materials for phenol foam,
It can also be used as a material for bathtubs, waterproof pans, sinks, corrugated boards, water tanks, and pleasure boats.
【００３０】[0030]
【実施例】以下に合成例と実施例をあげて本発明を説明
する。なお例中の部および％はすべて重量基準とする。The present invention will be described below with reference to Synthesis Examples and Examples. All parts and percentages in the examples are on a weight basis.
【００３１】実施例１ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４つ口３リットルフラスコに、メタクレゾール１０８
ｇ、溶媒としてキシレン１５ｇ、触媒として蓚酸を０．
５ｇ加え、１２０℃まで昇温した。滴下ロートより４１
％ホルムアルデヒド水溶液１００ｇをＤＤ法にて３時間
かけて滴下し、重縮合物１２０ｇが得られた。これに、
温度を１３０℃に昇温し留出水がなくなった後、純度９
６％ジビニルベンゼン２０ｇ（不純物はエチルスチレ
ン）を３時間かけて滴下した後、１時間反応させた。２
００℃まで昇温し減圧蒸留を１時間行った。反応容器よ
り取り出し、数平均分子量２５００のノボラックタイプ
の黄色塊状の合成樹脂を得た。Example 1 Metacresol 108 was placed in a 4-neck 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel.
g, xylene as a solvent 15 g, and oxalic acid as a catalyst at 0.
5 g was added and the temperature was raised to 120 ° C. 41 from the dropping funnel
% Aqueous formaldehyde solution was added dropwise by the DD method over 3 hours to obtain 120 g of polycondensate. to this,
After the temperature was raised to 130 ° C and there was no distilled water, the purity was 9
20 g of 6% divinylbenzene (impurity is ethylstyrene) was added dropwise over 3 hours, and then the reaction was carried out for 1 hour. 2
The temperature was raised to 00 ° C. and vacuum distillation was performed for 1 hour. The product was taken out of the reaction vessel, and a novolac-type yellow lump-shaped synthetic resin having a number average molecular weight of 2,500 was obtained.
【００３２】得られた合成樹脂を２００℃に加温して溶
融させた後、この溶液に対し予め加温（１００℃）して
おいたエポキシ樹脂である、エピクロン８５０（大日本
インキ化学工業株式会社製）を６７％混合し均一になっ
たところで１５０℃に冷却した。エポキシ樹脂の硬化促
進剤であるＮーメチルイミダゾール０．１部を加えて直
ちに攪拌し３ｍｍ厚に注形した。１８０℃にて２時間熱
処理して硬化物を得た。The obtained synthetic resin is heated to 200 ° C. to be melted, and then the solution is preheated (100 ° C.) to an epoxy resin, Epiclon 850 (Dainippon Ink and Chemicals Co., Ltd.). 67%) was mixed and cooled to 150 ° C. when uniform. 0.1 part of N-methylimidazole, which is a curing accelerator for the epoxy resin, was added and immediately stirred to cast to a thickness of 3 mm. A heat treatment was performed at 180 ° C. for 2 hours to obtain a cured product.
【００３３】実施例２ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４つ口３リットルフラスコに、オルソクレゾール１０８
ｇ、溶媒としてキシレン１５ｇ、触媒として蓚酸を０．
５ｇ加え、１２０℃まで昇温した。滴下ロートより４１
％ホルムアルデヒド水溶液１００ｇをＤＤ法にて３時間
かけて滴下し、重縮合物１２０ｇが得られた。これに、
温度を１３０℃に昇温し留出水がなくなった後、純度９
６％ジビニルベンゼン２０ｇ（不純物はエチルスチレ
ン）を３時間かけて滴下した後、１時間反応させた。２
００℃まで昇温し減圧蒸留を１時間行った。反応容器よ
り取り出し、数平均分子量２２００のノボラックタイプ
の黄色塊状の合成樹脂を得た。Example 2 Orthocresol 108 was placed in a 4-neck 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel.
g, xylene as a solvent 15 g, and oxalic acid as a catalyst at 0.
5 g was added and the temperature was raised to 120 ° C. 41 from the dropping funnel
% Aqueous formaldehyde solution was added dropwise by the DD method over 3 hours to obtain 120 g of polycondensate. to this,
After the temperature was raised to 130 ° C and there was no distilled water, the purity was 9
20 g of 6% divinylbenzene (impurity is ethylstyrene) was added dropwise over 3 hours, and then the reaction was carried out for 1 hour. 2
The temperature was raised to 00 ° C. and vacuum distillation was performed for 1 hour. The product was taken out of the reaction container, and a novolac-type yellow lump-shaped synthetic resin having a number average molecular weight of 2,200 was obtained.
【００３４】得られた合成樹脂を２００℃に加温して溶
融させた後、この溶液に対し予め加温（１００℃）して
おいたエポキシ樹脂である、エピクロン８５０（大日本
インキ化学工業株式会社製）を６７％混合し均一になっ
たところで１５０℃に冷却した。エポキシ樹脂の硬化促
進剤であるＮーメチルイミダゾール０．１部を加えて直
ちに攪拌し３ｍｍ厚に注形した。１８０℃にて２時間熱
処理して硬化物を得た。After the obtained synthetic resin is heated to 200 ° C. to be melted, the solution is preheated (100 ° C.) to an epoxy resin, Epicron 850 (Dainippon Ink and Chemicals Co., Ltd.). 67%) was mixed and cooled to 150 ° C. when uniform. 0.1 part of N-methylimidazole, which is a curing accelerator for the epoxy resin, was added and immediately stirred to cast to a thickness of 3 mm. A heat treatment was performed at 180 ° C. for 2 hours to obtain a cured product.
【００３５】実施例３ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４つ口３リットルフラスコに、オルソクレゾール５４ｇ
とｐクレゾール５４ｇ、溶媒としてキシレン１５ｇ、触
媒として蓚酸を０．５ｇ加え、１２０℃まで昇温した。
滴下ロートより４１％ホルムアルデヒド水溶液１２０ｇ
をＤＤ法にて３時間かけて滴下し、重縮合物１２０ｇが
得られた。これに温度を１３０℃まで昇温し留出水がな
くなった後、純度９６％ジビニルベンゼン２０ｇ（不純
物はエチルスチレン）を３時間かけて滴下した後、１時
間反応させた。２００℃まで昇温し減圧蒸留を１時間行
った。反応容器より取り出し、数平均分子量２０００の
ノボラックタイプの黄色塊状の合成樹脂を得た。Example 3 In a four-necked 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel, 54 g of orthocresol was added.
And p-cresol 54 g, xylene 15 g as a solvent, and oxalic acid 0.5 g as a catalyst were added, and the temperature was raised to 120 ° C.
120g of 41% formaldehyde aqueous solution from dropping funnel
Was added dropwise over 3 hours by the DD method to obtain 120 g of a polycondensate. After the temperature was raised to 130 ° C. to remove distilled water, 20 g of 96% pure divinylbenzene (impurity was ethylstyrene) was added dropwise over 3 hours, and then the reaction was carried out for 1 hour. The temperature was raised to 200 ° C. and vacuum distillation was performed for 1 hour. The product was taken out of the reaction container, and a novolac-type yellow lump-shaped synthetic resin having a number average molecular weight of 2000 was obtained.
【００３６】得られた合成樹脂を２００℃に加温して溶
融させた後、この溶液に対し予め加温（１００℃）して
おいたエポキシ樹脂である、エピクロン８５０（大日本
インキ化学工業株式会社製）を６７％混合し均一になっ
たところで１５０℃に冷却した。エポキシ樹脂の硬化促
進剤であるＮーメチルイミダゾール０．１部を加えて直
ちに攪拌し３ｍｍ厚に注形した。１８０℃にて２時間熱
処理して硬化物を得た。The synthetic resin thus obtained was heated to 200 ° C. and melted, and then the epoxy resin which had been preheated (100 ° C.) to this solution, Epicron 850 (Dainippon Ink and Chemicals Co., Ltd. 67%) was mixed and cooled to 150 ° C. when uniform. 0.1 part of N-methylimidazole, which is a curing accelerator for the epoxy resin, was added and immediately stirred to cast to a thickness of 3 mm. A heat treatment was performed at 180 ° C. for 2 hours to obtain a cured product.
【００３７】比較例１ 一般的な合成方法にて製造されたノボラック型フェノー
ル樹脂フェノライトＴＤ−２０９０（大日本インキ化学
工業株式会社製，数平均分子量９００）を１５０℃に加
温して溶融させた後、この溶液に対し予め加温（１００
℃）しておいたエポキシ樹脂である、エピクロン８５０
（大日本インキ化学工業株式会社製）を６７％混合し均
一にした。エポキシ樹脂の硬化促進剤であるＮーメチル
イミダゾール０．１部を加えて直ちに攪拌し３ｍｍ厚に
注形した。１８０℃にて２時間熱処理して硬化物を得
た。Comparative Example 1 Novolak type phenolic resin Phenolite TD-2090 (manufactured by Dainippon Ink and Chemicals, Inc., number average molecular weight 900) produced by a general synthesis method is heated to 150 ° C. and melted. Then, preheat (100
Epoxylon 850 which is the epoxy resin
(Manufactured by Dainippon Ink and Chemicals, Inc.) was mixed 67% to make it uniform. 0.1 part of N-methylimidazole, which is a curing accelerator for the epoxy resin, was added and immediately stirred to cast to a thickness of 3 mm. A heat treatment was performed at 180 ° C. for 2 hours to obtain a cured product.
【００３８】比較例２ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４口フラスコにｍクレゾール１０８ｇ、触媒として蓚酸
を０．５ｇ加え、１２０℃まで昇温した。滴下ロートよ
り純度９６％ジビニルベンゼン１００ｇ（不純物はエチ
ルスチレン）を３時間かけて滴下した後、１時間反応さ
せた。２００℃まで昇温し減圧蒸留を１時間行った。反
応容器より取り出し、数平均分子量９００のノボラック
タイプの黄色塊状の合成樹脂を得た。Comparative Example 2 108 g of m-cresol and 0.5 g of oxalic acid as a catalyst were added to a 4-neck flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, and the temperature was raised to 120 ° C. 100 g of 96% pure divinylbenzene (impurity is ethylstyrene) was added dropwise from the dropping funnel over 3 hours, and then the reaction was carried out for 1 hour. The temperature was raised to 200 ° C. and vacuum distillation was performed for 1 hour. The product was taken out of the reaction vessel, and a novolac-type yellow lump-shaped synthetic resin having a number average molecular weight of 900 was obtained.
【００３９】得られた合成樹脂を１５００℃に加温して
溶融させた後、この溶液に対し予め加温（１００℃）し
ておいたエポキシ樹脂である、エピクロン８５０（大日
本インキ化学工業株式会社製）を６７％混合し均一にし
た。エポキシ樹脂の硬化促進剤であるＮーメチルイミダ
ゾール０．１部を加えて直ちに攪拌し３ｍｍ厚に注形し
た。１８０℃にて２時間熱処理して硬化物を得た。After the obtained synthetic resin is heated to 1500 ° C. to be melted, the solution is preheated (100 ° C.) to the epoxy resin, Epiclon 850 (Dainippon Ink and Chemicals Co., Ltd.). (Manufactured by the company) was mixed 67% to make it uniform. 0.1 part of N-methylimidazole, which is a curing accelerator for the epoxy resin, was added and immediately stirred to cast to a thickness of 3 mm. A heat treatment was performed at 180 ° C. for 2 hours to obtain a cured product.
【００４０】参考例１ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４つ口３リットルフラスコに、メタクレゾール１０８
ｇ、溶媒としてキシレン１５ｇ、触媒として蓚酸を０．
５ｇ加え、１２０℃まで昇温した。滴下ロートより４１
％ホルムアルデヒド水溶液１４０ｇをＤＤ法にて３時間
かけて滴下したが、樹脂の分子量の増加と共に溶液粘度
が異常に高くなり攪拌不能になった。Reference Example 1 Metacresol 108 was placed in a 4-neck 3 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g, xylene as a solvent 15 g, and oxalic acid as a catalyst at 0.
5 g was added and the temperature was raised to 120 ° C. 41 from the dropping funnel
% Aqueous formaldehyde solution was added dropwise by the DD method over 3 hours, but as the molecular weight of the resin increased, the solution viscosity became abnormally high and stirring became impossible.
【００４１】参考例２ 攪拌機、コンデンサー、温度計及び滴下ロートを備えた
４つ口３リットルフラスコに、メタクレゾール１０８
ｇ、溶媒としてキシレン２００ｇ、触媒として蓚酸を
０．５ｇ加え、１２０℃まで昇温した。滴下ロートより
４１％ホルムアルデヒド水溶液１４０ｇをＤＤ法にて３
時間かけて滴下した。１時間反応させた後、２００℃ま
で昇温し減圧蒸留を１時間行った。反応容器より取り出
し、数平均分子量１７００のノボラックタイプの黄色塊
状の合成樹脂を得た。Reference Example 2 Metacresol 108 was placed in a 4-neck 3 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel.
g, 200 g of xylene as a solvent, and 0.5 g of oxalic acid as a catalyst were added, and the temperature was raised to 120 ° C. From the dropping funnel, add 140 g of 41% formaldehyde aqueous solution by DD method to 3
It was dropped over time. After reacting for 1 hour, the temperature was raised to 200 ° C. and vacuum distillation was performed for 1 hour. The product was taken out of the reaction container, and a novolac-type yellow lump-shaped synthetic resin having a number average molecular weight of 1,700 was obtained.
【００４２】参考例１及び２からわかるように、一般的
に高分子量のノボラック樹脂を合成しようとしても、溶
液粘度が高くなり合成できず、数平均分子量１５００以
上の高分子量ノボラックを得るには、合成中の溶液粘度
を下げ、攪拌可能にせしめるため、非常に多くの溶媒を
必要とする。As can be seen from Reference Examples 1 and 2, even if an attempt was made to synthesize a high molecular weight novolak resin, the solution viscosity became high and the synthesis could not be performed. In order to obtain a high molecular weight novolac having a number average molecular weight of 1500 or more, Very high amounts of solvent are required to reduce the solution viscosity and allow stirring during synthesis.
【００４３】これに対し各実施例のノボラック樹脂は溶
媒量が少なくても溶液粘度が低いため合成が簡単であ
る、しかも得られたノボラックは数平均分子量２０００
以上のものである。On the other hand, the novolak resins of the respective examples are easy to synthesize because the solution viscosity is low even when the amount of solvent is small, and the obtained novolaks have a number average molecular weight of 2000.
That's all.
【００４４】[0044]
【表１】 *1）アイゾット *2）沸騰水中５時間放置後の重量増加率 表１からわかるように、本発明によるエポキシ樹脂硬化
物は、従来の汎用ノボラックを硬化剤として用いた硬化
物（比較例１）に比較した場合、非常に低吸水性である
ばかりでなく耐衝撃性，低誘電率性にも優れている。[Table 1] * 1) Izot * 2) Weight increase rate after standing in boiling water for 5 hours As can be seen from Table 1, the epoxy resin cured product of the present invention is a cured product using a conventional general-purpose novolak as a curing agent (Comparative Example 1). Compared with the above, not only it has very low water absorption but also excellent impact resistance and low dielectric constant.
【００４５】さらに吸水性を改良した特開平５−７８４
５７号公報記載の硬化剤を用いた硬化物（比較例２）に
比べ、吸水性が同レベルで且つ耐熱性が著しく優れてい
ることがわかる。JP-A-5-784 with improved water absorption
It can be seen that the water absorption is at the same level and the heat resistance is remarkably excellent as compared with the cured product using the curing agent described in JP-A-57 (Comparative Example 2).
【００４６】また、フェノール性水酸基を含む炭化水素
（Ａ）としては、３官能性のメタクレゾールとホルムア
ルデヒドの重縮合物（実施例１）とするよりは２官能性
のオルソクレゾールやパラクレゾールとホルムアルデヒ
ドの重縮合物（実施例２，３）とした方が耐衝撃性に優
れることがわかる。As the hydrocarbon (A) containing a phenolic hydroxyl group, a bifunctional orthocresol or paracresol and formaldehyde are used rather than a polycondensation product of trifunctional metacresol and formaldehyde (Example 1). It can be seen that the polycondensate of (Examples 2 and 3) is more excellent in impact resistance.
【００４７】さらに、フェノール性水酸基を含む炭化水
素（Ａ）としては、オルソクレゾール単独とホルムアル
デヒドの重縮合物（実施例２）とするよりはオルソクレ
ゾールとパラクレゾールの混合物とホルムアルデヒドの
重縮合物（実施例３）とした方が耐熱性が若干優れるこ
とがわかる。Further, as the hydrocarbon (A) containing a phenolic hydroxyl group, a polycondensate of orthocresol and para-cresol and a polycondensate of formaldehyde (rather than a polycondensate of orthocresol alone and formaldehyde (Example 2)). It can be seen that the heat resistance is slightly better in Example 3).
【００４８】[0048]
【発明の効果】本発明のエポキシ樹脂硬化剤とエポキシ
樹脂とからなるエポキシ樹脂組成物は、耐熱性、低吸水
性、耐衝撃性、低誘電率性に優れるものであり、特に電
気、電子材料に用いると製品の信頼性を高めることが可
能となる。The epoxy resin composition comprising the epoxy resin curing agent and the epoxy resin of the present invention is excellent in heat resistance, low water absorption, impact resistance and low dielectric constant, and is particularly useful for electrical and electronic materials. When used for, it is possible to increase the reliability of the product.
Claims (6)
水素（Ａ）と一般式（I）で示される化合物（Ｂ）とを
付加してなり、１５００以上の数平均分子量を有する合
成樹脂からなるエポキシ樹脂硬化剤。 【化１】 Ｈ2Ｃ＝ＣＨ−Ｘ−ＣＨ＝ＣＨ2 （I） （式中、Ｘは二価の電子供与性官能基を示す。）1. A synthetic resin obtained by adding an aromatic hydrocarbon (A) having a phenolic hydroxyl group and a compound (B) represented by the general formula (I) and having a number average molecular weight of 1500 or more. Epoxy resin curing agent. Embedded image H 2 C═CH—X—CH═CH 2 (I) (In the formula, X represents a divalent electron-donating functional group.)
であることを特徴とする請求項１記載の硬化剤。2. The curing agent according to claim 1, wherein the divalent electron-donating functional group is a phenylene group.
水素（Ａ）が、２官能性フェノ−ルとホルムアルデヒド
との重縮合物であることを特徴とする請求項１又は２記
載の硬化剤。3. The curing according to claim 1, wherein the aromatic hydrocarbon (A) containing a phenolic hydroxyl group is a polycondensation product of a bifunctional phenol and formaldehyde. Agent.
水素（Ａ）と一般式で示される化合物（Ｂ）との割合
が、重量比で５０〜４０：５０〜６０であることを特徴
とする請求項１又は２記載の硬化剤。 【化２】 Ｈ2Ｃ＝ＣＨ−Ｘ−ＣＨ＝ＣＨ2 （I） （式中、Ｘは二価の電子供与性官能基を示す。）4. The weight ratio of the aromatic hydrocarbon (A) containing a phenolic hydroxyl group to the compound (B) represented by the general formula is 50 to 40:50 to 60. The curing agent according to claim 1. Embedded image H 2 C═CH—X—CH═CH 2 (I) (In the formula, X represents a divalent electron-donating functional group.)
水素（Ａ）と一般式で示される化合物（Ｂ）との割合
が、重量比で９５〜５０：５〜５０であることを特徴と
する請求項３項記載の硬化剤。 【化３】 Ｈ2Ｃ＝ＣＨ−Ｘ−ＣＨ＝ＣＨ2 （I） （式中、Ｘは二価の電子供与性官能基を示す。）5. The ratio of the aromatic hydrocarbon (A) containing a phenolic hydroxyl group to the compound (B) represented by the general formula is 95 to 50: 5 to 50 by weight. The curing agent according to claim 3. Embedded image H 2 C═CH—X—CH═CH 2 (I) (In the formula, X represents a divalent electron-donating functional group.)
脂硬化剤を配合してなるエポキシ樹脂組成物。6. An epoxy resin composition obtained by mixing the epoxy resin and the epoxy resin curing agent according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP742396A JPH09194575A (en) | 1996-01-19 | 1996-01-19 | Epoxy resin curing agent and epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP742396A JPH09194575A (en) | 1996-01-19 | 1996-01-19 | Epoxy resin curing agent and epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09194575A true JPH09194575A (en) | 1997-07-29 |
Family
ID=11665468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP742396A Pending JPH09194575A (en) | 1996-01-19 | 1996-01-19 | Epoxy resin curing agent and epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09194575A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002220437A (en) * | 2000-11-27 | 2002-08-09 | Dainippon Ink & Chem Inc | Thermosetting resin composition and material for sealing semiconductor |
| US6594973B1 (en) * | 1999-11-08 | 2003-07-22 | Romala Stone, Inc. | Method of packaging and selling natural stone |
| JP2008531785A (en) * | 2005-02-25 | 2008-08-14 | エスアイ・グループ・インコーポレイテッド | Modified novolac resin for use as a tackifier |
| WO2014051149A1 (en) * | 2012-09-28 | 2014-04-03 | 住友金属鉱山株式会社 | Conductive adhesive |
| KR20150111850A (en) * | 2014-03-26 | 2015-10-06 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
-
1996
- 1996-01-19 JP JP742396A patent/JPH09194575A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6594973B1 (en) * | 1999-11-08 | 2003-07-22 | Romala Stone, Inc. | Method of packaging and selling natural stone |
| US7240791B2 (en) | 1999-11-08 | 2007-07-10 | Romala Stone, Inc. | Method of packaging and selling natural stone |
| JP2002220437A (en) * | 2000-11-27 | 2002-08-09 | Dainippon Ink & Chem Inc | Thermosetting resin composition and material for sealing semiconductor |
| JP2008531785A (en) * | 2005-02-25 | 2008-08-14 | エスアイ・グループ・インコーポレイテッド | Modified novolac resin for use as a tackifier |
| KR101285959B1 (en) * | 2005-02-25 | 2013-07-12 | 에스아이 그룹 인코포레이티드 | Modified novolak resin for use as tackifier |
| WO2014051149A1 (en) * | 2012-09-28 | 2014-04-03 | 住友金属鉱山株式会社 | Conductive adhesive |
| JPWO2014051149A1 (en) * | 2012-09-28 | 2016-08-25 | 住友金属鉱山株式会社 | Conductive adhesive |
| KR20150111850A (en) * | 2014-03-26 | 2015-10-06 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Modified polyvalent hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
| JP2015187190A (en) * | 2014-03-26 | 2015-10-29 | 新日鉄住金化学株式会社 | Modified polyhydric hydroxy resin, epoxy resin, epoxy resin composition and cured product thereof |
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