TW201437254A - Method for manufacturing polyhydroxy polyether resin, polyhydroxy polyether resin, its resin composition and its cured product - Google Patents

Method for manufacturing polyhydroxy polyether resin, polyhydroxy polyether resin, its resin composition and its cured product Download PDF

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TW201437254A
TW201437254A TW103111410A TW103111410A TW201437254A TW 201437254 A TW201437254 A TW 201437254A TW 103111410 A TW103111410 A TW 103111410A TW 103111410 A TW103111410 A TW 103111410A TW 201437254 A TW201437254 A TW 201437254A
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resin
group
epoxy resin
compound
carbon atoms
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TWI623566B (en
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Hidenori Nozawa
Masao Gunji
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Nippon Steel & Sumikin Chem Co
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G59/40—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 curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs

Abstract

Object of this invention is to provide a manufacturing method of a polyhydroxy polyether resin, and a resin composition containing the polyhydroxy polyether resin, the polyhydroxy polyether resin has good solubility and film-forming properties, and high heat resistance and adhesion, and has moderate viscosity and good liquidity as an adhesive. In this invention, bifunctional epoxy resins (X), dihydric phenol compounds (Y), a compound having three or more functional groups selected from an epoxy group or an active hydrogen group capable of reacting with an epoxy group (A), and a compound having one functional group (B) are as reaction raw materials, a polymerization reaction is performed in the presence of a catalyst, any (mass ratio) of the polyhydroxy polyether resin with a weight-average molecular weight of 15, 000 to 100, 000 is more than 0 and equal to or less than 0.05.

Description

多羥基聚醚樹脂之製造方法，多羥基聚醚樹脂，其樹脂組成物及其硬化物 Method for producing polyhydroxy polyether resin, polyhydroxy polyether resin, resin composition thereof and cured product thereof

本發明係關於多羥基聚醚樹脂之製造方法、及以該製造方法所得之多羥基聚醚樹脂，以及使用該多羥基聚醚樹脂之樹脂組成物、接著劑、及電性積層板。 The present invention relates to a method for producing a polyhydroxy polyether resin, a polyhydroxy polyether resin obtained by the production method, and a resin composition, an adhesive, and an electrical laminate using the polyhydroxy polyether resin.

近年來，由於對地球環境的顧慮，針對電性積層板所使用之焊料之無鉛化之要求高漲。由於不含鉛的焊料之熔點較以往使用的Sn/Pb共晶焊料高，故迴焊處理溫度係伴隨著無鉛化而從以往的240℃上昇至260℃。因此，對積層板所使用之有機材料要求進一步提升耐熱性。 In recent years, due to concerns about the global environment, the demand for lead-free solder for electrical laminates has increased. Since the melting point of the lead-free solder is higher than that of the conventional Sn/Pb eutectic solder, the reflow processing temperature rises from the conventional 240 ° C to 260 ° C with lead-free. Therefore, the organic material used for the laminate is required to further improve the heat resistance.

對電性積層板之薄型化、小型化之要求亦高漲。因此，就所使用之半導體晶片的組裝方式而言，使用金屬導線連接之以往的打線接合(wire bonding)方式被取代，而在晶片電極上形成稱為突狀體(bump)之突起電極，將基板電極與晶片電極隔著突狀體而直接連接之覆晶 (flip-chip)連接方式係備受注目。 The demand for thinning and miniaturization of electrical laminates is also increasing. Therefore, in the assembly method of the semiconductor wafer to be used, a conventional wire bonding method using metal wire bonding is replaced, and a bump electrode called a bump is formed on the wafer electrode. A flip chip in which a substrate electrode and a wafer electrode are directly connected via a protrusion The (flip-chip) connection method is attracting attention.

就覆晶連接方式而言，已知使用焊料突狀 體之方式、使用金屬突狀體與導電性接著劑之方式、熱壓接方式、超音波方式等。該等方式中，會有因晶片與基板之熱膨張係數差使熱壓力集中於連接部分而導致連接信賴性降低之問題。欲防止此種連接信賴性之降低，一般填充晶片與基板之間隙之底部填膠(under fill)係由樹脂所形成。因藉由分散至底部填膠而緩和熱壓力，故可提升連接可靠性。 In the case of a flip chip connection, it is known to use a solder bump The form of the body, the use of a metal protrusion and a conductive adhesive, a thermocompression bonding method, an ultrasonic method, and the like. In these methods, there is a problem that the thermal stress is concentrated on the connection portion due to the difference in thermal expansion coefficient between the wafer and the substrate, resulting in a decrease in connection reliability. To prevent such a reduction in connection reliability, the underfill of the gap between the filled wafer and the substrate is generally formed of a resin. Since the heat stress is alleviated by being dispersed to the bottom of the glue, the connection reliability can be improved.

就形成底部填膠之方法而言，有在連接晶 片與基板後將液狀樹脂注入晶片與基板之間隙之方法；或者將底部填膠所成之樹脂預先供給於基板上或晶片上，而在連接晶片與基板之步驟中亦完成形成底部填膠之方法。 In terms of the method of forming the underfill, there is a connection crystal a method of injecting a liquid resin into the gap between the wafer and the substrate after the sheet and the substrate; or pre-feeding the resin formed by the bottom filling on the substrate or the wafer, and forming the underfill in the step of connecting the wafer and the substrate The method.

注入液狀樹脂之方法中，將樹脂填充於100 μm以下之狹窄間隙中需要長時間，而有導致生產性降低之傾向。另一方面，預先供給底部填膠之樹脂之方法，可分為使用NCP(Non Conductive Paste)等膏狀樹脂之方法(專利文獻1)、使用NCF(Non Conductive Film)等薄膜狀樹脂之方法(專利文獻2)，而使用膏狀樹脂之方法中，有殘留空隙(void)、使用薄型晶片時發生之晶片背面的污染等問題。若藉由使用薄膜狀樹脂之方法，則容易處理且可簡化生產製程。 In the method of injecting a liquid resin, the resin is filled in 100 A narrow gap of less than μm takes a long time, and there is a tendency to cause a decrease in productivity. On the other hand, the method of supplying the resin of the underfill in advance can be classified into a method of using a paste resin such as NCP (Non Conductive Paste) (Patent Document 1), and a method of using a film-like resin such as NCF (Non Conductive Film) ( Patent Document 2), in the method using a paste resin, there are problems such as residual voids and contamination of the back surface of the wafer which occurs when a thin wafer is used. If the method of using a film-like resin is used, it is easy to handle and the production process can be simplified.

用於形成底部填膠之樹脂，可廣泛使用環 氧樹脂等含三維交聯性樹脂成分之樹脂組成物。特別在使 用薄膜狀樹脂之方法時，將可單獨形成薄膜之樹脂與三維交聯性樹脂組合而可使用確保良好的薄膜形成性之樹脂組成物。 A resin used to form the underfill, which can be widely used. A resin composition containing a three-dimensional crosslinkable resin component such as an oxygen resin. Especially making In the case of a film-form resin, a resin which can form a film alone and a three-dimensional crosslinkable resin are combined, and a resin composition which ensures good film formability can be used.

與三維交聯性樹脂組合之樹脂，主要可使用苯氧樹脂、聚醯亞胺樹脂等熱可塑性樹脂(專利文獻3)。 A resin which is combined with a three-dimensional crosslinkable resin can be mainly a thermoplastic resin such as a phenoxy resin or a polyimide resin (Patent Document 3).

另外，就緩和環氧樹脂的內部應力而強韌化之目的而言，已知於含環氧樹脂之樹脂組成物中分散液狀橡膠、交聯橡膠、核殼型橡膠粒子之方法(非專利文獻1)。然而，已知與不使用橡膠者相比，分散橡膠之硬化物之玻璃轉移溫度降低，在要求高耐熱性之領域中，會成為可靠性降低之原因。為了提升橡膠分散系統中之玻璃轉移溫度，可思及增加環氧樹脂的交聯密度之方法。然而此情況下，會有使橡膠分散的效果降低而硬化物變脆，同時吸水率增加，從而導致信賴性降低之問題。 Further, a method of dispersing a liquid rubber, a crosslinked rubber, or a core-shell type rubber particle in a resin composition containing an epoxy resin for the purpose of tempering the internal stress of the epoxy resin (non-patent) Document 1). However, it is known that the glass transition temperature of the cured product of the dispersion rubber is lowered as compared with the case where no rubber is used, and the reliability is lowered in the field requiring high heat resistance. In order to increase the glass transition temperature in the rubber dispersion system, a method of increasing the crosslinking density of the epoxy resin can be considered. However, in this case, there is a problem that the effect of dispersing the rubber is lowered and the cured product becomes brittle, and the water absorption rate is increased, resulting in a decrease in reliability.

另一方面，不降低玻璃轉移溫度便使環氧樹脂強韌化之方法，已知有將聚醚碸、聚醚醯亞胺等稱為工程塑膠之高耐熱性熱可塑樹脂與環氧樹脂摻合，於硬化物中形成相分離構造之方法。然而此情況下，為了使含量少之熱可塑性樹脂成分成為基質(matrix)(連續相)，而有失去環氧樹脂原本的電特性等之可能性(非專利文獻2)。 On the other hand, a method of strengthening and toughening an epoxy resin without lowering the glass transition temperature is known as a high heat resistant thermoplastic resin and an epoxy resin which are called polyether oxime, polyether sulfimine, etc., which are called engineering plastics. A method of forming a phase separation structure in a hardened material. In this case, however, in order to make the thermoplastic resin component having a small content a matrix (continuous phase), there is a possibility that the original electrical properties of the epoxy resin are lost (Non-Patent Document 2).

又，亦提案有摻合玻璃轉移溫度為130℃以上之多羥基聚醚樹脂。然而此情況下，由於樹脂黏度較大，故欲降低至實用黏度則需使用大量稀釋成分。若該稀釋成分的使用量多，則可能使接著劑層的耐濕性變差，絕緣可 靠性降低(專利文獻4、5)。 Further, a polyhydroxy polyether resin having a glass transition temperature of 130 ° C or higher is also proposed. However, in this case, since the viscosity of the resin is large, it is necessary to use a large amount of diluted components in order to reduce the practical viscosity. If the amount of the diluted component used is large, the moisture resistance of the adhesive layer may be deteriorated, and the insulation may be The reliability is lowered (Patent Documents 4 and 5).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開第2001-127215號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-127215

[專利文獻2]日本特開第2004-315688號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-315688

[專利文獻3]國際公開第01/059007號小冊 [Patent Document 3] International Publication No. 01/059007

[專利文獻4]日本特開第2002-327162號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-327162

[專利文獻5]日本特開第2007-009183號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-009183

[專利文獻6]日本專利第3747221號 [Patent Document 6] Japanese Patent No. 3747221

[專利文獻7]日本專利第3809273號 [Patent Document 7] Japanese Patent No. 3908273

[專利文獻8]日本特開第2004-233095號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2004-233095

[專利文獻9]日本特開第1999-181047號公報 [Patent Document 9] Japanese Patent Laid-Open Publication No. 1999-181047

[非專利文獻] [Non-patent literature]

[非專利文獻1]「高分子微粒子改質劑所致之環氧樹脂高韌性化與剝離接著強度提升」，岸肇及其他3人，日本接著學會誌，2004年，vol.40，No.5，p.177-183 [Non-patent Document 1] "High-toughness of epoxy resin and improvement of peeling strength by polymer microparticle modifier", Kishiwa and three others, Japan Society of Learning, 2004, vol. 40, No. 5, p.177-183

[非專利文獻2]「環氧樹脂摻合」，村上惇及其他1人，日本接著學會誌，2001年，vol.37，No.11，p.459-468 [Non-Patent Document 2] "Epoxy Resin Blending", Murakami and 1 other person, Japan Society of Learning, 2001, vol. 37, No. 11, p. 459-468

[非專利文獻3]「總論環氧樹脂第1卷基礎篇I」，ISBN4-9900150-1-0C3058，p.19-40 [Non-Patent Document 3] "General Epoxy Resin Volume 1 Basics I", ISBN 4-9900150-1-0C3058, p.19-40

以往，將晶片與基板隔著底部填膠之接著 劑而連接時，會有在高溫高濕下接著劑與晶片或基板之界面的接著力降低之問題。又，以往，甚至要求改善在高溫高濕下之連接可靠性。例如，溫度週期試驗條件下，藉由於連接部產生源自晶片與基板之熱膨張係數差之熱壓力，而會有連接阻力增大、產生接著劑剝離之情況。又，半導體封裝中，由於在高溫高濕條件吸濕後進行迴焊處理，因接著劑中所吸收之水分急遽膨脹，而會有連接阻力增大、產生接著劑剝離之情況。 In the past, the wafer and the substrate were glued through the bottom. When the agent is connected, there is a problem that the adhesion of the interface between the adhesive and the wafer or the substrate is lowered under high temperature and high humidity. Further, in the past, it has been required to improve the connection reliability under high temperature and high humidity. For example, under the temperature cycle test condition, the thermal stress caused by the difference in thermal expansion coefficient between the wafer and the substrate is generated by the joint portion, and the connection resistance is increased to cause peeling of the adhesive. Further, in the semiconductor package, since the reflow process is performed after moisture absorption under high temperature and high humidity conditions, the moisture absorbed by the adhesive rapidly expands, and the connection resistance increases and the adhesive peeling occurs.

使用玻璃轉移溫度為130℃以上之多羥基 聚醚樹脂之接著劑系統係有高耐熱性，但由於熔融黏度較大，有為了降低至實用黏度而使用需求以上之反應性稀釋劑等稀釋成分之問題。若該反應性稀釋劑等稀釋成分之使用量多，則有使接著劑層的耐濕性變差，絕緣可靠性降低之情況。 Use a polyhydroxy group with a glass transition temperature of 130 ° C or higher The adhesive system of the polyether resin has high heat resistance. However, since the melt viscosity is large, there is a problem in that a component such as a reactive diluent or more is required to be used in order to reduce the practical viscosity. When the amount of the diluted component such as the reactive diluent is large, the moisture resistance of the adhesive layer may be deteriorated, and the insulation reliability may be lowered.

本發明係有鑒於上述課題而成者，本發明 之目的係提供一種多羥基聚醚樹脂，其可獲得具有良好的薄膜形成性與高耐熱性，並且黏度較低而作為接著劑使用時，不需要需求以上之稀釋成分，故即使在暴露於高溫高濕環境下之後仍可維持高接著力之樹脂組成物。 The present invention has been made in view of the above problems, and the present invention has been made. The purpose is to provide a polyhydroxy polyether resin which can obtain good film formability and high heat resistance, and has low viscosity and is used as an adhesive, and does not require the above diluted components, so even when exposed to high temperature A resin composition that maintains a high adhesion after a high humidity environment.

又，本發明之目的係提供一種樹脂組成 物，其具有良好的薄膜形成性與高耐熱性，並且作為接著劑使用時，即使在暴露於高溫高濕環境下之後仍可維持高接著力。 Moreover, the object of the present invention is to provide a resin composition It has good film formability and high heat resistance, and when used as an adhesive, maintains a high adhesion even after exposure to a high temperature and high humidity environment.

又，本發明之目的係提供一種電性積層板 用構件之接著劑，其可顯現高耐熱性及在暴露於高溫高濕環境下之後之高接著力，並且可提升連接可靠性。 Moreover, the object of the present invention is to provide an electrical laminate With the adhesive of the member, it can exhibit high heat resistance and high adhesion after exposure to a high temperature and high humidity environment, and can improve connection reliability.

再者，本發明之目的係提供一種電性積層 板，其中，電性積層板用構件彼此間以高接著力接著，並且改善連接可靠性。 Furthermore, the object of the present invention is to provide an electrical laminate The board in which the members for the electric laminate are followed by a high adhesion force with each other and improves the connection reliability.

本發明係提案，在使用2官能環氧樹脂與2 元酚化合物製造多羥基聚醚樹脂時，藉由規定具有3個以上官能基之化合物與僅具有1個官能基之化合物之量，而即使導入茀骨架等高耐熱骨架仍不會變為高黏度之較低黏度之多羥基聚醚樹脂。 The present invention proposes the use of a bifunctional epoxy resin and 2 When a polyhydroxy polyether resin is produced from a phenolic compound, by specifying a compound having three or more functional groups and a compound having only one functional group, even if a high heat resistant skeleton such as an anthracene skeleton is introduced, it does not become a high viscosity. The lower viscosity polyhydroxy polyether resin.

亦即，本發明係多羥基聚醚樹脂之製造方 法，其特徵為，將2官能環氧樹脂(X)、2元酚化合物(Y)、具有3個以上選自環氧基或與環氧基有反應性之含有活性氫之基中之官能基之化合物(A)、及具有1個該官能基之化合物(B)作為反應原料，在觸媒存在下進行聚合反應，製造重量平均分子量為15,000至100,000之多羥基聚醚樹脂之方法，其中，反應原料中之化合物(A)與(B)之量係滿足下述式：0<A/(X+Y+A+B)≦0.05 That is, the present invention is a manufacturer of a polyhydroxy polyether resin. The method is characterized in that a bifunctional epoxy resin (X), a divalent phenol compound (Y), and a functional group having three or more active hydrogen-containing groups selected from an epoxy group or an epoxy group a method of producing a polyhydroxyl polyether resin having a weight average molecular weight of from 15,000 to 100,000 by reacting a compound (A) having a compound (A) and a compound (B) having one such functional group as a reaction raw material in the presence of a catalyst. The amount of the compounds (A) and (B) in the reaction raw material satisfies the following formula: 0 < A / (X + Y + A + B) ≦ 0.05

0<B/(X+Y+A+B)≦0.05(X、Y、A、及B分別係2官能環氧樹脂(X)、2元酚化合物(Y)、化合物(A)、及化合物(B)之進料量(質量))。 0<B/(X+Y+A+B)≦0.05 (X, Y, A, and B are a bifunctional epoxy resin (X), a divalent phenol compound (Y), a compound (A), and a compound, respectively. (B) Feed amount (mass)).

本發明之多羥基聚醚樹脂之製造方法的較 佳態樣如下所示。 Comparison of the method for producing the polyhydroxy polyether resin of the present invention The best aspect is shown below.

(1)前述具有3個以上官能基之化合物(A)係3官能以上之多官能環氧樹脂、3元以上之多元酚化合物、或該兩者。 (1) The compound (A) having three or more functional groups is a polyfunctional epoxy resin having three or more functional groups, a polyhydric phenol compound having three or more members, or both.

(2)前述具有1個官能基之化合物(B)係1官能環氧樹脂、1元酚化合物、或該兩者。 (2) The compound (B) having one functional group is a monofunctional epoxy resin, a monovalent phenol compound, or both.

(3)前述2官能環氧樹脂(X)係由以2元酚化合物為主成分之酚化合物與表鹵醇(epihalohydrin)之反應所得之環氧樹脂，作為副生成物而含有之3官能以上之多官能環氧樹脂(A)之含量為0.05至5質量%，且作為副生成物而含有之1官能環氧樹脂類(B)之含量為0.05至5質量%。 (3) The bifunctional epoxy resin (X) is an epoxy resin obtained by reacting a phenol compound containing a divalent phenol compound as a main component and epihalohydrin, and a trifunctional or higher compound as a by-product. The content of the polyfunctional epoxy resin (A) is 0.05 to 5% by mass, and the content of the monofunctional epoxy resin (B) contained as a by-product is 0.05 to 5% by mass.

(4)前述2官能環氧樹脂類(X)係下述者中 之至少任一者：a)由下述通式(1)所示之酚化合物與表鹵醇之反應所得之環氧樹脂、b)下述通式(2)所示之酚化合物與表鹵醇之反應所得之環氧樹脂、或c)下述通式(3)所示之酚化合物與表鹵醇之反應所得之環氧樹脂。 (4) The above-mentioned bifunctional epoxy resin (X) is as follows At least one of: a) an epoxy resin obtained by reacting a phenol compound represented by the following formula (1) with an epihalohydrin, b) a phenol compound represented by the following formula (2), and an epihalide An epoxy resin obtained by the reaction of an alcohol or c) an epoxy resin obtained by reacting a phenol compound represented by the following formula (3) with an epihalohydrin.

(式(1)至(3)中，R1至R3分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基)。 (In the formulae (1) to (3), R1 to R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a ring having a carbon number of 6; An alkyl group, an aryl group which may have a substituent, or an aralkyl group which may have a substituent).

(5)前述2元酚化合物(Y)係以2元酚化合物 (Y)中之50至100質量%而含有選自上述通式(1)、通式(2)或通式(3)所示之酚化合物之至少一者。 (5) The above 2-valent phenol compound (Y) is a 2-valent phenol compound At least one of the phenol compounds selected from the above formula (1), formula (2) or formula (3) is contained in the range of 50 to 100% by mass in (Y).

又，本發明係一種多羥基聚醚樹脂，其特 徵係由上述多羥基聚醚樹脂之製造方法所製造。 Moreover, the present invention is a polyhydroxy polyether resin, which is characterized by The system is produced by the above-described method for producing a polyhydroxy polyether resin.

該多羥基聚醚樹脂之較佳態樣係由示差掃描熱量測定所得之玻璃轉移溫度為130℃以上，且240℃之熔融黏度未達10,000Pa‧s。 A preferred aspect of the polyhydroxy polyether resin is a glass transition temperature of from 130 ° C or more as measured by differential scanning calorimetry, and a melt viscosity of less than 10,000 Pa s at 240 ° C.

又，本發明係一種樹脂組成物，其含有上 述多羥基聚醚樹脂、與三維交聯性樹脂成分，其質量比係多羥基聚醚樹脂/三維交聯性樹脂成分=1/99至99/1。 Further, the present invention is a resin composition containing the upper The polyhydroxy polyether resin and the three-dimensional crosslinkable resin component have a mass ratio of polyhydroxy polyether resin/three-dimensional crosslinkable resin component = 1/99 to 99/1.

該樹脂組成物之較佳實施態樣係前述三維交聯性樹脂成分為環氧樹脂與硬化劑，且係藉由加熱及/或光照射而硬化者。 In a preferred embodiment of the resin composition, the three-dimensional crosslinkable resin component is an epoxy resin and a hardener, and is cured by heating and/or light irradiation.

又，本發明係一種絕緣薄膜，其特徵係將 上述樹脂組成物在支撐基底薄膜上形成薄膜狀。再者，本發明係一種附有印刷配線板用樹脂之金屬箔，其特徵係將上述樹脂組成物塗佈於金屬箔而成。又，本發明係一種預浸體，其特徵係將上述樹脂組成物塗佈及/或含浸於包含有纖維之薄片狀補強基材。 Moreover, the present invention is an insulating film characterized by The above resin composition forms a film on the support base film. Furthermore, the present invention relates to a metal foil with a resin for a printed wiring board, which is characterized in that the resin composition is applied to a metal foil. Further, the present invention is a prepreg characterized in that the resin composition is coated and/or impregnated into a sheet-like reinforcing substrate comprising fibers.

又，本發明係一種將上述樹脂組成物硬化 而得之硬化物。再者，本發明係一種電性積層板，其係由上述樹脂組成物所得之電性積層板，又係由上述絕緣薄膜所得之電性積層板，更係由上述附有印刷配線板用樹脂之金屬箔所得之電性積層板，又係由上述預浸體所得之電性積層板。 Further, the present invention is a method of hardening the above resin composition And get hardened. Furthermore, the present invention is an electrical laminate which is an electrical laminate obtained from the above resin composition, and an electrical laminate obtained from the above-mentioned insulating film, and more preferably a resin for printed wiring board. The electrical laminated board obtained from the metal foil is an electrical laminated board obtained from the above prepreg.

藉由本發明之多羥基聚醚樹脂之製造方法 所得之多羥基聚醚樹脂，因吸濕性小、流動性佳，而在含有該樹脂之樹脂組成物時，不需大量使用反應性稀釋材等使吸濕性變差之成分。因此，有高耐熱性，並且作為接著劑使用時，即使在暴露於高溫高濕環境下之後仍可維持高接著力。 Method for producing polyhydroxy polyether resin by the present invention The polyhydroxy polyether resin obtained has a small hygroscopic property and good fluidity, and when the resin composition containing the resin is contained, it is not necessary to use a large amount of a component such as a reactive diluent to deteriorate hygroscopicity. Therefore, it has high heat resistance and, when used as an adhesive, maintains a high adhesion even after exposure to a high-temperature and high-humidity environment.

第1圖係環氧樹脂(1)之液相層析圖表。 Figure 1 is a liquid chromatogram of epoxy resin (1).

以下，詳細說明本發明之較佳實施形態。惟，本發明不受限於以下實施形態。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

多羥基聚醚樹脂之製造，已知有由2元酚化合物與表鹵醇之直接反應之方法、由2官能環氧樹脂與2元酚化合物之加成聚合反應之方法，本發明所用之多羥基聚醚樹脂係由2官能環氧樹脂與2元酚化合物之加成聚合反應而得者。然後，使少量之具有3個以上官能基之化合物(A)與具有1個官能基之化合物(B)共存。以下，有時將具有3個以上官能基之化合物(A)簡稱為化合物(A)，將具有1個官能基之化合物(B)簡稱為化合物(B)。 For the production of a polyhydroxy polyether resin, a method of directly reacting a divalent phenol compound with an epihalohydrin, a method of addition polymerization of a bifunctional epoxy resin and a divalent phenol compound, and many methods used in the present invention are known. The hydroxypolyether resin is obtained by addition polymerization of a bifunctional epoxy resin and a divalent phenol compound. Then, a small amount of the compound (A) having three or more functional groups is allowed to coexist with the compound (B) having one functional group. Hereinafter, the compound (A) having three or more functional groups may be simply referred to as the compound (A), and the compound (B) having one functional group may be simply referred to as the compound (B).

本發明之多羥基聚醚樹脂係由使2官能環氧樹脂(X)與2元酚化合物(Y)共存、化合物(A)與化合物(B)共存，且在胺系、咪唑系、三苯基鏻、鏻鹽系等公知觸媒存在下反應而得者。若將2官能環氧樹脂(X)之使用量作為X，將2元酚化合物之使用量作為Y，則該反應中之X/Y 之較佳當量比係1/0.94至1.06，更佳係1/0.96至1.04，最佳係1/0.975至1.025。超過該範圍之當量比便無法獲得預定之重量平均分子量。 The polyhydroxy polyether resin of the present invention is obtained by coexisting a bifunctional epoxy resin (X) with a divalent phenol compound (Y), a compound (A) and a compound (B), and an amine system, an imidazole system, and a triphenyl group. It is obtained by reacting in the presence of a known catalyst such as a base or a sulfonium salt. When the amount of the bifunctional epoxy resin (X) is used as X and the amount of the divalent phenol compound used is Y, X/Y in the reaction is used. The preferred equivalent ratio is from 1/0.94 to 1.06, more preferably from 1/0.96 to 1.04, and most preferably from 1/0.975 to 1.025. Exceeding the equivalent ratio of the range, the predetermined weight average molecular weight cannot be obtained.

本發明中所謂的官能基係選自環氧基或與 環氧基有反應性之含有活性氫之基。由於該等環氧基與酚性羥基有反應性，而含有活性氫之基與環氧基有反應性，因此若在反應系統中，作為反應原料而參予，且為一定範圍之量，則改良所得之多羥基聚醚樹脂之特性。因此，官能基可為環氧基，亦可為含有活性氫之基中之任一者，在包含具有環氧基之化合物、與具有含有活性氫之基之化合物之兩化合物時，以兩者之合計作為化合物(A)或化合物(B)之量。例如，單環氧樹脂類為1質量%且單酚化合物類為2質量%時，化合物類(B)之含量為3質量%。 The so-called functional group in the present invention is selected from epoxy groups or An epoxy group reactive reactive hydrogen-containing group. Since the epoxy group is reactive with a phenolic hydroxyl group, and the active hydrogen-containing group is reactive with the epoxy group, if it is used as a reaction raw material in the reaction system and is in a certain range, The properties of the resulting polyhydroxy polyether resin are improved. Therefore, the functional group may be an epoxy group, or may be any one of active hydrogen-containing groups, in the case of a compound containing an epoxy group and a compound having a compound containing an active hydrogen, The total amount is the amount of the compound (A) or the compound (B). For example, when the monoepoxy resin is 1% by mass and the monophenol compound is 2% by mass, the content of the compound (B) is 3% by mass.

就含有活性氫之基而言，有與環氧基具有 反應性之官能基之羥基、胺基、羧基、活性磷等官能基，較佳之官能基係酚性羥基。 In the case of a group containing an active hydrogen, it has an epoxy group A functional group such as a hydroxyl group, an amine group, a carboxyl group or a reactive phosphorus of a reactive functional group, preferably a functional group is a phenolic hydroxyl group.

相對於X+Y+A+B之合計，具有3個以上官 能基之化合物(A)之使用量之較佳範圍為0.05至5質量%，更佳範圍係0.2至3質量%，最佳係0.3至2質量%。 在此，A係化合物(A)之使用量，B係2元酚化合物(B)之使用量。 Compared with X+Y+A+B, there are more than 3 officials The amount of the compound (A) to be used is preferably from 0.05 to 5% by mass, more preferably from 0.2 to 3% by mass, most preferably from 0.3 to 2% by mass. Here, the amount of the A-based compound (A) used, and the amount of the B-based divalent phenol compound (B).

化合物(A)較5質量%多時，無論化合物(B)之使用量在哪個範圍，仍無法調控聚合反應時之3維交聯反應而有不溶化之虞。又，若不含化合物(A)而進行聚合反應，則無 法獲得較低黏度之多羥基聚醚樹脂。 When the amount of the compound (A) is more than 5% by mass, the three-dimensional crosslinking reaction at the time of the polymerization reaction cannot be regulated and the insolubilization is ineffective regardless of the range of the amount of the compound (B) used. Further, if the polymerization reaction is carried out without the compound (A), then The method obtains a lower viscosity polyhydroxy polyether resin.

相對於X+Y+A+B之合計，具有1個官能基 之化合物(B)之使用量之較佳範圍為0.05至5質量%，更佳範圍係0.1至4質量%，最佳係0.2至3質量%。化合物(B)較5質量%多時，無論具有3個以上官能基之化合物類(A)之含量在哪個範圍，所得之多羥基聚醚樹脂之低分子量成分增加，失去可塑性而無法獲得充分的薄膜性能。又，若不含化合物(B)而進行聚合反應，則無法調控3維交聯反應而有不溶化之虞。 One functional group relative to the total of X+Y+A+B The compound (B) is preferably used in an amount of from 0.05 to 5% by mass, more preferably from 0.1 to 4% by mass, most preferably from 0.2 to 3% by mass. When the amount of the compound (B) is more than 5% by mass, the content of the compound (A) having three or more functional groups is in a range, and the low molecular weight component of the obtained polyhydroxy polyether resin increases, and plasticity is lost, and sufficient content cannot be obtained. Film properties. Further, when the polymerization reaction is carried out without the compound (B), the three-dimensional crosslinking reaction cannot be regulated and the insolubilization is not obtained.

又，本發明之多羥基聚醚樹脂，重量平均 分子量Mw為15,000至100,000之範圍。在此，重量平均分子量係指聚苯乙烯換算重量平均分子量。Mw未達15,000，則失去熱可塑性而無法獲得充分的薄膜性能，超過100,000則會極度高黏度化，樹脂之處理會變困難。從薄膜性能與低黏度化這兩個層面來看，較佳係15,000至70,000，更佳係20,000至60,000，最佳係25,000至40,000。 Mw可藉由調控環氧基與OH基之莫耳比等手段而變化。 Further, the polyhydroxy polyether resin of the present invention has an average weight The molecular weight Mw is in the range of 15,000 to 100,000. Here, the weight average molecular weight means a polystyrene-equivalent weight average molecular weight. When the Mw is less than 15,000, the thermoplasticity is lost and sufficient film properties are not obtained, and if it exceeds 100,000, the viscosity is extremely high, and the treatment of the resin becomes difficult. From the two aspects of film properties and low viscosity, it is preferably from 15,000 to 70,000, more preferably from 20,000 to 60,000, and most preferably from 25,000 to 40,000. Mw can be varied by means of adjusting the molar ratio of the epoxy group to the OH group.

說明本發明所使用之2官能環氧樹脂(X)。一般而言，使2官能環氧樹脂類與2元酚化合物類反應，而製造高分子量環氧樹脂(亦即，所謂的苯氧樹脂)時之2官能環氧樹脂之純度較佳係96質量%以上。若未達96質量%，單環氧樹脂多時，則反應不進行而無法高分子量化。又，已知未達96質量%，3官能以上之多官能環氧樹脂多時，反應時係進行3維網目構造化，則反應調控變困難(專 利文獻6、專利文獻7)。 The bifunctional epoxy resin (X) used in the present invention will be described. In general, a 2-functional epoxy resin is reacted with a divalent phenol compound to produce a high molecular weight epoxy resin (that is, a so-called phenoxy resin). The purity of the bifunctional epoxy resin is preferably 96 mass. %the above. If it is less than 96% by mass, if the amount of the single epoxy resin is large, the reaction does not proceed and the polymer cannot be polymerized. Further, it is known that when the amount of the polyfunctional epoxy resin is less than 96% by mass and the trifunctional or higher functional group is used, the three-dimensional network structure is formed during the reaction, and the reaction regulation becomes difficult. Li document 6, patent document 7).

另一方面，已知一般以酚化合物與表鹵醇 製造環氧樹脂時，除了主反應所得之環氧樹脂以外尚會生成多種副生成物(非專利文獻3)。 On the other hand, it is known that phenol compounds and epihalohydrin are generally used. When an epoxy resin is produced, a plurality of by-products are formed in addition to the epoxy resin obtained by the main reaction (Non-Patent Document 3).

由2元酚化合物類與表氯醇之反應之副生 成物之中，在製造本發明之多羥基聚醚樹脂上，就必須考慮其含量之副生成物而言，可列舉(1)水解性氯體、(2)1,2-二醇體、(3)與反應溶媒之醇成分之加成體、(4)成為高分子量體之2級羥基與環氧基之加成反應物。 By-product of the reaction between 2-phenolic compounds and epichlorohydrin Among the preparations, in the production of the polyhydroxy polyether resin of the present invention, it is necessary to consider (1) a hydrolyzable chlorine, (2) a 1,2-diol, and a by-product of the content. (3) an addition product to the alcohol component of the reaction solvent, and (4) an addition reaction product of a secondary hydroxyl group and an epoxy group which are high molecular weight bodies.

該等副生成物可由液相層析而簡單地定性/ 定量(專利文獻8)。理論上，該等副生成物應具有重複體，但n=0體以外係在液相層析中為檢測極限以下而可無視之含量。 These by-products can be simply characterized by liquid chromatography. Quantification (Patent Document 8). In theory, the by-products should have repeats, but the n=0 body is a content that can be ignored in liquid chromatography below the detection limit.

該等副生成物中，具有3個以上官能基之化 合物(A)，亦即，3官能以上之多官能環氧樹脂類係(4)於高分子量體生成之2級羥基與環氧基之加成反應物(以下，稱為成分A1)，具有1個官能基之化合物(B)，亦即，單環氧樹脂類係(1)水解性氯體(以下，稱為成分B1)、(2)1,2-二醇體(以下，稱為成分B2)、(3)與反應溶媒之醇成分之加成體(以下，稱為成分B3)。 The by-products have three or more functional groups The compound (A), that is, a trifunctional or higher polyfunctional epoxy resin (4) is an addition reaction product of a second-order hydroxyl group and an epoxy group formed by a high molecular weight body (hereinafter referred to as component A1). The compound (B) having one functional group, that is, the monoepoxy resin type (1) hydrolyzable chlorine (hereinafter referred to as component B1) and (2) 1,2-diol (hereinafter referred to as It is an additive of the components B2) and (3) and the alcohol component of the reaction solvent (hereinafter referred to as component B3).

又，市售之2元酚化合物之中，亦有含有作 為不純物之如雙酚F之3元以上的多元酚化合物類者。由該等酚化合物與表鹵醇所得之環氧樹脂中含有3官能以上之多官能環氧樹脂。該等成分相當於化合物(A)。以下，原 料酚中所含之3元以上之多元酚類稱為成分A2，環氧樹脂中所生成之3官能以上之多官能環氧樹脂稱為成分A3。 Also, among the commercially available 2-phenol compounds, there are also It is a polyphenol compound of 3 or more bisphenol F which is an impurity. The epoxy resin obtained from the phenol compound and the epihalohydrin contains a trifunctional or higher polyfunctional epoxy resin. These components correspond to the compound (A). Below, the original The polyhydric phenol which is more than ternary or more contained in the phenol is referred to as component A2, and the trifunctional or higher functional epoxy resin formed in the epoxy resin is referred to as component A3.

2官能環氧樹脂所含之作為不純物之3官能 以上之多官能環氧樹脂(成分A3)在多數的情況係以通常精製步驟而去除，但亦有為了步驟的簡化、提升環氧樹脂反應性而刻意殘留之情況。又，2元酚化合物類所含之作為不純物之3元以上之多元酚化合物(成分A2)在多數的情況係以通常精製步驟而去除，但亦有為了步驟的簡化而殘留之情況。本發明中，具有3個以上官能基之化合物(A)之含量，係不區分2官能環氧樹脂類之不純物成分、2元酚化合物類之不純物成分、反應時添加之多官能成分，而以其總和來算。惟，化合物(A)不限於上述成分A1、A2、A3，係包含具有3個以上上述官能基之任意的其他的3官能以上之化合物。再者，將在檢測極限以下之情況當作0。 2-functional epoxy resin as a non-purity The above polyfunctional epoxy resin (component A3) is usually removed by a usual purification step in many cases, but it may be intentionally left for the simplification of the steps and the improvement of the epoxy resin reactivity. Further, in the case where the divalent phenol compound (component A2) having three or more members as the impurity contained in the divalent phenol compound is removed in the usual purification step, it may remain in order to simplify the steps. In the present invention, the content of the compound (A) having three or more functional groups is such that the impurity component of the bifunctional epoxy resin, the impurity component of the divalent phenol compound, and the polyfunctional component added during the reaction are not distinguished. The sum is counted. However, the compound (A) is not limited to the above components A1, A2, and A3, and includes any other trifunctional or higher compound having three or more of the above functional groups. Furthermore, the case below the detection limit is taken as 0.

2官能環氧樹脂類所含之作為不純物之單 環氧樹脂類係以通常精製步驟而幾乎去除，但有以環氧樹脂之改質為目的而刻意殘留許多之情況。例如，專利文獻9揭示增加1,2-二醇體(成分B2)之製造方法。 a single-function epoxy resin containing a single impurity The epoxy resin is almost removed by a usual purification step, but there are many cases where a lot of intention is left for the purpose of modifying the epoxy resin. For example, Patent Document 9 discloses a method of producing a 1,2-diol (component B2).

又，以十二酸等單羧酸、對第三丁基酚等 單酚類為代表之具有1價含有活性氫之基之化合物與2官能環氧樹脂之加成反應後所得之環氧樹脂類成為單環氧樹脂類(以下，稱為成分B4)。 Further, monocarboxylic acid such as dodecanoic acid, p-tert-butylphenol, etc. The epoxy resin obtained by the addition reaction of a compound having a monovalent active hydrogen-containing group and a bifunctional epoxy resin represented by a monophenol is a monoepoxy resin (hereinafter referred to as component B4).

本發明中，具有1個官能基之化合物類(B) 之含量係以包含下述者之總和來計算：2官能環氧樹脂類 之副生成成分、苯基環氧丙基醚等單環氧樹脂類、具有1價活性氫基之化合物類、由具有1價活性氫基之化合物類與2官能環氧樹脂類所生成之1官能環氧樹脂類(B)、2元酚化合物類之副生成成分、具有1價活性氫基之化合物類。惟，化合物(B)不限於上述成分B1、B2、B3、B4，係包含具有1個上述官能基之任意的其他的1官能之化合物。 In the present invention, a compound having one functional group (B) The content is calculated by the sum of the following: 2-functional epoxy resin a mono-epoxy resin such as a by-product, a phenylepoxypropyl ether, a compound having a monovalent active hydrogen group, a compound having a monovalent active hydrogen group, and a bifunctional epoxy resin. A functional epoxy resin (B), a by-product of a divalent phenol compound, and a compound having a monovalent active hydrogen group. However, the compound (B) is not limited to the above components B1, B2, B3, and B4, and includes any other monofunctional compound having one of the above functional groups.

例如，使用將2官能環氧樹脂：97.99質量 %、成分B1：0.05質量%、成分B2：0.5質量%、成分B3：0.5質量%、成分A1：1質量%之環氧樹脂95份(質量份，以下，相同)，及包含2官能環氧樹脂30質量%、與3官能以上之環氧樹脂70質量%所成之酚醛清漆環氧樹脂5份作為環氧樹脂(X)，將含有0.5質量%之作為不純物之3核體(3元酚化合物)之2元酚化合物99份作為2元酚化合物(Y)，而製造本發明之多羥基聚醚樹脂時，化合物(A)與化合物(B)之個別的含量係由計算而簡單地求得。亦即，具有3個以上官能基之化合物(A)為(1×95+70×5+0.5×99)/(95+5+99)=2.48質量%，具有1個官能基之化合物(B)為((0.05+0.5+0.5)×95+0×5+0×99)/(95+5+99)=0.50質量%。 For example, use a 2-functional epoxy resin: 97.99 mass %, component B1: 0.05% by mass, component B2: 0.5% by mass, component B3: 0.5% by mass, component A1:1% by mass of epoxy resin 95 parts (parts by mass, hereinafter the same), and 2-functional epoxy 5 parts of a novolak epoxy resin made of 30% by mass of a resin and 70% by mass of a trifunctional or higher epoxy resin as an epoxy resin (X), and containing 0.5% by mass of a 3 nucleus (trivalent phenol) as an impurity 99 parts of the divalent phenol compound of the compound) is used as the divalent phenol compound (Y), and when the polyhydroxy polyether resin of the present invention is produced, the individual contents of the compound (A) and the compound (B) are simply calculated by calculation. Got it. That is, the compound (A) having three or more functional groups is (1 × 95 + 70 × 5 + 0.5 × 99) / (95 + 5 + 99) = 2.48 mass%, and has one functional group (B) ) is ((0.05 + 0.5 + 0.5) × 95 + 0 × 5 + 0 × 99) / (95 + 5 + 99) = 0.50% by mass.

以往之多羥基聚醚樹脂之製造中，如同前 述，一般選擇使用無該等不純物之原料、或僅有可無視的程度的微量之量的原料。 In the manufacture of polyhydroxy polyether resins in the past, as before As described above, it is generally preferred to use a raw material having no such impurities or a trace amount of a raw material which can be ignored.

本發明之製造方法所使用之環氧樹脂(X)， 可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚茀型等雙酚型環氧樹脂、聯苯酚型環氧 樹脂、兒茶酚、間苯二酚、氫醌等單環2元酚之二環氧丙基醚、二羥基萘之二環氧丙基醚、2元醇之二環氧丙基醚、酞酸、異酞酸、四氫酞酸、六氫酞酸等2元羧酸之二環氧丙基醚之環氧樹脂，較佳係由通式(1)至(3)所示之酚化合物與表鹵醇之反應所得之雙酚茀型環氧樹脂、雙酚S型環氧樹脂、或聯苯酚型環氧樹脂。該等環氧樹脂可經烷基、芳基、醚基、酯基等無不良影響之取代基取代。該等環氧樹脂可併用複數種而使用。 The epoxy resin (X) used in the production method of the present invention, Examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol type epoxy resin such as a bisphenol type, and a biphenol type epoxy. Di-epoxypropyl ether of monocyclic divalent phenol such as resin, catechol, resorcinol or hydroquinone, diepoxypropyl ether of dihydroxynaphthalene, diepoxypropyl ether of dihydric alcohol, hydrazine An epoxy resin of a di-epoxypropyl ether of a divalent carboxylic acid such as an acid, isophthalic acid, tetrahydrofurfuric acid or hexahydrophthalic acid, preferably a phenol compound represented by the general formulae (1) to (3) A bisphenol quinone type epoxy resin, a bisphenol S type epoxy resin, or a biphenol type epoxy resin obtained by a reaction with an epihalohydrin. These epoxy resins may be substituted with substituents which are not adversely affected, such as an alkyl group, an aryl group, an ether group, or an ester group. These epoxy resins can be used in combination with a plurality of types.

就具體例而言，可列舉：EPOTOHTO ZX-1201 (新日鐵住金化學股份有限公司製雙酚茀型環氧樹脂)，EPOTOHTO TX-0710、EPOTOHTO TX-0902(新日鐵住金化學股份有限公司製雙酚S型環氧樹脂)，EPICLON EXA-1515(大日本化學工業股份有限公司製雙酚S型環氧樹脂)，jER YX4000H(三菱化學股份有限公司製聯苯基型環氧樹脂)，EPOTOHTO YD-128、EPOTOHTO YD-8125、EPOTOHTO YD-825GS(新日鐵住金化學股份有限公司製雙酚A型環氧樹脂)，EPOTOHTO YDF-170、EPOTOHTO YDF-8170、YDF-870GS(新日鐵住金化學股份有限公司製雙酚F型環氧樹脂)，YSLV-80XY(新日鐵住金化學股份有限公司製四甲基雙酚F型環氧樹脂)，EPOTOHTO YDC-1312(氫醌型環氧樹脂)，EPOTOHTO ZX-1355、EPOTOHTO ZX-1711(新日鐵住金化學股份有限公司製萘二酚型環氧樹脂)，YSLV-120TE(新日鐵住金化學股份有限公司製雙硫醚型環氧樹脂)，EPOTOHTO ZX-1684(新日鐵住金化學股份有限公 司製間苯二酚型環氧樹脂)，TX-0929、TX-0934、TX-1032(新日鐵住金化學股份有限公司製烷二醇型環氧樹脂)。 For specific examples, mention: EPOTOHTO ZX-1201 (Nippon Steel & Sumitomo Chemical Co., Ltd. made bisphenol oxime epoxy resin), EPOTOHTO TX-0710, EPOTOHTO TX-0902 (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol S type epoxy resin), EPICLON EXA- 1515 (D-phenol S-type epoxy resin manufactured by Dainippon Chemical Industry Co., Ltd.), jER YX4000H (biphenyl type epoxy resin manufactured by Mitsubishi Chemical Corporation), EPOTOHTO YD-128, EPOTOHTO YD-8125, EPOTOHTO YD- 825GS (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol A epoxy resin), EPOTOHTO YDF-170, EPOTOHTO YDF-8170, YDF-870GS (Nippon Steel & Sumitomo Chemical Co., Ltd. bisphenol F epoxy resin ), YSLV-80XY (Tetramethyl bisphenol F epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPOTOHTO YDC-1312 (hydrogen oxime epoxy resin), EPOTOHTO ZX-1355, EPOTOHTO ZX-1711 ( Nippon Steel & Sumitomo Chemical Co., Ltd. Naphthalene Diphenol Epoxy Resin), YSLV-120TE (Nissin Sumi Chemical Co., Ltd. Disulfide Epoxy Resin), EPOTOHTO ZX-1684 (Nippon Steel & Sumitomo Chemical Co., Ltd. Limited company Synthetic resorcinol type epoxy resin), TX-0929, TX-0934, TX-1032 (alkalidiol type epoxy resin manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).

又，2元酚化合物(Y)，可列舉雙酚A、雙酚F、雙酚B、雙酚D、雙酚S、雙酚茀等雙酚類、聯苯酚、兒茶酚、間苯二酚、氫醌、二羥基萘等酚化合物，較佳係通式(1)至(3)所示之雙酚茀、雙酚S、或聯苯酚。可以2元酚化合物(Y)中之50至100質量%而含有該等者中之至少1個。 Further, examples of the divalent phenol compound (Y) include bisphenols such as bisphenol A, bisphenol F, bisphenol B, bisphenol D, bisphenol S, and bisphenol oxime, biphenol, catechol, and isophthalene. The phenol compound such as phenol, hydroquinone or dihydroxynaphthalene is preferably a bisphenol hydrazine, a bisphenol S or a biphenol represented by the general formulae (1) to (3). At least one of these may be contained in an amount of 50 to 100% by mass of the divalent phenol compound (Y).

2元酚化合物可經烷基、芳基、醚基、酯基等無不良影響之取代基取代。該等2元酚化合物可併用複數種而使用。具體上，該等2元酚中較佳係4,4’-(9H-茀-9,9-二基)雙酚、雙酚S、3,3’,5,5’-四甲基-4,4’-二羥基二苯基碸、4,4’-聯苯酚、3,3’,5,5’-四甲基-4,4’-聯苯酚。 The divalent phenol compound may be substituted with a substituent which does not adversely affect the alkyl group, the aryl group, the ether group, the ester group or the like. These divalent phenol compounds can be used in combination with a plurality of kinds. Specifically, among the divalent phenols, 4,4'-(9H-fluorene-9,9-diyl)bisphenol, bisphenol S, 3,3', 5,5'-tetramethyl- 4,4'-dihydroxydiphenylanthracene, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-biphenol.

式(1)至(3)中，R1至R3分別獨立地表示氫 原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基。 In the formulae (1) to (3), R1 to R3 each independently represent hydrogen Atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, an aryl group which may have a substituent, or an aralkyl group which may have a substituent base.

可具有取代基之芳基，較佳可列舉碳數6至12之芳基，可具有取代基之芳烷基，較佳可列舉碳數7至13之芳基。 The aryl group which may have a substituent is preferably an aryl group having 6 to 12 carbon atoms, an aralkyl group having a substituent, and preferably an aryl group having 7 to 13 carbon atoms.

具體例，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己基等碳數1至6之直鏈或分支烷基，甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第二丁氧基、第三丁氧 基、正戊氧基、正己氧基、環己氧基等碳數1至6之烷氧基，環己基等碳數6之環狀烷基，苯基、萘基、甲苯基、三苯甲基、二甲苯基、茚基等可具有取代基之芳基，苯甲基、苯乙基、2-甲基苯甲基、3-甲基苯甲基、4-甲基苯甲基、2,6-二甲基苯甲基、3,5-二甲基苯甲基、α-甲基苯甲基等可具有取代基之芳烷基等之取代基，較佳取代基係甲基、乙基、第三丁基、甲氧基、乙氧基、環己基、苯基、α-甲基苯甲基。該等取代基可以1種亦可複數種取代。 Specific examples thereof include a carbon number of 1 to 6 such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a t-butyl group, a n-pentyl group, and a n-hexyl group. Linear or branched alkyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, third butoxy Alkyloxy group having 1 to 6 carbon atoms such as a group, n-pentyloxy group, n-hexyloxy group or cyclohexyloxy group, a cyclic alkyl group having 6 carbon atoms such as a cyclohexyl group, a phenyl group, a naphthyl group, a tolyl group and a triphenyl group. An aryl group which may have a substituent such as a benzyl group, a xylyl group or a fluorenyl group, a benzyl group, a phenethyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, 2 a substituent such as a 6-dimethylbenzyl group, a 3,5-dimethylbenzyl group or an α-methylbenzyl group which may have a substituent such as an aralkyl group, and a preferred substituent is a methyl group. Ethyl, tert-butyl, methoxy, ethoxy, cyclohexyl, phenyl, a-methylbenzyl. These substituents may be substituted in one type or in plural forms.

本發明之多羥基聚醚樹脂之製造方法中， 其合成反應之步驟中可使用溶媒，該溶媒只要是溶解多羥基聚醚樹脂，且對反應無不良影響者則可為任意者。例如，可列舉芳香族系烴、酮類、醯胺系溶媒、二醇醚類等。芳香族系烴之具體例，可列舉苯、甲苯、二甲苯等。酮類，可列舉丙酮、甲基乙基酮、甲基異丁基酮、2-庚酮、4-庚酮、2-辛酮、環己酮、乙醯基丙酮、二烷等。醯胺系溶媒之具體例，可列舉甲醯胺、N-甲基甲醯胺、N,N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、2-吡咯啶酮、N-甲基吡咯啶酮等。二醇醚類之具體例，可列舉乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丁基醚、乙二醇二甲基醚、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單正丁基醚、二乙二醇二甲基醚、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚、丙二醇單正丁基醚、丙二醇單甲基醚乙酸酯等。該等溶媒可併用2種以上。使用之溶媒之量可因應反應條件而適宜 地選擇，較佳係使固形分濃度成為35%至95%。又，反應中產生高黏性生成物時可在反應中途添加溶媒而繼續反應。反應結束後，溶媒可因應需要藉由蒸餾等而除去，亦可進一步追加。 In the method for producing a polyhydroxy polyether resin of the present invention, a solvent may be used in the step of the synthesis reaction, and the solvent may be any one as long as it dissolves the polyhydroxy polyether resin and does not adversely affect the reaction. For example, an aromatic hydrocarbon, a ketone, a guanamine-based solvent, a glycol ether, etc. are mentioned. Specific examples of the aromatic hydrocarbons include benzene, toluene, and xylene. Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, etidylacetone, and Alkane, etc. Specific examples of the guanamine-based solvent include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-di Methylacetamide, 2-pyrrolidone, N-methylpyrrolidone, and the like. Specific examples of the glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, and ethylene glycol monoethyl ether. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether An acid ester, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, or the like. These solvents may be used in combination of two or more kinds. The amount of the solvent to be used can be appropriately selected depending on the reaction conditions, and it is preferred to set the solid content concentration to 35% to 95%. Further, when a highly viscous product is generated in the reaction, a solvent can be added in the middle of the reaction to continue the reaction. After completion of the reaction, the solvent may be removed by distillation or the like as needed, or may be further added.

反應溫度係在使用的觸媒不會分解的程度 之溫度範圍內進行。反應溫度較佳係50至230℃，更佳係120至200℃，最佳係150至170℃。反應壓力通常係常壓，但在使用如丙酮、甲基乙基酮之低沸點溶媒時，可藉由使用高壓釜(autoclave)在高壓下進行反應而確保反應溫度。 又，在必須除去反應熱時，通常藉由反應熱所致之使用溶劑的急驟蒸餾/冷凝回流法、間接冷卻法、或併用該等而進行。 The reaction temperature is such that the catalyst used does not decompose. It is carried out within the temperature range. The reaction temperature is preferably from 50 to 230 ° C, more preferably from 120 to 200 ° C, and most preferably from 150 to 170 ° C. The reaction pressure is usually atmospheric pressure, but when a low-boiling solvent such as acetone or methyl ethyl ketone is used, the reaction temperature can be ensured by carrying out a reaction under high pressure using an autoclave. Further, when it is necessary to remove the heat of reaction, it is usually carried out by a flash distillation/condensation reflux method using a solvent, an indirect cooling method, or a combination thereof by a heat of reaction.

本發明之多羥基聚醚樹脂，為了賦予阻燃 性可導入鹵素元素、磷元素。藉由導入鹵素元素而賦予阻燃性時，鹵素含量未達5質量%則無法賦予充分的阻燃性。雖然5質量%以上之任何濃度均可賦予阻燃性，但由於即使設為40質量%以上之濃度，仍未確認到阻燃性之提升，故實用上，較佳係將鹵素含量調控於5質量%至40質量%之範圍。本發明中，鹵素元素之種類係任一種皆可，從商業生產的觀點來看，係利用市售之溴化合物、氯化合物、氟化合物中之在上述鹵素含量範圍內者。 The polyhydroxy polyether resin of the present invention, in order to impart flame retardancy It can introduce halogen and phosphorus. When the flame retardancy is imparted by introducing a halogen element, if the halogen content is less than 5% by mass, sufficient flame retardancy cannot be imparted. Although the flame retardancy can be imparted at any concentration of 5% by mass or more, since the flame retardancy is not confirmed even if it is set to a concentration of 40% by mass or more, it is preferable to adjust the halogen content to 5 mass in practical use. From % to 40% by mass. In the present invention, any of the halogen elements may be used, and from the viewpoint of commercial production, a commercially available bromine compound, a chlorine compound or a fluorine compound is used in the above halogen content range.

又，藉由導入磷元素而賦予阻燃性時，磷 含量未達0.5質量%則無法賦予充分的阻燃性。雖然6質量%以上之任何濃度均可賦予阻燃性，但由於即使設為6 質量%以上之濃度，仍未確認到阻燃性之提升，故實用上，較佳係將磷含量調控為0.5質量%至6質量%之範圍。本發明中，磷元素之導入，從商業生產的觀點來看，係於具有1個官能基之化合物類(B)之含量範圍內利用市售之9,10-二氫-10-(2,5-二羥基苯基)-9-氧雜-10-磷雜菲-10-氧化物等含有磷之2元酚化合物、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物等具有1價之含有活性氫之基之磷化合物。 Moreover, when flame retardancy is imparted by introducing a phosphorus element, phosphorus When the content is less than 0.5% by mass, sufficient flame retardancy cannot be imparted. Although any concentration of 6 mass% or more can impart flame retardancy, even if it is set to 6 Since the flame retardancy is not confirmed at a concentration of more than % by mass, it is preferable to adjust the phosphorus content to a range of 0.5% by mass to 6% by mass. In the present invention, the introduction of the phosphorus element utilizes a commercially available 9,10-dihydro-10-(2, in the range of the content of the compound (B) having one functional group from the viewpoint of commercial production. 5-dihydroxyphenyl)-9-oxa-10-phosphaphenanthrene-10-oxide and other divalent phenolic compounds containing phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- A phosphorus compound having a monovalent active hydrogen-containing group such as 10-oxide.

以往之含多羥基聚醚樹脂之樹脂組成物 中，若提高玻璃轉移溫度則雖得到高耐熱性但樹脂黏度亦提高，實用黏度降低，故需要調配不欲之稀釋成分，本發明不需要調配不欲之稀釋成分。該等效果係玻璃轉移溫度越高越顯著地表現，多羥基聚醚樹脂之玻璃轉移溫度為130℃以上時，黏度降低效果變顯著。玻璃轉移溫度為150℃以上則顯示更佳之效果，玻璃轉移溫度為180℃以上則更大幅顯示效果。再者，200℃以上之玻璃轉移溫度之情況，若不採用本發明之手法，則無法獲得可實用之較低黏度的多羥基聚醚樹脂。調配時需要之物性上不欲之稀釋成分之熔融黏度依用途而異，大致上係於240℃之熔融黏度為10,000Pa‧s以上之情況。240℃之熔融黏度為5,000至10,000Pa‧s時，以稀釋成分以外之調配物，例如，環氧樹脂、硬化劑之選擇而可實用調配。 Conventional resin composition containing polyhydroxy polyether resin In the case where the glass transition temperature is increased, the resin has a high heat resistance, the resin viscosity is also improved, and the practical viscosity is lowered. Therefore, it is necessary to prepare an undesired diluted component, and the present invention does not require the formulation of an undesired diluted component. These effects are more pronounced as the glass transition temperature is higher, and the viscosity reduction effect becomes remarkable when the glass transition temperature of the polyhydroxy polyether resin is 130 ° C or more. A glass transition temperature of 150 ° C or more shows a better effect, and a glass transition temperature of 180 ° C or more gives a larger effect. Further, in the case of a glass transition temperature of 200 ° C or higher, a practically low viscosity polyhydroxy polyether resin cannot be obtained unless the method of the present invention is employed. The melt viscosity of the diluted component which is required for the physical properties to be blended varies depending on the application, and is substantially the case where the melt viscosity at 240 ° C is 10,000 Pa ‧ or more. When the melt viscosity at 240 ° C is 5,000 to 10,000 Pa ‧ s, it can be practically formulated by a formulation other than the diluted component, for example, an epoxy resin or a hardener.

本發明所述之玻璃轉移溫度係依據JIS K-7121。亦即，示差掃描熱量測定(DSC)中，表示以5℃/分鐘之昇溫速度，從室溫昇溫至280℃時之第2次的切線 所求之值。 The glass transition temperature of the present invention is based on JIS K-7121. That is, the differential scanning calorimetry (DSC) indicates the second tangent when the temperature is raised from room temperature to 280 ° C at a temperature increase rate of 5 ° C /min. The value sought.

又，熔融黏度係使用HAAKE公司製 RheoStress600作為分析裝置，將剪切之應力調控使用直徑20mm之Parallel Cone，以Ghamma：0.2%、間隙：0.5mm之設定測定試料0.2g，由240℃之剪切應力之黏度換算值而求得。 In addition, the melt viscosity is made by HAAKE. RheoStress 600 was used as an analysis device, and the shear stress was controlled by Parallel Cone having a diameter of 20 mm, and 0.2 g of a sample was measured with a Ghamma: 0.2% and a gap of 0.5 mm, and the viscosity was converted from a shear stress of 240 ° C.

將本發明之多羥基聚醚樹脂作為必須成分 之樹脂組成物中，不僅多羥基聚醚樹脂，尚可併用環氧樹脂、硬化劑、硬化促進劑、溶劑、無機填充劑、纖維基材等多種材料。 The polyhydroxy polyether resin of the present invention is an essential component In the resin composition, not only a polyhydroxy polyether resin but also a plurality of materials such as an epoxy resin, a curing agent, a curing accelerator, a solvent, an inorganic filler, and a fibrous substrate can be used in combination.

就可併用之環氧樹脂而言，可使用分子中 具有2個以上環氧基之通常的環氧樹脂。例如，可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、聯苯基型環氧樹脂、酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂，酚類和乙二醛、羥基苯甲醛、巴豆醛等醛類之縮合酚醛清漆類與表鹵醇反應所得之環氧樹脂等環氧丙基醚型環氧樹脂，環氧丙基酯型環氧樹脂、環氧丙基胺型環氧樹脂、脂肪族環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂等多種環氧樹脂。該等環氧樹脂可使用1種或2種以上混合而使用。 In the case of an epoxy resin that can be used in combination, it can be used in a molecule. A typical epoxy resin having two or more epoxy groups. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolak type Epoxy epoxide, phenolic and aldehydes, aldehydes such as aldehydes, hydroxybenzaldehydes, crotonaldehydes, aldehydes, phenolic varnishes, epoxidized phenolic varnishes, epoxy resins, etc. Epoxy resin, epoxy propyl amine epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and other epoxy resins. These epoxy resins can be used by using one type or a mixture of two or more types.

本發明之樹脂組成物中可使用之硬化劑，可列舉各種酚酚醛清漆樹脂、酸酐類、胺類、二氰二胺等。若具體例示，就各種酚酚醛清漆樹脂而言，例如，雙酚A、雙酚F、雙酚S、茀雙酚、4,4’-聯苯酚、2,2’-聯苯酚、氫醌、 間苯二酚、萘二酚等2元酚類，或者以參(4-羥基苯基)甲烷、1,1,2,2-肆(4-羥基苯基)乙烷、酚酚醛清漆、鄰-甲酚酚醛清漆、萘酚酚醛清漆、聚乙烯酚等為代表之3元以上酚類。再者，可列舉由酚類、萘酚類等1元酚類，或雙酚A、雙酚F、雙酚S、茀雙酚、4,4’-聯苯酚、2,2’-聯苯酚、氫醌、間苯二酚、萘二酚等2元酚類，與甲醛、乙醛、苯甲醛、對-羥基苯甲醛、對-苯二甲醇等縮合劑而合成之多元酚性化合物等。該等酚性硬化劑與茚或苯乙烯反應而成者亦可用於硬化劑。酸酐，可列舉酞酸酐、四氫酞酸酐、甲基四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、甲基海米克酸酐(methylhimic anhydride)、鈉迪克酸酐(nadic anhydride)、偏苯三甲酸酐等。又，胺類，可列舉4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基丙烷、4,4’-二胺基二苯基碸、間-苯二胺、對-二甲苯二胺等芳香族胺類，乙二胺、己二胺、二乙三胺、三乙四胺等脂肪族胺類。該等硬化劑可使用1種或2種以上混合使用。相對於本發明之樹脂組成物中之環氧樹脂100質量份，硬化劑之添加量通常係10至100質量份之範圍。 Examples of the curing agent which can be used in the resin composition of the present invention include various phenol novolak resins, acid anhydrides, amines, dicyandiamide and the like. Specifically, for various phenol novolak resins, for example, bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, a divalent phenol such as resorcinol or naphthalenediol, or ginseng (4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl)ethane, phenol novolac, or adjacent a cresol novolac, a naphthol novolac, a polyvinyl phenol, etc., represented by a phenol or a phenol. Further, examples thereof include monohydric phenols such as phenols and naphthols, or bisphenol A, bisphenol F, bisphenol S, bisphenol, 4,4'-biphenol, and 2,2'-biphenol. A polyphenolic compound synthesized by a divalent phenol such as hydroquinone, resorcin or naphthol, and a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde or p-phenylenediethanol. These phenolic hardeners can also be used as a hardener in the reaction with hydrazine or styrene. Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, nadic anhydride, and Pyromellitic anhydride and the like. Further, examples of the amines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylanthracene, and m-benzene. An aromatic amine such as an amine or p-xylene diamine; an aliphatic amine such as ethylenediamine, hexamethylenediamine, diethylenetriamine or triethylenetetramine. These hardeners can be used singly or in combination of two or more kinds. The amount of the hardener added is usually in the range of 10 to 100 parts by mass based on 100 parts by mass of the epoxy resin in the resin composition of the present invention.

再者，本發明之樹脂組成物可因應需要而 使用公知之硬化促進劑。可使用之硬化促進劑若具體例示，可列舉2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑等咪唑類，2-(二甲基胺基甲基)酚、1,8-二氮雜-雙環(5,4,0)十一烯-7等第3級胺類，三苯基膦、三環己基膦、三苯基膦三苯基硼烷等膦類，辛酸錫等金屬化合物、路易斯酸等。該 等硬化促進劑可使用1種或2種以上混合使用。相對於本發明之樹脂組成物中之環氧樹脂100質量份，硬化促進劑可因應需要使用0.02至5.0質量份。藉由使用硬化促進劑，可降低硬化溫度，且可縮短硬化時間。 Furthermore, the resin composition of the present invention can be used as needed A known hardening accelerator is used. Specific examples of the hardening accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl)phenol. a third-order amine such as 1,8-diaza-bicyclo(5,4,0)undecene-7, a phosphine such as triphenylphosphine, tricyclohexylphosphine or triphenylphosphine triphenylborane a metal compound such as tin octylate or a Lewis acid. The The curing accelerator may be used alone or in combination of two or more. The hardening accelerator may be used in an amount of 0.02 to 5.0 parts by mass as required, based on 100 parts by mass of the epoxy resin in the resin composition of the present invention. By using a hardening accelerator, the hardening temperature can be lowered, and the hardening time can be shortened.

再者，可因應需要添加溶劑，該溶劑，具 體上可列舉丙酮、甲基乙基酮、甲苯、二甲苯、甲基異丁基酮、乙酸乙酯、乙二醇單甲基醚、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、甲醇、乙醇等，該等溶劑可單獨使用或2種以上混合使用。 Furthermore, a solvent may be added as needed, and the solvent has The body may, for example, be acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N, N - dimethyl acetamide, methanol, ethanol, etc., These solvents may be used alone or in combination of two or more.

再者，本發明之組成物可因應需要使用填 料。具體上可列舉氫氧化鋁、氧化鋁、碳酸鈣、氫氧化鎂、滑石、鍛燒滑石、黏土、高嶺土、水鋁石、氧化鈦、玻璃粉末、球狀或破碎狀熔融氧化矽、結晶氧化矽等氧化矽粉末、氧化矽球(silica balloon)等無機填料。一般使用無機填充材之理由，可列舉提升耐衝擊性。又，使用氫氧化鋁、氫氧化鎂等金屬氫氧化物時，作用為阻燃助劑，而可減少阻燃劑之量。特別係調配量沒有10%以上，則耐衝擊性的效果少。然而，若調配量超過150%，則作為積層板用途之必需項目之接著性會降低。又，可於上述樹脂組成物含有玻璃纖維、紙漿纖維、合成纖維、陶瓷纖維等纖維質填充材，或微粒子橡膠、熱可塑性彈性體等有機填充材。 Furthermore, the composition of the present invention can be used as needed material. Specific examples thereof include aluminum hydroxide, aluminum oxide, calcium carbonate, magnesium hydroxide, talc, calcined talc, clay, kaolin, diaspore, titanium oxide, glass powder, spherical or broken molten cerium oxide, and crystalline cerium oxide. An inorganic filler such as cerium oxide powder or silica balloon. The reason why the inorganic filler is generally used is to improve the impact resistance. Further, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is used, it acts as a flame retardant auxiliary agent, and the amount of the flame retardant can be reduced. In particular, when the blending amount is not more than 10%, the effect of impact resistance is small. However, if the blending amount exceeds 150%, the adhesion of the necessary items for the use of the laminate will be lowered. Further, the resin composition may contain a fibrous filler such as glass fiber, pulp fiber, synthetic fiber or ceramic fiber, or an organic filler such as a fine particle rubber or a thermoplastic elastomer.

再者，本發明之組成物可因應需要使用其 他之保存安定性用之紫外線防止劑、可塑劑等，作為偶合劑之矽烷偶合劑、鈦酸鹽系偶合劑等，纖維基材。纖維基 材，例如，可列舉玻璃布等無機纖維布、玻璃纖維不織布、有機纖維不織布等。又，為了賦予阻燃性，可添加鹵系、磷系、氮系、矽氧系等阻燃劑等。 Furthermore, the composition of the present invention can be used as needed A UV-blocking agent, a plasticizer, etc. for storing stability, a decane coupling agent as a coupling agent, a titanate coupling agent, and the like, and a fibrous base material. Fiber based Examples of the material include inorganic fiber cloth such as glass cloth, glass fiber nonwoven fabric, and organic fiber nonwoven fabric. Further, in order to impart flame retardancy, a flame retardant such as a halogen-based, phosphorus-based, nitrogen-based or xenon-based system may be added.

再者，本發明之樹脂組成物中可適宜地調 配聚酯、聚醯胺、聚醯亞胺、聚醚、聚胺甲酸酯、石油樹脂、茚苯并呋喃樹脂、苯氧樹脂等寡聚物或高分子化合物，亦可調配顏料、阻燃劑、觸變性賦予劑、偶合劑、提升流動性劑等添加劑。顏料係有有機系或無機系體質顏料、鱗片狀顏料等。觸變性賦予劑，可列舉矽氧系、蓖麻油系、脂肪族醯胺蠟、氧化聚乙烯蠟、有機膨土系等。又，本發明之環氧樹脂組成物可因應需要進一步使用棕櫚蠟、OP蠟等脫模劑，γ-環氧丙氧基丙基三甲氧基矽烷等偶合劑、碳黑等著色劑、三氧化銻等阻燃劑、矽氧油等低應力化劑、硬脂酸鈣等潤滑劑等。 Furthermore, the resin composition of the present invention can be suitably adjusted It is formulated with oligomers or polymer compounds such as polyester, polyamide, polyimine, polyether, polyurethane, petroleum resin, benzofuran resin, phenoxy resin, and can also be blended with pigments and flame retardant. Additives such as a thixotropy-imparting agent, a coupling agent, and a fluidizing agent. The pigment is an organic or inorganic pigment, a flaky pigment, or the like. Examples of the thixotropy-imparting agent include an anthraquinone-based, a castor oil-based, an aliphatic guanamine wax, an oxidized polyethylene wax, and an organic bentonite. Further, the epoxy resin composition of the present invention may further use a release agent such as palm wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxydecane, a coloring agent such as carbon black, or a trioxide. A low-stressing agent such as a flame retardant or a helium-oxygen oil, or a lubricant such as calcium stearate.

該等樹脂組成物可使用於以往之多層電子 電路基板、增層(build-up)法等新穎印刷配線板。特佳係使用於作為增層法印刷配線板用材料而使用之附有樹脂之銅箔、接著薄膜等形態。增層法，係在將積層有玻璃預浸體之內層電路板上，積層40至90μm之薄膜(絕緣層)或包含附有銅箔之薄膜(銅箔：9至18μm)之絕緣層之增層之層之方法，一般而言，作為電路形成步驟，係積層擠壓步驟、由雷射或鑽頭之鑽孔步驟、除膠渣(Desmear)/鍍覆步驟。然後，與以往之積層板相比，若為相同性能者，則組裝面積/重量皆成為約1/4，係小型/輕量化用之優異工法。特別係， 本發明之多羥基聚醚樹脂適於薄膜化，而可適宜使用作為增層絕緣層。 These resin compositions can be used in conventional multilayer electronic A novel printed wiring board such as a circuit board or a build-up method. The film is preferably used as a resin-attached copper foil or a film which is used as a material for a build-up printed wiring board. The build-up method is to laminate a film of 40 to 90 μm (insulating layer) or an insulating layer containing a film with copper foil (copper foil: 9 to 18 μm) on an inner circuit board on which a glass prepreg is laminated. The method of layering, in general, as a circuit forming step, a layer extrusion step, a drilling step by a laser or a drill bit, a desmear/plating step. Then, compared with the conventional laminated board, if it is the same performance, the assembly area/weight is about 1/4, and it is excellent in small size and weight reduction. Special department, The polyhydroxy polyether resin of the present invention is suitable for film formation, and can be suitably used as a build-up insulating layer.

本發明之電性積層板，係指包含印刷配線板、增層積層板及可撓積層板等之絕緣基板所用之積層板。 The electrical laminated board of the present invention refers to a laminated board used for an insulating substrate including a printed wiring board, a build-up laminate, and a flexible laminate.

製造本發明之絕緣薄膜之方法無特別限 定，例如，可列舉：(I)將本發明之樹脂組成物使用擠壓機捏和後擠壓，使用T模、圓模等成形為薄片狀之擠壓成形法、(II)將本發明之樹脂組成物溶解或分散於有機溶劑等溶媒中之後，鑄造而成形為薄片狀之鑄造成形法、(III)以往公知之其他薄片成形法等。又，絕緣薄膜之膜厚無特別限定，例如10至300μm，較佳係25至200μm，更佳係40至180μm。於使用增層法時，最佳係40至90μm。若膜厚為10μm以上則可得絕緣性，300μm以下則電極間的電路距離不會長達所需要之長度以上。再者，絕緣薄膜的溶媒之含量無特別限定，相對於樹脂組成物全體，較佳係0.01至5質量%。若相對於樹脂組成物全體，薄膜中之溶媒之含量為0.01質量%以上，則於電路基板積層時，可獲得密著性、接著性，又，若為5質量%以下則可獲得加熱硬化後之平坦性。再者，該等絕緣薄膜亦包含具有接著性之接著薄膜。 There is no particular limitation on the method of manufacturing the insulating film of the present invention. For example, (I) an extrusion molding method in which a resin composition of the present invention is kneaded by an extruder, and extruded into a sheet shape using a T die or a circular die, and (II) the present invention is used. The resin composition is dissolved or dispersed in a solvent such as an organic solvent, and then cast into a sheet-like casting molding method, and (III) other conventionally known sheet forming methods. Further, the film thickness of the insulating film is not particularly limited, and is, for example, 10 to 300 μm, preferably 25 to 200 μm, more preferably 40 to 180 μm. When using the build-up method, the optimum is 40 to 90 μm. When the film thickness is 10 μm or more, the insulating property can be obtained, and when the film thickness is 300 μm or less, the circuit distance between the electrodes does not become longer than the required length. In addition, the content of the solvent of the insulating film is not particularly limited, and is preferably 0.01 to 5% by mass based on the entire resin composition. When the content of the solvent in the film is 0.01% by mass or more based on the entire resin composition, adhesion and adhesion can be obtained when the circuit board is laminated, and if it is 5% by mass or less, heat curing can be obtained. Flatness. Furthermore, the insulating films also comprise an adhesive film having an adhesive property.

藉由將本發明之樹脂組成物硬化，可獲得 樹脂硬化物。硬化時，以例如作為樹脂薄片、附有樹脂之金屬箔、預浸體等形態進行積層且加熱加壓硬化，而可獲得積層板。 By hardening the resin composition of the present invention, Hardened resin. In the case of curing, for example, a laminate is formed in the form of a resin sheet, a metal foil with a resin, a prepreg, or the like, and is heated and pressed to obtain a laminate.

(實施例) (Example)

以下，依據實施例及比較例具體說明本發明。以下合成例、實施例及比較例中，「份」表示「質量份」。 Hereinafter, the present invention will be specifically described based on examples and comparative examples. In the following synthesis examples, examples, and comparative examples, "parts" means "parts by mass".

本發明使用以下分析方法。 The present invention uses the following analytical methods.

(環氧當量)JIS K-7236所記載之方法。亦即，將試料溶解於氯仿10mL，分別添加乙酸酐20mL、20%溴化四乙基乙酸銨溶液10mL，使用電位差滴定裝置，以0.1mol/L過氯酸乙酸標準液進行滴定。 (Epoxy equivalent) The method described in JIS K-7236. That is, the sample was dissolved in 10 mL of chloroform, and 10 mL of acetic anhydride and 10 mL of a 20% ammonium tetraethylammonium bromide solution were added thereto, and titrated with a 0.1 mol/L perchloric acid acetic acid standard solution using a potentiometric titration apparatus.

(水解性氯)JIS K-7243-2所記載之方法。亦即，將試料溶解於2-丁氧基乙醇25mL，添加120g/L氫氧化鈉之2-丁氧基乙醇溶液25mL，於室溫反應30分鐘。然後，使用電位差滴定裝置，以0.01mol/L硝酸銀溶液進行滴定。 (Hydrolyzable chlorine) A method described in JIS K-7243-2. That is, the sample was dissolved in 25 mL of 2-butoxyethanol, and 25 mL of a solution of 120 g/L sodium hydroxide in 2-butoxyethanol was added thereto, and the mixture was reacted at room temperature for 30 minutes. Then, titration was carried out with a 0.01 mol/L silver nitrate solution using a potentiometric titration apparatus.

(1,2-二醇)將試料溶解於氯仿25mL，添加0.2mol/L過碘酸之甲醇溶液，於室溫反應2小時。反應後，添加冷水100mL、10%硫酸水溶液5mL，再添加20%碘化鉀水溶液20mL，將澱粉溶液作為指示劑，以0.1mol/L硫代硫酸鈉溶液進行滴定。同時實施空白試驗，將與空白試驗之滴定量的差除以試樣量之值作為1,2-二醇(meq/100g)。 (1,2-diol) The sample was dissolved in 25 mL of chloroform, and a methanol solution of 0.2 mol/L of periodic acid was added thereto, and the mixture was reacted at room temperature for 2 hours. After the reaction, 100 mL of cold water and 5 mL of a 10% sulfuric acid aqueous solution were added, and 20 mL of a 20% potassium iodide aqueous solution was further added thereto, and the starch solution was used as an indicator, and titrated with a 0.1 mol/L sodium thiosulfate solution. At the same time, a blank test was carried out, and the difference from the titer of the blank test was divided by the value of the sample amount as 1,2-diol (meq/100 g).

(黏度)JIS K-7233所記載之方法。亦即，於500mL之圓筒罐秤取樹脂400g，於25±0.2℃之恆溫水槽放置5小時使其為恆溫。將旋轉黏度計之轉子浸漬於樹脂進行測定。 (Viscosity) The method described in JIS K-7233. That is, 400 g of a resin was weighed in a 500 mL cylindrical can, and placed in a constant temperature water bath of 25 ± 0.2 ° C for 5 hours to make it a constant temperature. The rotor of the rotary viscometer was immersed in a resin for measurement.

(液相層析分析)秤取試料0.10g且溶解於 乙腈10mL。溶解之試料設置於自動採樣器，以注入量0.8μL進行測定。 (liquid chromatography analysis), the sample was taken up to 0.10 g and dissolved in Acetonitrile 10 mL. The dissolved sample was placed in an automatic sampler and measured at an injection amount of 0.8 μL.

再者，分析條件如同以下。 Furthermore, the analysis conditions are as follows.

HPLC分析裝置：Hewlett-Packard公司製系列1100 HPLC analysis device: Hewlett-Packard company series 1100

檢測器：紫外線可見光檢測器測定波長260nm Detector: UV visible light detector measuring wavelength 260nm

管柱：Imtakt公司製Cadenza CD-C18內徑4.6mm×長度10cm Pipe column: Cadenza CD-C18 made by Imtakt Co., Ltd. 4.6 mm × length 10 cm

管柱溫度：40℃ Column temperature: 40 ° C

移動相：水/乙腈(梯度分析) Mobile phase: water / acetonitrile (gradient analysis)

乙腈60%(保持5分鐘)→13分鐘→乙腈100%(保持7分鐘) Acetonitrile 60% (for 5 minutes) → 13 minutes → acetonitrile 100% (for 7 minutes)

流量：1mL/分鐘 Flow rate: 1mL/min

(分子量)藉由凝膠滲透層析(GPC)測定，將由標準聚苯乙烯之重量平均分子量之換算值設為分子量。再者，分析條件如同以下。 (Molecular weight) The value converted from the weight average molecular weight of the standard polystyrene was determined by gel permeation chromatography (GPC). Furthermore, the analysis conditions are as follows.

GPC分析裝置：Tosoh公司製HLC-8020 GPC analyzer: HLC-8020 manufactured by Tosoh

管柱：Tosoh公司製HXL-H×1根+G2000HXL×1根+GMHXL×2根 Pipe column: HXL-H×1+G2000HXL×1+GMHXL×2 from Tosoh

試料濃度：1%四氫呋喃溶液 Sample concentration: 1% tetrahydrofuran solution

注入溶液量：100μL Injection solution amount: 100 μL

管柱溫度：40℃ Column temperature: 40 ° C

溶離液：四氫呋喃 Dissolution: tetrahydrofuran

流量：1mL/分鐘 Flow rate: 1mL/min

檢測器：示差折射率計 Detector: differential refractometer

校正法：由標準聚苯乙烯所換算 Calibration method: converted from standard polystyrene

(熔融黏度)使用HAAKE公司製 RheoStress600作為分析裝置，剪切之應力調控係使用直徑20mm之Parallel Cone，以Ghamma：0.2%，間隙：0.5mm之設定測定試料0.2g，將由240℃之剪切應力之黏度換算值作為熔融黏度。 (melt viscosity) using HAAKE company RheoStress 600 was used as an analysis device, and the shear stress control system used a Parallel Cone having a diameter of 20 mm, and a sample of 0.2 g was measured with a Ghamma: 0.2% and a gap of 0.5 mm, and a viscosity converted from a shear stress of 240 ° C was used as the melt viscosity.

(玻璃轉移溫度)依據JISK-7121。亦即， 示差掃描熱量測定(DSC)中，以5℃/分鐘之昇溫速度，從室溫昇溫至280℃時之第2次之切線而求得者。 (glass transition temperature) according to JIS K-7121. that is, The differential scanning calorimetry (DSC) was obtained by raising the temperature from room temperature to the second tangent at 280 ° C at a temperature increase rate of 5 ° C /min.

(接著力)JIS K6854-1所記載之方法。亦 即，於測圖儀(autograph)，將90度剝離強度，在23℃，65% RH之環境下，以剝離速度：50mm/分鐘之條件而測定。 (Continuing force) The method described in JIS K6854-1. also That is, the autograph was measured at a peeling speed of 50 mm/min in an environment of 23 ° C and 65% RH at a 90-degree peel strength.

(焊料耐熱性試驗)將於100℃煮沸2小時 後之試樣以n=5浸漬於260℃之焊料浴中，在20秒以上全部未發生膨脹、剝離者為○，除此以外為×。 (Solder heat resistance test) will boil for 2 hours at 100 ° C The subsequent sample was immersed in a solder bath of 260 ° C at n = 5, and all of the samples were not expanded for 20 seconds or longer, and the peeling was ○, and other than this, it was ×.

(吸濕率)測定將試驗片於125℃之烘箱中 乾燥24小時後之乾燥質量，然後，接著測定在調整為溫度85℃，濕度85% RH之處理槽內存放168小時後之質量，依據乾燥質量之增加量而測定吸濕率。 (Moisture absorption rate) Determination of the test piece in an oven at 125 ° C The dry mass after drying for 24 hours was measured, and then the mass after storage for 168 hours in a treatment tank adjusted to a temperature of 85 ° C and a humidity of 85% RH was measured, and the moisture absorption rate was measured in accordance with the increase in the dry mass.

(電路埋入性)於剝除外層銅箔後之內層 電路中，樹脂埋入所有地方者為○，除此以外為×。 (circuit embedding) in the inner layer after peeling off the copper foil In the circuit, the resin is buried in all places as ○, and otherwise it is ×.

(2官能環氧樹脂(X)之品質) (Quality of 2-functional epoxy resin (X))

使用由3,3’,5,5’-四甲基聯苯酚(試劑，羥基當量=121g/eq)與表氯醇所得之3,3’,5,5’-四甲基聯苯酚之二環氧丙基醚(依品質差異而區分為環氧樹脂(1)與環氧樹脂(2)之2種)、 由9,9’-雙(4-羥基苯基)茀(大阪GAS股份有限公司製，製品名：BPF，羥基當量=175g/eq)與表氯醇所得之9,9’-雙(4-羥基苯基)茀之二環氧丙基醚(依品質差異而區分為環氧樹脂(3)至環氧樹脂(5)之3種)、及 由3,3’,5,5’-四甲基-4,4’-二羥基二苯基碸(試劑，製品名：TMBPS，羥基當量=153g/eq)與表氯醇所得之3,3’,5,5’-四甲基-4,4’-二羥基二苯基碸之二環氧丙基醚(環氧樹脂(6))作為2官能環氧樹脂(X)。 Using 3,3',5,5'-tetramethylbiphenol obtained from 3,3',5,5'-tetramethylbiphenol (reagent, hydroxyl equivalent = 121 g/eq) and epichlorohydrin Epoxy propyl ether (different into epoxy resin (1) and epoxy resin (2) depending on the quality), 9,9'-bis (4-) obtained from 9,9'-bis(4-hydroxyphenyl)fluorene (manufactured by Osaka GAS Co., Ltd., product name: BPF, hydroxyl equivalent = 175 g/eq) and epichlorohydrin Dihydroxyepoxy ether of hydroxyphenyl) oxime (3 types of epoxy resin (3) to epoxy resin (5) depending on the quality), and 3,3 from 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl hydrazine (reagent, product name: TMBPS, hydroxyl equivalent = 153 g/eq) and epichlorohydrin ',5,5'-tetramethyl-4,4'-dihydroxydiphenylphosphonium diepoxypropyl ether (epoxy resin (6)) as a bifunctional epoxy resin (X).

又，使用YDPN-638(新日鐵住金化學股份有限公司製，酚酚醛清漆環氧樹脂)作為多官能環氧樹脂。 Further, YDPN-638 (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., phenol novolac epoxy resin) was used as the polyfunctional epoxy resin.

又，作為副生成物而含有之具有3個以上官能基之化合物(A)之含量與具有1個官能基之化合物(B)之含量係由液相層析分析而求得。第1圖表示環氧樹脂(1)之液相層析圖表。表1表示使用之各種環氧樹脂之品質。 Further, the content of the compound (A) having three or more functional groups contained as a by-product and the content of the compound (B) having one functional group are determined by liquid chromatography analysis. Fig. 1 shows a liquid chromatogram of the epoxy resin (1). Table 1 shows the qualities of the various epoxy resins used.

第1圖中，分別表示下列各者：(a)表示1,2- 二醇體(成分B1)、(b)表示水解性氯體(成分B2)、(c)表示n=0之2官能環氧樹脂、(d)表示n=0之2官能環氧樹脂與反應溶媒之2-丙醇的加成體(成分B3)、(e)表示n=1之2官能環氧樹脂、(f)表示n=1之2官能環氧樹脂之2級羥基與表氯醇的加成體(成分A1)、(g)表示n=2之2官能環氧樹脂、(h)表示n=1之2官能環氧樹脂之2級羥基與n=0之2官能環氧樹脂的加成體(成分A1)、(i)表示n=3之2官能環氧樹脂、(j)表示n=2之2官能環氧樹脂之2級羥基與n=0之2官能環氧樹脂的加成體(成分A1)。具有3個以上官能 基之化合物(A)係(f)與(h)與(j)，具有1個官能基之化合物(B)係(a)與(b)與(d)。 In the first figure, the following are respectively indicated: (a) indicates 1,2- The diol (components B1) and (b) represent a hydrolyzable chlorine (component B2), (c) a 2-functional epoxy resin with n = 0, and (d) a 2-functional epoxy resin with n = 0 and reaction. An adduct of a solvent of 2-propanol (components B3), (e) represents a 2-functional epoxy resin of n=1, and (f) a hydroxyl group of a 2-functional epoxy resin of n=1 and epichlorohydrin Additives (components A1) and (g) represent a 2-functional epoxy resin of n=2, (h) a 2-stage hydroxyl group representing a 2-functional epoxy resin of n=1, and a 2-functional epoxy resin of n=0. Additives (component A1), (i) represent a 2-functional epoxy resin of n=3, (j) a 2-stage hydroxyl group representing a n-functional epoxy resin of n=2, and a 2-functional epoxy resin of n=0 Additive (component A1). Has more than 3 functional groups The compound (A) is based on (f) and (h) and (j), and the compound (B) having one functional group is (a) and (b) and (d).

(2元酚(Y)之品質) (Quality of 2-membered phenol (Y))

使用9,9’-雙(4-羥基苯基)茀(前述，BPF)、4,4’-聯苯酚(本州化學工業股份有限公司製，製品名：聯苯酚，羥基當量=93g/eq)、3,3’,5,5’-四甲基-4,4’-二羥基二苯基碸(前述，TMBPS)作為2元酚(Y)。 9,9'-bis(4-hydroxyphenyl)anthracene (previously, BPF), 4,4'-biphenol (manufactured by Honshu Chemical Industry Co., Ltd., product name: biphenol, hydroxyl equivalent = 93 g/eq) 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl hydrazine (described above, TMBPS) is used as a divalent phenol (Y).

又，使用酚酚醛清漆樹脂(本州化學工業股份有限公司 製，製品名：BRG-555，羥基當量=105g/eq)作為3元以上之多元酚化合物。 Also, use phenol novolac resin (Honzhou Chemical Industry Co., Ltd. The product name: BRG-555, hydroxyl equivalent = 105 g/eq) is a polyhydric phenol compound of 3 or more.

又，使用對苯基酚(特級試劑，羥基當量=170g/eq)作為1元酚化合物。 Further, p-phenylphenol (special grade reagent, hydroxyl equivalent = 170 g/eq) was used as a monovalent phenol compound.

就其他原料而言，使用對胺基酚(特級試劑，活性氫當量=36g/eq)作為具有3個以上官能基之化合物類(A)，使用十二酸(特級試劑，羧基當量=200g/eq)作為具有1個官能基之化合物類(B)。 For other raw materials, an aminophenol (special grade reagent, active hydrogen equivalent = 36 g/eq) was used as the compound (A) having three or more functional groups, and dodecanoic acid (special grade reagent, carboxyl equivalent = 200 g/) was used. Eq) as a compound (B) having one functional group.

具有3個以上官能基之化合物類(A)之含量與具有1個官能基之化合物類(B)之含量係由液相層析分析而求得。表2表示使用之各種化合物之品質。 The content of the compound (A) having three or more functional groups and the content of the compound (B) having one functional group are determined by liquid chromatography analysis. Table 2 shows the qualities of the various compounds used.

實施例1 Example 1

將環氧樹脂(1)106.7g、BPF 93.4g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2-乙基-4-甲基咪唑(四國化成股份有限公司製，製品名：2E4MZ)0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌6小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後，保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(I))190g。 106.7 g of the epoxy resin (1), 93.4 g of BPF, and 67 g of cyclohexanone were placed in a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and heated using a heating pack. After being stirred at 130 ° C, it was completely dissolved. Then, 0.06 g of 2-ethyl-4-methylimidazole (product name: 2E4MZ, manufactured by Shikoku Chemicals Co., Ltd.) was added while maintaining the reaction temperature at 160 ° C. Stirring was continued until 170 °C. After stirring for 6 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. After the internal pressure of the oven reached 0.4 kPa, it was kept. The solvent was removed for 60 minutes to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (I)).

使樹脂(I)30g溶解於混合溶媒(甲基乙基酮/ 甲苯/四氫呋喃=2/2/1[質量比])30g中，使用輥塗機將該溶液塗佈於分離薄膜(PET薄膜)上，於130℃之烘箱中乾燥30分鐘，獲得厚度50μm之樹脂薄膜。將樹脂薄膜切取成4mm×20mm之尺寸，作為玻璃轉移溫度測定用試驗片。 Dissolving 30 g of the resin (I) in a mixed solvent (methyl ethyl ketone / Toluene / tetrahydrofuran = 2 / 2 / 1 [mass ratio] 30 g, the solution was applied onto a separation film (PET film) using a roll coater, and dried in an oven at 130 ° C for 30 minutes to obtain a resin having a thickness of 50 μm. film. The resin film was cut into a size of 4 mm × 20 mm to prepare a test piece for measuring the glass transition temperature.

樹脂(I)之重量平均分子量(Mw)係43,800， 數量平均分子量(Mn)係10,100，Mw/Mn係4.34。樹脂(I)之熔融黏度係2,000Pa‧s。樹脂(I)之玻璃轉移溫度係158℃。 結果表示於表3。 The weight average molecular weight (Mw) of the resin (I) is 43,800, The number average molecular weight (Mn) was 10,100, and the Mw/Mn system was 4.34. The melt viscosity of the resin (I) is 2,000 Pa‧s. The glass transition temperature of the resin (I) was 158 °C. The results are shown in Table 3.

實施例2 Example 2

將環氧樹脂(1)77.8g、環氧樹脂(2)29g、BPF 93.4g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包 加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之三苯基膦(北興化學股份有限公司製，製品名：TPP)0.3g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌5小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(II))190g。與實施例1同樣地操作，將評估結果表示於表3。 77.8 g of epoxy resin (1), 29 g of epoxy resin (2), 93.4 g of BPF, and 67 g of cyclohexanone were fed into a 4-port glass separable type equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. In the flask, use a heating pack on one side After being heated to 130 ° C, the mixture was completely dissolved by stirring, and then 0.3 g of triphenylphosphine (manufactured by Kitagawa Chemical Co., Ltd., product name: TPP) was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. . After stirring for 5 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (II)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例3 Example 3

將環氧樹脂(2)106.8g、BPF 93.4g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌9小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(III))190g。與實施例1同樣地操作，將評估結果表示於表3。 106.8 g of the epoxy resin (2), 93.4 g of BPF, and 67 g of cyclohexanone were placed in a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and heated using a heating pack. The mixture was completely dissolved by stirring at 130 ° C. Thereafter, 0.06 g of 2E4MZ of a catalyst was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. After stirring for 9 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (III)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例4 Example 4

將環氧樹脂(3)135.3g、對苯基酚(特級試劑，羥基當量=170g/eq)6.8g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而均勻熔融，之後，添加觸媒之 正丁基三苯基鏻溴化物(日本化學工業股份有限公司製，製品名：HISHICOLIN BTPPBr)0.05g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌2小時。然後，添加YDPN-638(前述)8.7g、聯苯酚(前述)49.3g、及環己酮67g，均勻溶解後，添加觸媒之HISHICOLIN BTPPBr(前述)0.25g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌5小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(IV))190g。與實施例1同樣地操作，將評估結果表示於表3。 135.3 g of epoxy resin (3) and 6.8 g of p-phenylphenol (special grade reagent, hydroxyl equivalent = 170 g/eq) were fed into a 4-port glass separable type equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. The flask was stirred while being heated to 130 ° C with a heating pack to be uniformly melted, and then a catalyst was added thereto. 0.05 g of n-butyltriphenylphosphonium bromide (manufactured by Nippon Chemical Industry Co., Ltd., product name: HISHICOLIN BTPPBr) was continuously stirred for 2 hours while maintaining the reaction temperature at 160 ° C to 170 ° C. Then, 8.7 g of YDPN-638 (described above), 49.3 g of biphenol (described above), and 67 g of cyclohexanone were added, and after uniformly dissolved, 0.25 g of HISHICOLIN BTPPBr (described above) of a catalyst was added thereto while maintaining the reaction temperature at 160 ° C. Stirring was continued until 170 °C. After stirring for 5 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (IV)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例5 Example 5

將環氧樹脂(3)59.7g、環氧樹脂(4)59.7g、BPF 80.6g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌4小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(V))190g。與實施例1同樣地操作，將評估結果表示於表3。 59.7 g of epoxy resin (3), 59.7 g of epoxy resin (4), 80.6 g of BPF, and 67 g of cyclohexanone were fed into a 4-port glass equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. In the flask, the mixture was stirred and completely dissolved by heating to 130 ° C. Then, 0.06 g of 2E4MZ of a catalyst was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. After stirring for 4 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (V)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例6 Example 6

將環氧樹脂(4)55.3g、環氧樹脂(5)64.0g、BPF 80.7g、 及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌9小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(VI))190g。與實施例1同樣地操作，將評估結果表示於表3。 55.3 g of epoxy resin (4), 64.0 g of epoxy resin (5), and 80.7 g of BPF. And 67 g of cyclohexanone was added to a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and the mixture was stirred and completely dissolved by heating to 130° C., and then a catalyst was added thereto. 2E4MZ 0.06g, stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. After stirring for 9 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (VI)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例7 Example 7

將環氧樹脂(6)118.5g、TMBPS 72.0g、對苯基酚3.6g、BRG-555 5.9g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ(前述)0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌6小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(VII))190g。與實施例1同樣地操作，將評估結果表示於表3。 118.5 g of epoxy resin (6), 72.0 g of TMBPS, 3.6 g of p-phenylphenol, 5.9 g of BRG-555, and 67 g of cyclohexanone were fed to a 4-neck equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device. In a glass separable flask, the mixture was stirred and completely dissolved by heating to 130 ° C, and then 0.06 g of 2E4MZ (described above) of a catalyst was added thereto, and stirring was continued while maintaining the reaction temperature at 160 to 170 °C. After stirring for 6 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (VII)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

實施例8 Example 8

將環氧樹脂(5)120.3g、BPF 77.0g、對胺基酚1.0g、十 二酸1.7g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之TPP 0.3g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌8小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(VIII))190g。與實施例1同樣地操作，將評估結果表示於表3。 Epoxy resin (5) 120.3g, BPF 77.0g, p-aminophenol 1.0g, ten 1.7 g of diacid and 67 g of cyclohexanone were placed in a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and were stirred and completely dissolved by heating to 130 ° C using a heating pack. Thereafter, 0.3 g of a TPP of a catalyst was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. After stirring for 8 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (VIII)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

比較例1 Comparative example 1

將環氧樹脂(5)119.3g、BPF 80.8g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。攪拌8小時後，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(IX))190g。與實施例1同樣地操作，將評估結果表示於表3。 119.3 g of epoxy resin (5), 80.8 g of BPF, and 67 g of cyclohexanone were placed in a 4-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and heated using a heating pack. The mixture was completely dissolved by stirring at 130 ° C. Thereafter, 0.06 g of 2E4MZ of a catalyst was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. After stirring for 8 hours, 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction solution was placed in a stainless steel tank and placed in a vacuum oven maintained at 160 ° C. The internal pressure of the oven reached 0.4 kPa and remained 60. In a minute, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (IX)). The evaluation results were shown in Table 3 in the same manner as in Example 1.

比較例2 Comparative example 2

將環氧樹脂(2)113.6g、TMBPS 86.5g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4 口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。在攪拌1.5小時的時候，反應液開始增黏，雖然追加環己酮67g且均勻化，但增黏傾向仍不停止，到2小時的時候，變得無法攪拌。雖欲將反應液溶解於四氫呋喃，但因不溶而無法測定分子量。 113.6 g of epoxy resin (2), 86.5 g of TMBPS, and 67 g of cyclohexanone were fed to a stirring device, a thermometer, a cooling tube, and a nitrogen introducing device. In a separable flask made of a glass, the mixture was stirred and completely dissolved by heating to 130 ° C, and then 0.06 g of 2E4MZ of a catalyst was added thereto, and stirring was continued while maintaining the reaction temperature at 160 to 170 °C. When the mixture was stirred for 1.5 hours, the reaction liquid began to increase in viscosity. Although 67 g of cyclohexanone was added and homogenized, the tendency to increase the viscosity did not stop, and when it was 2 hours, it became impossible to stir. Although the reaction solution was to be dissolved in tetrahydrofuran, the molecular weight could not be measured because it was insoluble.

比較例3 Comparative example 3

將環氧樹脂(4)147.3g、聯苯酚52.8g、及環己酮67g進料於具備攪拌裝置、溫度計、冷卻管、氮氣導入裝置之4口玻璃製可分離式燒瓶中，一邊使用加熱包加熱至130℃一邊攪拌而完全溶解，之後，添加觸媒之2E4MZ 0.06g，一邊將反應溫度保持在160℃至170℃一邊持續攪拌。6小時的時候分子量係14,600。雖然進一步持續攪拌，但12小時的時候分子量係14,900，因此判斷未進行反應，添加甲基乙基酮134g且使其均勻，之後，將反應液承接於不銹鋼製槽中，放入保持在160℃之真空烘箱中，烘箱之內部壓力到達0.4kPa後保持60分鐘，將溶劑除去，獲得多羥基聚醚樹脂(稱為樹脂(X))190g。 147.3 g of an epoxy resin (4), 52.8 g of biphenol, and 67 g of cyclohexanone were placed in a four-port separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device, and a heating pack was used. After heating to 130 ° C, the mixture was completely dissolved by stirring. Thereafter, 0.06 g of 2E4MZ of a catalyst was added, and stirring was continued while maintaining the reaction temperature at 160 ° C to 170 ° C. The molecular weight was 14,600 at 6 hours. Although the stirring was further continued, the molecular weight was 14,900 at 12 hours. Therefore, it was judged that the reaction was not carried out, and 134 g of methyl ethyl ketone was added and made uniform. Thereafter, the reaction liquid was taken up in a stainless steel tank and placed at 160 ° C. In the vacuum oven, after the internal pressure of the oven reached 0.4 kPa and held for 60 minutes, the solvent was removed to obtain 190 g of a polyhydroxy polyether resin (referred to as a resin (X)).

除了使用樹脂(X)取代樹脂(I)以外，與實施例1完全同樣地進行操作，但乾燥後之樹脂未能成為薄膜狀。 The operation was carried out in the same manner as in Example 1 except that the resin (X) was used instead of the resin (I), but the resin after drying did not become a film.

將結果整理並表示於表3，係成分(A)量、成分(B)量係化合物(A)、化合物(B)之含有率(質量%)。 The results are shown in Table 3, and the content (% by mass) of the component (A) and the component (B) are the compound (A) and the compound (B).

比較例1係由高純度的2官能環氧樹脂與高 純度的2元酚化合物所得之以往製法之多羥基聚醚樹脂。 實施例5、實施例6與比較例1相比，分子量幾乎不變，但實施例之熔融黏度變得相當低。又，雖然實施例6為高分子量，但其熔融黏度只有比較例1的一半以下。比較例2中，由於3官能以上之多官能環氧樹脂(A)多，因此多羥基聚醚樹脂之製造有很大的問題。比較例3中，由於具有1個官能基之化合物類(B)多，因此無法將多羥基聚醚樹脂提高到可薄膜化之分子量。然而，即使使用此種原料，如實施例2、實施例3，可藉由調控3官能以上之多官能環氧樹脂(A)與具有1個官能基之化合物(B)之量而獲得目的之多羥基聚醚樹脂。又，如實施例4、實施例7，即使蓄意使用單環氧改質之樹脂，仍可藉由調配適當量之3官能以上之多官能環氧樹脂、3元以上之多元酚化合物而獲得目的之多羥基聚醚樹脂。如實施例8，可藉由蓄意且同時調配適當量之具有3官能以上之官能基之化合物(A)與具有1個官能基之化合物(B)而獲得目的之多羥基聚醚樹脂。 Comparative Example 1 was made of high-purity bifunctional epoxy resin and high A polyhydroxy polyether resin obtained by a conventional method of obtaining a pure divalent phenol compound. In Example 5 and Example 6, the molecular weight was almost unchanged as compared with Comparative Example 1, but the melt viscosity of the Example became quite low. Further, although Example 6 has a high molecular weight, its melt viscosity is only half or less of Comparative Example 1. In Comparative Example 2, since the polyfunctional epoxy resin (A) having three or more functional groups was contained, the production of the polyhydroxy polyether resin was problematic. In Comparative Example 3, since the compound (B) having one functional group was large, the polyhydroxy polyether resin could not be increased to a film-formable molecular weight. However, even if such a raw material is used, as in the case of Example 2 and Example 3, the purpose can be attained by controlling the amount of the trifunctional or higher polyfunctional epoxy resin (A) and the compound (B) having one functional group. Polyhydroxy polyether resin. Further, as in Example 4 and Example 7, even if a resin having a monoepoxy modification was deliberately used, it was possible to obtain an object by blending an appropriate amount of a trifunctional or higher polyfunctional epoxy resin or a trihydric or higher polyhydric phenol compound. Polyhydroxy polyether resin. As in Example 8, the desired polyhydroxy polyether resin can be obtained by deliberately and simultaneously blending an appropriate amount of the compound (A) having a functional group having three or more functional groups with the compound (B) having one functional group.

實施例9 Example 9

(樹脂組成物之評估) (Evaluation of resin composition)

將實施例1所得之樹脂(I)100g與雙酚A型液狀環氧樹脂(新日鐵住金化學股份有限公司製，製品名：YD-128，環氧當量：187g/eq，黏度：12,800mPa‧s/25℃，水解性氯：240ppm)100g溶解於混合溶媒(前述)200g中，之後，添加另外混合溶解有作為硬化劑之二氰二胺(日本CARBIDE股份 有限公司製，以後稱為DICY)5.6g之DICY溶液(DICY(前述)/乙二醇單甲基醚/N,N-二甲基甲醯胺(質量比)=5.6/21/21)，進一步將作為硬化促進劑之2E4MZ 0.5g作為10質量%甲基乙基酮溶液添加，均勻地混合而獲得樹脂組成物清漆(varnish)。將該樹脂組成物清漆使用輥塗機塗佈於分離薄膜(聚醯亞胺薄膜)上，在130℃之烘箱中乾燥30分鐘，獲得厚度50μm之樹脂薄膜。從分離薄膜將樹脂薄膜剝下，進一步將樹脂薄膜在200℃之烘箱中硬化60分鐘，獲得硬化薄膜。由硬化薄膜切取出4mm×20mm之尺寸，作為玻璃轉移溫度測定用試驗片。由硬化薄膜切取出20mm×20mm之尺寸，作為吸濕率測定用試驗片。此外，另外將樹脂組成物清漆以使溶劑乾燥後之樹脂厚度成為50μm之方式使用輥塗機塗佈於厚度35μm之銅箔的固定(anchor)面，在130℃之烘箱進行溶劑乾燥10分鐘，獲得附有接著劑之銅箔。另一方面，使用線間100μm節距(pitch)之經銅黑化處理完畢之玻璃環氧包銅兩面板積層板作為模擬內層電路基板，將前述附有接著劑之銅箔使用乾燥積層機積層於該模擬內層電路基板的兩面，於180℃加熱硬化2小時，獲得4層之印刷配線板。結果表示於表4。 100 g of the resin (I) obtained in Example 1 and a bisphenol A type liquid epoxy resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., product name: YD-128, epoxy equivalent: 187 g/eq, viscosity: 12,800 mPa‧s/25°C, hydrolyzable chlorine: 240ppm) 100g dissolved in 200g of a mixed solvent (described above), and then added separately mixed with dicyandiamide as a hardener (Japan CARBIDE shares) Ltd., hereinafter referred to as DICY) 3.6g of DICY solution (DICY (previously) / ethylene glycol monomethyl ether / N, N-dimethylformamide (mass ratio) = 5.6 / 21/21), Further, 0.5 g of 2E4MZ as a curing accelerator was added as a 10% by mass methyl ethyl ketone solution, and uniformly mixed to obtain a resin composition varnish. This resin composition varnish was applied onto a separation film (polyimine film) using a roll coater, and dried in an oven at 130 ° C for 30 minutes to obtain a resin film having a thickness of 50 μm. The resin film was peeled off from the separation film, and the resin film was further cured in an oven at 200 ° C for 60 minutes to obtain a cured film. A size of 4 mm × 20 mm was cut out from the cured film to obtain a test piece for measuring the glass transition temperature. A size of 20 mm × 20 mm was cut out from the cured film to obtain a test piece for moisture absorption rate measurement. Further, the resin composition varnish was applied to an anchor surface of a copper foil having a thickness of 35 μm by a roll coater so that the thickness of the resin after drying the solvent was 50 μm, and the solvent was dried in an oven at 130 ° C for 10 minutes. A copper foil with an adhesive is obtained. On the other hand, a copper epoxy-clad two-panel laminate having a copper blackening treatment using a pitch of 100 μm between lines is used as a dummy inner layer circuit substrate, and the above-mentioned copper foil with an adhesive is used as a dry laminator. The both sides of the dummy inner layer circuit board were laminated and heat-hardened at 180 ° C for 2 hours to obtain a 4-layer printed wiring board. The results are shown in Table 4.

實施例10 Example 10

除了使用實施例3所得之樹脂(III)以外，與實施例9完全同樣地進行操作而獲得硬化薄膜、玻璃轉移溫度測定用試驗片、吸濕率測定用試驗片、附有接著劑之銅箔、及4層之印刷配線板。結果表示於表4。 In the same manner as in Example 9, except that the resin (III) obtained in Example 3 was used, a cured film, a test piece for measuring glass transition temperature, a test piece for moisture absorption rate measurement, and a copper foil with an adhesive were obtained. And 4 layers of printed wiring boards. The results are shown in Table 4.

實施例11 Example 11

除了使用實施例4所得之樹脂(IV)以外，與實施例9完全同樣地進行操作而獲得硬化薄膜、玻璃轉移溫度測定用試驗片、吸濕率測定用試驗片、附有接著劑之銅箔、及4層之印刷配線板。結果表示於表4。 In the same manner as in Example 9, except that the resin (IV) obtained in Example 4 was used, a cured film, a test piece for measuring glass transition temperature, a test piece for moisture absorption rate measurement, and a copper foil with an adhesive were obtained. And 4 layers of printed wiring boards. The results are shown in Table 4.

實施例12 Example 12

除了使用實施例6所得之樹脂(VI)以外，與實施例9完全同樣地進行操作而獲得硬化薄膜、玻璃轉移溫度測定用試驗片、吸濕率測定用試驗片、附有接著劑之銅箔、及4層之印刷配線板。結果表示於表4。 In the same manner as in Example 9, except that the resin (VI) obtained in Example 6 was used, a cured film, a test piece for measuring glass transition temperature, a test piece for moisture absorption rate measurement, and a copper foil with an adhesive were obtained. And 4 layers of printed wiring boards. The results are shown in Table 4.

比較例4 Comparative example 4

除了使用比較例1所得之樹脂(IX)以外，與實施例9完全同樣地進行操作而獲得硬化薄膜、玻璃轉移溫度測定用試驗片、吸濕率測定用試驗片、附有接著劑之銅箔、及4層之印刷配線板。結果表示於表4。 In the same manner as in Example 9, except that the resin (IX) obtained in Comparative Example 1 was used, a cured film, a test piece for measuring glass transition temperature, a test piece for moisture absorption rate measurement, and a copper foil with an adhesive were obtained. And 4 layers of printed wiring boards. The results are shown in Table 4.

比較例5 Comparative Example 5

將比較例1所得之樹脂(IX)100g、YD-128(前述)80g、由反應性稀釋材料之環己烷二甲醇及表氯醇而得之環己烷二甲醇之二環氧丙基醚(新日鐵住金化學股份有限公司製，製品名：ZX-1658，環氧當量：139g/eq，黏度：45mPa‧s/25℃，水解性氯：90ppm)20g溶解於混合溶媒(前述)200g中，之後，添加另外混合溶解有作為硬化劑之DICY(前述)6g之DICY溶液(前述)，進一步將作為硬化促進劑之2E4MZ(前述)0.55g作為10質量%甲基乙基酮溶液添加，均勻地混合而 獲得樹脂組成物清漆。除了使用該樹脂組成物清漆以外，與實施例9完全同樣地進行操作而獲得硬化薄膜、玻璃轉移溫度測定用試驗片、吸濕率測定用試驗片、附有接著劑之銅箔、及4層之印刷配線板。結果表示於表4。 100 g of the resin (IX) obtained in Comparative Example 1, 80 g of YD-128 (described above), diglycidyl ether of cyclohexanedimethanol obtained from cyclohexanedimethanol of reactive diluent and epichlorohydrin (Nippon Steel & Sumitomo Chemical Co., Ltd., product name: ZX-1658, epoxy equivalent: 139g/eq, viscosity: 45mPa‧s/25°C, hydrolyzable chlorine: 90ppm) 20g dissolved in mixed solvent (described above) 200g In the following, a DICY solution (described above) in which 6 g of DICY (described above) as a curing agent was dissolved was further added, and 0.55 g of 2E4MZ (described above) as a curing accelerator was further added as a 10% by mass methyl ethyl ketone solution. Evenly mixed A resin composition varnish was obtained. In the same manner as in Example 9, except that the resin composition varnish was used, a cured film, a test piece for measuring glass transition temperature, a test piece for moisture absorption rate measurement, a copper foil with an adhesive, and 4 layers were obtained. Printed wiring board. The results are shown in Table 4.

實施例與比較例相比，僅多羥基聚醚樹脂 之熔融黏度高之比較例4之電路埋入性差。又，為了使樹脂黏度降低而使用反應性稀釋材之比較例5，雖改善電路埋入性，但吸濕性變差，焊料耐熱性變差。 Example Compared with the comparative example, only the polyhydroxy polyether resin The circuit of Comparative Example 4 having a high melt viscosity was poor in embedding property. Further, in Comparative Example 5 in which a reactive diluent was used to lower the viscosity of the resin, the embedding property was deteriorated, and the heat resistance of the solder was deteriorated.

由於本案的圖為實驗數據，不足以代表本案。故本案無指定代表圖。 Since the picture in this case is experimental data, it is not enough to represent the case. Therefore, there is no designated representative map in this case.

Claims (18)

一種多羥基聚醚樹脂之製造方法，其係將2官能環氧樹脂(X)、2元酚化合物(Y)、具有3個以上選自環氧基或與環氧基有反應性之含有活性氫之基中之官能基之化合物(A)、及具有1個該官能基之化合物(B)作為反應原料，在觸媒存在下進行聚合反應而製造重量平均分子量為15,000至100,000之多羥基聚醚樹脂的方法，其中，反應原料中之化合物(A)與(B)之量係滿足下述式：0<A/(X+Y+A+B)≦0.05 0<B/(X+Y+A+B)≦0.05(X、Y、A、及B分別係2官能環氧樹脂(X)、2元酚化合物(Y)、化合物(A)、及化合物(B)之進料量(質量))。 A method for producing a polyhydroxy polyether resin, which comprises a bifunctional epoxy resin (X), a divalent phenol compound (Y), and three or more reactive groups selected from epoxy groups or reactive with epoxy groups The compound (A) having a functional group in the hydrogen group and the compound (B) having one such functional group are used as a reaction raw material, and a polymerization reaction is carried out in the presence of a catalyst to produce a polyhydroxy group having a weight average molecular weight of 15,000 to 100,000. A method of an ether resin, wherein the amounts of the compounds (A) and (B) in the reaction raw material satisfy the following formula: 0 < A / (X + Y + A + B) ≦ 0.05 0 < B / (X + Y +A+B)≦0.05 (X, Y, A, and B are the feed amounts of the bifunctional epoxy resin (X), the divalent phenol compound (Y), the compound (A), and the compound (B), respectively ( quality)). 如申請專利範圍第1項所述之多羥基聚醚樹脂之製造方法，其中，前述具有3個以上官能基之化合物(A)係3官能以上之多官能環氧樹脂、3元以上之多元酚化合物、或該兩者。 The method for producing a polyhydroxy polyether resin according to the first aspect of the invention, wherein the compound (A) having three or more functional groups is a polyfunctional epoxy resin having three or more functional groups, and a polyhydric phenol having three or more members. a compound, or both. 如申請專利範圍第1或2項所述之多羥基聚醚樹脂之製造方法，其中，前述具有1個官能基之化合物(B)係1官能環氧樹脂、1元酚化合物、或該兩者。 The method for producing a polyhydroxy polyether resin according to claim 1 or 2, wherein the compound (B) having one functional group is a monofunctional epoxy resin, a monovalent phenol compound, or both . 如申請專利範圍第1項至第3項中任一項所述之多羥基聚醚樹脂之製造方法，其中，前述2官能環氧樹脂(X)係由以2元酚化合物為主成分之酚化合物與表鹵醇之反應所得之環氧樹脂，作為副生成物而含有之3官能以上之多官能環氧樹脂之含量為0.05至5質量%，且 作為副生成物而含有之1官能環氧樹脂之含量為0.05至5質量%。 The method for producing a polyhydroxy polyether resin according to any one of claims 1 to 3, wherein the bifunctional epoxy resin (X) is a phenol having a divalent phenol compound as a main component. The epoxy resin obtained by the reaction of the compound with an epihalohydrin has a content of a trifunctional or higher polyfunctional epoxy resin contained as a by-product of 0.05 to 5% by mass, and The content of the monofunctional epoxy resin contained as a by-product is 0.05 to 5% by mass. 如申請專利範圍第1項至第4項中任一項所述之多羥基聚醚樹脂之製造方法，其中，前述2官能環氧樹脂類(X)係下述者中之至少任一者：由下述通式(1)所示之酚化合物與表鹵醇之反應所得之環氧樹脂、由下述通式(2)所示之酚化合物與表鹵醇之反應所得之環氧樹脂、或由下述通式(3)所示之酚化合物與表鹵醇之反應所得之環氧樹脂： (式中，R1分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基) (式中，R2分別獨立地表示氫原子、碳數1至6之直鏈 或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基) (式中，R3分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、可具有取代基之芳烷基)。 The method for producing a polyhydroxy polyether resin according to any one of claims 1 to 4, wherein the bifunctional epoxy resin (X) is at least one of: An epoxy resin obtained by reacting a phenol compound represented by the following formula (1) with an epihalohydrin, an epoxy resin obtained by reacting a phenol compound represented by the following formula (2) with an epihalohydrin, Or an epoxy resin obtained by reacting a phenol compound represented by the following formula (3) with an epihalohydrin: (wherein R1 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and a aryl group which may have a substituent Or an aralkyl group which may have a substituent) (wherein R2 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and a aryl group which may have a substituent Or an aralkyl group which may have a substituent) (wherein R3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and an aromatic group which may have a substituent a aryl group which may have a substituent. 如申請專利範圍第1項至第5項中任一項所述之多羥基聚醚樹脂之製造方法，其中，前述2元酚化合物(Y)係以2元酚化合物(Y)中之50至100質量%而含有選自下述通式(1)、通式(2)或通式(3)所示之酚化合物之至少一者： (式中，R1分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、 可具有取代基之芳基、或可具有取代基之芳烷基) (式中，R2分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基) (式中，R3分別獨立地表示氫原子、碳數1至6之直鏈或分支烷基、碳數1至6之烷氧基、碳數6之環狀烷基、可具有取代基之芳基、或可具有取代基之芳烷基)。 The method for producing a polyhydroxy polyether resin according to any one of claims 1 to 5, wherein the divalent phenol compound (Y) is 50% of the divalent phenol compound (Y) 100% by mass and containing at least one selected from the group consisting of phenol compounds represented by the following formula (1), formula (2) or formula (3): (wherein R1 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and a aryl group which may have a substituent Or an aralkyl group which may have a substituent) (wherein R2 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and a aryl group which may have a substituent Or an aralkyl group which may have a substituent) (wherein R3 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyclic alkyl group having 6 carbon atoms, and an aromatic group which may have a substituent a group or an aralkyl group which may have a substituent. 一種多羥基聚醚樹脂，其係藉由申請專利範圍第1項至第6項中任一項所述之多羥基聚醚樹脂之製造方法所製造者。 A polyhydroxy polyether resin produced by the method for producing a polyhydroxy polyether resin according to any one of claims 1 to 6. 如申請專利範圍第7項所述之多羥基聚醚樹脂，其中，由示差掃描熱量測定所得之玻璃轉移溫度係130℃以上，且240℃之熔融黏度未達10,000Pa‧s者。 The polyhydroxy polyether resin according to claim 7, wherein the glass transition temperature obtained by differential scanning calorimetry is 130 ° C or higher, and the melt viscosity at 240 ° C is less than 10,000 Pa ‧ s. 一種樹脂組成物，其含有申請專利範圍第7或8項所述之多羥基聚醚樹脂、及三維交聯性樹脂成分，且其 質量比係多羥基聚醚樹脂/三維交聯性樹脂成分=1/99至99/1。 A resin composition comprising the polyhydroxy polyether resin according to claim 7 or 8 and a three-dimensional crosslinkable resin component, and The mass ratio is polyhydroxy polyether resin / three-dimensional crosslinkable resin component = 1 / 99 to 99 / 1. 如申請專利範圍第9項所述之樹脂組成物，其中，前述三維交聯性樹脂成分係環氧樹脂與硬化劑，且係藉由加熱及/或光照射而硬化者。 The resin composition according to claim 9, wherein the three-dimensional crosslinkable resin component is an epoxy resin and a curing agent, and is cured by heating and/or light irradiation. 一種絕緣薄膜，其係將申請專利範圍第9或10項所述之樹脂組成物之任一者在支撐基底薄膜上形成薄膜狀而成者。 An insulating film obtained by forming a film on a supporting base film by any one of the resin compositions described in claim 9 or 10. 一種附有印刷配線板用樹脂之金屬箔，其係將申請專利範圍第9或10項所述之樹脂組成物塗佈於金屬箔而成者。 A metal foil with a resin for a printed wiring board, which is obtained by applying a resin composition according to claim 9 or 10 to a metal foil. 一種預浸體，其係將申請專利範圍第9或10項所述之樹脂組成物塗佈及/或含浸於包含有纖維之薄片狀補強基材而成者。 A prepreg obtained by coating and/or impregnating a resin composition according to claim 9 or 10 with a sheet-like reinforcing substrate comprising fibers. 一種硬化物，其係將申請專利範圍第9或10項所述之樹脂組成物硬化而得者。 A cured product obtained by hardening a resin composition as described in claim 9 or 10. 一種電性積層板，其係由申請專利範圍第9或10項所述之樹脂組成物而得者。 An electric laminated board obtained by the resin composition described in claim 9 or 10. 一種電性積層板，其係由申請專利範圍第11項所述之絕緣薄膜而得者。 An electrical laminated board obtained by the insulating film described in claim 11 of the patent application. 一種電性積層板，其係由申請專利範圍第12項所述之附有印刷配線板用樹脂之金屬箔而得者。 An electric laminated board obtained by the metal foil with a resin for printed wiring boards as described in claim 12 of the patent application. 一種電性積層板，其係由申請專利範圍第13項所述之預浸體而得者。 An electrical laminate which is obtained from the prepreg described in claim 13 of the patent application.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI607031B (en) * 2015-06-09 2017-12-01 三星Ｓｄｉ股份有限公司 Polymer resin having formula 1 or 2, adhesive film comprising the same, and display device connected by adhesive film

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017115055A (en) * 2015-12-25 2017-06-29 日立化成株式会社 Phenoxy resin
JP6722485B2 (en) * 2016-03-24 2020-07-15 日鉄ケミカル＆マテリアル株式会社 Phenoxy resin containing bisphenol F skeleton, method for producing the same, and resin composition using the same

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4675373A (en) * 1985-04-18 1987-06-23 Mitsui Petrochemical Industries, Ltd. Polyhydroxy polyether, process for its production, and its use
JPS62106925A (en) * 1985-11-06 1987-05-18 Mitsui Petrochem Ind Ltd Polyhydroxy polyether and its use
JPS63146925A (en) * 1986-08-20 1988-06-18 Mitsui Petrochem Ind Ltd Polyhydroxypolyether and use thereof
JPH08127651A (en) * 1994-10-28 1996-05-21 Kureha Chem Ind Co Ltd Production of phenoxy resin
JP3760612B2 (en) 1997-12-18 2006-03-29 大日本インキ化学工業株式会社 Production method of epoxy resin
JP3809273B2 (en) 1998-03-25 2006-08-16 東都化成株式会社 Epoxy resin composition
JP2001127215A (en) 1999-10-28 2001-05-11 Sumitomo Bakelite Co Ltd Liquid resin composition and semiconductor device using the composition
JP3747221B2 (en) 1999-11-18 2006-02-22 ジャパンエポキシレジン株式会社 Method for producing polymer epoxy resin and coating composition
MY124944A (en) 2000-02-09 2006-07-31 Hitachi Chemical Co Ltd Resin composition, adhesives prepared therewith for bonding circuit members,and circuits boards
JP2002327162A (en) 2001-03-01 2002-11-15 Hitachi Chem Co Ltd Anisotropically conductive adhesive composition, method for connecting circuit terminal and connection structure of the circuit terminal
JP4148789B2 (en) 2003-01-28 2008-09-10 東都化成株式会社 Analysis method of liquid epoxy resin
JP4449325B2 (en) 2003-04-17 2010-04-14 住友ベークライト株式会社 Adhesive film for semiconductor, semiconductor device, and manufacturing method of semiconductor device.
JP5055830B2 (en) 2005-06-03 2012-10-24 日立化成工業株式会社 Polyhydroxypolyether resin, resin composition using the same, adhesive for connecting circuit members, and circuit board
JP5376767B2 (en) * 2007-03-26 2013-12-25 新日鉄住金化学株式会社 Novel thermoplastic polyhydroxy polyether resin and resin composition containing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI607031B (en) * 2015-06-09 2017-12-01 三星Ｓｄｉ股份有限公司 Polymer resin having formula 1 or 2, adhesive film comprising the same, and display device connected by adhesive film

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