TWI498378B - Thermal-curable resin composition comprising carboxyl-containing modified ester resin - Google Patents

Thermal-curable resin composition comprising carboxyl-containing modified ester resin Download PDF

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TWI498378B
TWI498378B TW100143888A TW100143888A TWI498378B TW I498378 B TWI498378 B TW I498378B TW 100143888 A TW100143888 A TW 100143888A TW 100143888 A TW100143888 A TW 100143888A TW I498378 B TWI498378 B TW I498378B
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compound
group
anhydride
resin
ester resin
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TW100143888A
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TW201241081A (en
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Naoto Ogiwara
Hidenobu Kobayashi
Sei Jun
Koichi Tosaki
Kazunori Matsudo
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Toyo Ink Sc Holdings Co Ltd
Toyochem Co Ltd
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/08—Polyesters modified with higher fatty oils or their acids, or with resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyesters Or Polycarbonates (AREA)

Description

包含含有羧基之改質酯樹脂的熱硬化性樹脂組成物Thermosetting resin composition containing a modified ester resin containing a carboxyl group

本發明關於一種用於接著劑及塗佈劑的熱硬化性樹脂組成物。更關於一種用於以印刷配線板為首之電子材料週邊所用之接著劑及塗佈劑的熱硬化性樹脂組成物。The present invention relates to a thermosetting resin composition for an adhesive and a coating agent. More specifically, it relates to a thermosetting resin composition for an adhesive and a coating agent used for the periphery of an electronic material including a printed wiring board.

近年來電子學領域的發展卓越，尤其是電子機器的小型化、輕量化、高密度化的進步，對此等性能的要求越來越高程度。為了對應此種要求，以印刷配線板為首之電子材料的薄型化、多層化、高精密化之研究盛行。伴隨而來，對該等中所使用之接著劑、塗佈劑要求有先前於以玻璃環氧等為代表之厚實硬質基板所未被要求之高度可撓性、屈曲性、接著性、伴隨空間狹窄化的高電絕緣性、密著性、熱安定性。進一步要求在使用焊錫膏(solder cream)或後焊劑(post flux)等之焊接步驟時必要的焊劑耐性等。用於這種電子材料週邊之接著劑/塗佈劑，具體而言可例舉如後述的(1)至(6)。In recent years, the development of the field of electronics has been excellent, especially the advancement of miniaturization, weight reduction, and high density of electronic devices, and the requirements for such performance have become higher and higher. In order to meet such requirements, research on thinning, multilayering, and high precision of electronic materials including printed wiring boards is prevalent. Along with the adhesives and coating agents used in the above-mentioned materials, high flexibility, buckling, adhesion, and accompanying space which are not required for a thick hard substrate typified by glass epoxy or the like are required. Narrowing high electrical insulation, adhesion, thermal stability. Further, it is required to have flux resistance and the like necessary when using a soldering step such as solder cream or post flux. Specific examples of the adhesive/coating agent used for the periphery of such an electronic material include (1) to (6) which will be described later.

(1)　層間接著劑：為了使電路基板之間貼合而使用者，直接接至銅或銀電路。使用於多層基板的層間，有液狀或薄片狀者。(1) Interlayer adhesive: In order to bond the circuit boards, the user directly connects to a copper or silver circuit. Used in the layer of the multilayer substrate, there are liquid or flakes.

(2)　覆蓋層薄膜用接著劑：為了使覆蓋層薄膜(以保護電路的最表面為目的而使用之聚醯亞胺膜等)與底板之電路基板貼合而使用，多為預先使聚醯亞胺膜與接著層一體化者。(2) Adhesive for the cover film: In order to bond the cover film (such as a polyimide film used for the purpose of protecting the outermost surface of the circuit) to the circuit board of the substrate, it is often used in advance. The imine film is integrated with the subsequent layer.

(3)　銅包覆膜(CCL)用接著劑：為了使聚醯亞胺膜與銅箔貼合而使用。銅電路形成時施以蝕刻等加工。(3) Adhesive for copper clad film (CCL): used to bond a polyimide film to a copper foil. When the copper circuit is formed, etching or the like is performed.

(4)　覆蓋層：以保護電路的最表面為目的而使用，將印刷油墨印刷於電路上，使接著薄片貼合後，硬化而形成。有感光性和熱硬化性者。(4) Cover layer: It is used for the purpose of protecting the outermost surface of the circuit, and the printing ink is printed on the circuit, and the subsequent sheets are bonded and cured. Sensitive and thermostable.

(5)補強板用接著劑：以補足配線板的機械性強度為目的，為了將配線板的一部份固定於金屬、玻璃環氧、聚醯亞胺等補強板而使用。(5) Adhesive for reinforcing plate: For the purpose of complementing the mechanical strength of the wiring board, a part of the wiring board is used for fixing to a reinforcing plate such as metal, glass epoxy, or polyimide.

(6)電磁波屏蔽用接著劑：以遮蔽由電子電路產生之電磁噪音為目的，貼著於撓性印刷配線板。(6) Electromagnetic wave shielding adhesive: It is attached to a flexible printed wiring board for the purpose of shielding electromagnetic noise generated by an electronic circuit.

此等之形態有液狀(印刷用而油墨化者)和薄片狀(預先膜化者)等，因應用途而選擇適宜的形態。In the form of a liquid (for ink for printing) and a sheet (pre-membrane), an appropriate form is selected depending on the application.

為了回應對於這一類電子材料週邊部材的高要求，雖進行各式各樣的研究，未能得到充分滿足全部的特性者。例如，已揭示以具有特定酸價之聚酯-聚胺甲酸酯及環氧樹脂作為主成分之接著劑組成物(專利文獻1)。此雖顯示源自胺甲酸酯鍵之良好的接著性，但交聯點之間的距離遠而難以形成充分的交聯，因此有缺乏耐熱性之問題。為了補足這點而增加環氧樹脂量時，有對基材的潤濕性降低、接著強度降低之問題。再者，因使用聚酯骨架作為主鏈，而有在高溫加濕時的絕緣信賴性顯著低劣之問題。In response to the high demands on the peripheral materials of this type of electronic materials, various studies have not been performed to fully satisfy all the characteristics. For example, an adhesive composition having a polyester-polyurethane having a specific acid value and an epoxy resin as a main component has been disclosed (Patent Document 1). Although this shows a good adhesion derived from a urethane bond, the distance between the crosslinking points is too large to form sufficient crosslinking, and thus there is a problem of lack of heat resistance. When the amount of the epoxy resin is increased in order to complement this point, there is a problem that the wettability to the substrate is lowered and the strength of the adhesive is lowered. Further, since the polyester skeleton is used as the main chain, there is a problem that the insulation reliability at the time of high-temperature humidification is remarkably inferior.

又，已揭示包含胺甲酸酯改質之含有羧基之聚酯樹脂、環氧樹脂及硬化劑之接著劑組成物(專利文獻2)。此雖顯示源自胺甲酸酯鍵之良好的接著性，但有缺乏耐熱性之問題。又，胺甲酸酯樹脂的分子量低，用壓機(press)等而熱硬化時產生過多超出部分之加工性差之問題。再者，與專利文獻1相同，因使用聚酯骨架作為主鏈，而有在高溫加濕時的絕緣信賴性顯著低劣之問題。Further, an adhesive composition containing a carboxyl group-containing polyester resin, an epoxy resin, and a curing agent, which is modified by a carbamate, has been disclosed (Patent Document 2). Although this shows good adhesion from the urethane bond, there is a problem of lack of heat resistance. Further, the urethane resin has a low molecular weight, and when it is thermally cured by a press or the like, there is a problem that excessive workability is excessive. Further, similarly to Patent Document 1, since the polyester skeleton is used as the main chain, there is a problem that the insulation reliability at the time of high-temperature humidification is remarkably inferior.

又，已揭示包含聚醯亞胺矽氧烷、兩末端環氧矽氧烷及硬化劑之樹脂組成物(專利文獻3)。其系中雖具有矽氧烷樹脂特有的屈曲性和優異耐熱性，但矽氧烷骨架本身缺乏對基材的密著性，而由交聯密度低的環氧矽氧烷之硬化，有無法得到充分的接著強度之問題。又，環氧基的交聯點之間的距離大，用壓機等而熱硬化時產生過多超出部分之加工性差之問題。再者，因與其他成分的互溶性顯著不佳，而有缺乏組成物設計的自由度、以組成物而言塗膜耐性不充分等問題。Further, a resin composition comprising a polyimine oxime, a two-terminal epoxy siloxane and a curing agent has been disclosed (Patent Document 3). Although the system has buckling properties and excellent heat resistance which are characteristic of the decane resin, the siloxane skeleton itself lacks adhesion to the substrate, and the epoxy oxirane having a low crosslinking density is hard to be cured. A sufficient problem of strength is obtained. Further, the distance between the crosslinking points of the epoxy groups is large, and when it is thermally cured by a press or the like, there is a problem that the workability of the excess portion is excessive. Further, since the mutual solubility with other components is remarkably poor, there is a problem that the degree of freedom in designing the composition is insufficient, and the film resistance is insufficient in terms of the composition.

又，已揭示以環氧樹脂、盡可能減少離子性不純物之NBR橡膠、含氮之酚醛清漆樹脂(phenol novolac resin)作為主成分之熱硬化性樹脂組成物(專利文獻4)。此接著劑組成物，用壓機等而熱硬化時過多源自NBR橡膠之超出部分，有加工性差之缺點。又，為了補足這點而添加過多環氧樹脂和酚類，則有接著強度降低之問題。再者，盡可能減少離子性不純物之NBR橡膠高價而有工業上的使用困難之情況。Further, a thermosetting resin composition containing an epoxy resin, an NBR rubber which reduces ionic impurities as much as possible, and a phenol novolac resin as a main component has been disclosed (Patent Document 4). This adhesive composition is excessively derived from the excess of the NBR rubber when it is thermally cured by a press or the like, and has a disadvantage of poor workability. Further, in order to complement this point, if too much epoxy resin and phenol are added, there is a problem that the strength of the bonding is lowered. Further, it is difficult to reduce the NBR rubber of ionic impurities as much as possible and it is difficult to use industrially.

又，已揭示包含環氧樹脂、酚樹脂、環氧樹脂用硬化促進劑及彈性體之樹脂組成物(專利文獻5)。此情況同樣有難以同時改善源自彈性體之加工性惡化、源自環氧-酚硬化系之接著強度降低之問題。Further, a resin composition containing an epoxy resin, a phenol resin, a curing accelerator for an epoxy resin, and an elastomer has been disclosed (Patent Document 5). In this case as well, it is difficult to simultaneously improve the deterioration of the workability due to the elastomer and the decrease in the strength of the adhesive derived from the epoxy-phenol curing system.

又，已揭示包含柔軟骨架之聚丁二烯之樹脂組成物。Further, a resin composition of a polybutadiene comprising a soft skeleton has been disclosed.

例如，已揭示使用調配具有聚丁二烯骨架之聚醯亞胺樹脂、聚丁二烯多元醇及嵌段異氰酸酯之樹脂組成物作為可撓性電路的保護膜(overcoat)劑的例子(專利文獻6)。For example, an example of using an epoxy resin composition having a polybutadiene skeleton, a polybutadiene polyol, and a blocked isocyanate as an overcoat agent for a flexible circuit has been disclosed (Patent Document) 6).

又，已揭示調配具有聚丁二烯骨架及聚矽氧烷骨架之聚醯胺醯亞胺樹脂以及環氧樹脂之樹脂組成物(專利文獻7)。Further, a resin composition in which a polyamidoxime imine resin having a polybutadiene skeleton and a polyoxyalkylene skeleton and an epoxy resin are blended is disclosed (Patent Document 7).

再者，已揭示調配具有聚丁二烯骨架之聚醯亞胺樹脂以及環氧樹脂之樹脂組成物(專利文獻8)。Further, a resin composition in which a polyimide resin having a polybutadiene skeleton and an epoxy resin are blended has been disclosed (Patent Document 8).

然而，此等之丁二烯系樹脂，需要於高溫反應、丁二烯骨架特有的氧化而引起分子內交聯，有樹脂在反應中膠化、組成物之保存安定性顯著降低之問題。However, such butadiene-based resins are required to undergo intramolecular crosslinking due to oxidation at a high temperature and peculiar oxidation of a butadiene skeleton, and there is a problem that the resin is gelled during the reaction and the storage stability of the composition is remarkably lowered.

又，已揭示著眼於氫化聚丁二烯骨架(專利文獻9)。此系使用由具有羧基之氫化聚丁二烯樹脂、具有環氧基之丙烯酸樹脂所成之複合樹脂。因此，源自氫化聚丁二烯骨架之優異可撓性、具有對銅的密著性。然而，因合成複合樹脂時導入酯骨架，高溫加濕時的絕緣信賴性和耐藥品性等作為一般電氣電路基板的絕緣材料之基本特性有問題。Further, it has been revealed that a hydrogenated polybutadiene skeleton is disclosed (Patent Document 9). This is a composite resin composed of a hydrogenated polybutadiene resin having a carboxyl group and an acrylic resin having an epoxy group. Therefore, the hydrogenated polybutadiene skeleton is excellent in flexibility and has adhesion to copper. However, when an ester skeleton is introduced during the synthesis of a composite resin, insulation reliability and chemical resistance at the time of high-temperature humidification have problems as basic properties of an insulating material of a general electric circuit board.

又，已揭示源自酯鍵之具有鏈狀結構的含有羧基之改質環氧樹脂(專利文獻10)。此系因藉由二元酸和二環氧丙基醚型環氧化合物之聚合反應而導入酯鍵至主鏈，對銅或各種基材具有優異接著強度和耐熱性。然而，因以水解性差之酯骨架作為主鏈，有高溫加濕時的絕緣信賴性和耐藥品性顯著低劣問題。又，因二元酸為主要原料，相較於使用胺甲酸酯樹脂或NBR橡膠系不易呈現可撓性，有難以兼得耐熱性之問題。Further, a modified carboxyl group-containing epoxy resin having a chain structure derived from an ester bond has been disclosed (Patent Document 10). This is because the ester bond is introduced into the main chain by polymerization of a dibasic acid and a diepoxypropyl ether type epoxy compound, and has excellent adhesion strength and heat resistance to copper or various substrates. However, since the ester skeleton having poor hydrolyzability is used as the main chain, there is a problem that insulation reliability and chemical resistance at the time of high-temperature humidification are remarkably inferior. Further, since the dibasic acid is the main raw material, it is less likely to exhibit flexibility than the use of the urethane resin or the NBR rubber, and it is difficult to achieve both heat resistance.

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

[專利文獻1]　日本特開平11-116930號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-116930

[專利文獻2]　日本特開2007-51212號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-51212

[專利文獻3]　日本特開2004-91648號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-91648

[專利文獻4]　日本特開2003-165898號公報[Patent Document 4] Japanese Patent Laid-Open Publication No. 2003-165898

[專利文獻5]　日本特開2007-161811號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-161811

[專利文獻6]　日本特開平11-199669號公報[Patent Document 6] Japanese Patent Laid-Open No. Hei 11-199669

[專利文獻7]　日本特開平11-246760號公報[Patent Document 7] Japanese Patent Laid-Open No. Hei 11-246760

[專利文獻8]　日本特開2003-292575號公報[Patent Document 8] Japanese Patent Laid-Open Publication No. 2003-292575

[專利文獻9]　日本特開2000-302839號公報[Patent Document 9] Japanese Patent Laid-Open Publication No. 2000-302839

[專利文獻10]　日本特開2005-60662號公報[Patent Document 10] Japanese Patent Laid-Open Publication No. 2005-60662

本發明之目的係提供優異於接著性、耐熱性、可撓性、屈曲性、密著性、電氣絕緣性、耐濕熱性等，尤其是兼顧接著性與電氣絕緣性、兼顧屈曲性與耐熱性這點來看非常優異的接著劑及塗佈劑。An object of the present invention is to provide excellent adhesion, heat resistance, flexibility, buckling, adhesion, electrical insulation, moisture and heat resistance, and the like, in particular, adhesion and electrical insulation, and both buckling and heat resistance. This is a very excellent adhesive and coating agent.

再者，以提供適宜用於以印刷配線板為首之電子材料週邊所用之接著劑及塗佈劑之熱硬化性樹脂組成物為目的。Furthermore, it is intended to provide a thermosetting resin composition suitable for use as an adhesive and a coating agent for use in the periphery of an electronic material such as a printed wiring board.

本發明者們為了解決前述課題而深入研究的結果，發現特定的含有羧基之改質酯樹脂係解決前述問題者，而達成本發明。As a result of intensive studies to solve the above problems, the present inventors have found that a specific carboxyl group-containing modified ester resin solves the above problems and achieves the present invention.

亦即，第1發明係關於一種熱硬化性樹脂組成物，其係包含：(A)含有羧基之改質酯樹脂；(B)選自含有環氧基之化合物、含有異氰酸酯基之化合物、及含有封端化異氰酸酯基之化合物所成之群組之至少一種化合物；以及(C)熱硬化助劑；(A)含有羧基之改質酯樹脂係由下述步驟製成者：使(a)多元醇化合物與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應而生成(c)含有羧基之酯樹脂；使前述(c)含有羧基之酯樹脂與(d)於1分子中具有至少2個環氧基之環氧化合物進行反應而生成(e)含有側鏈羥基之改質酯樹脂；再來，使(e)含有側鏈羥基之改質酯樹脂與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應。In other words, the first aspect of the invention relates to a thermosetting resin composition comprising: (A) a modified ester resin containing a carboxyl group; (B) a compound selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and At least one compound comprising a group of blocked isocyanate groups; and (C) a thermosetting assistant; (A) a modified ester resin containing a carboxyl group produced by the following steps: (a) The polyol compound is reacted with (b) at least one compound containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride to form (c) a carboxyl group-containing ester resin; and the above (c) a carboxyl group-containing ester resin And (d) reacting an epoxy compound having at least two epoxy groups in one molecule to form (e) a modified ester resin containing a side chain hydroxyl group; and further, (e) modifying a side chain hydroxyl group The ester resin is reacted with (b) at least one compound containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride.

又，第2發明係關於第1發明之熱硬化性樹脂組成物，其中，(a)多元醇化合物係選自聚酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚丁二烯多元醇及聚矽氧烷多元醇所成之群組之至少一種化合物。In the thermosetting resin composition of the first aspect of the invention, the (a) polyol compound is selected from the group consisting of polyester polyols, polycarbonate polyols, polyether polyols, and polybutadiene polyols. At least one compound of the group formed by an alcohol and a polyoxyalkylene polyol.

又，第3發明係關於第1或第2發明之熱硬化性樹脂組成物，其中，(b)含有酸酐基之化合物係選自甲基四氫酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、納迪克酸酐(nadic acid anhydride)、甲基納迪克酸酐、氫化甲基納迪克酸酐、苯乙烯基內苯乙烯四氫酞酸酐(styrendostyrene tetrahydrophthalic anhydride)、3,6-內亞甲基四氫酞酸酐、甲基內亞甲基四氫酞酸酐、三烷基四氫酞酸酐、酞酸酐、四溴酞酸酐、苯偏三酸酐及焦蜜石酸二酐所成之群組之至少一種化合物。According to a third aspect of the invention, in the thermosetting resin composition of the first or second aspect, the (b) acid anhydride group-containing compound is selected from the group consisting of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. , methyl hexahydrophthalic anhydride, nadic acid anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, styrendostyrene tetrahydrophthalic anhydride, 3,6- Methylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, trialkyltetrahydrofurfuric anhydride, phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride and pyromellitic dianhydride At least one compound of the group.

又，第4發明係關於第1至第3發明中任一項之熱硬化性樹脂組成物，其中，(A)含有羧基之改質酯樹脂的酸價係1至100mgKOH/g。In the thermosetting resin composition according to any one of the first to third aspects, the acid ester of the (A) carboxyl group-containing modified ester resin is from 1 to 100 mgKOH/g.

又，第5發明係關於第1至第4發明中任一項之熱硬化性樹脂組成物，其中，(A)含有羧基之改質酯樹脂的重量平均分子量係5000至500000。The thermosetting resin composition according to any one of the first to fourth aspects of the present invention, wherein (A) the carboxyl group-containing modified ester resin has a weight average molecular weight of 5,000 to 500,000.

又，第6發明係關於第1至第5發明中任一項之熱硬化性樹脂組成物，其中，(C)熱硬化助劑係選自氮雜環丙烷(aziridine)化合物、含有碳二亞胺(carbodiimide)基之化合物、苯并(benzoxazine)化合物、酚樹脂、咪唑類及二氰二胺所成之群組之至少一種。The thermosetting resin composition according to any one of the first to fifth aspects, wherein the (C) thermosetting assistant is selected from the group consisting of aziridine compounds and carbon dioxide. Carbodiimide-based compound, benzo At least one of the group consisting of a benzoxazine compound, a phenol resin, an imidazole, and dicyandiamide.

再者，第7發明係關於一種硬化物，其係藉由加熱使第1至第6發明中任一項之熱硬化性樹脂組成物硬化而得到者。Furthermore, the seventh invention relates to a cured product obtained by curing the thermosetting resin composition according to any one of the first to sixth inventions by heating.

再來，第8發明係關於一種印刷配線板，其具有由第7發明之硬化物所成之層。According to a eighth aspect of the invention, there is provided a printed wiring board comprising the layer formed of the cured product of the seventh aspect of the invention.

本發明之熱硬化性樹脂組成物優異於接著性、耐熱性、可撓性、屈曲性、密著性、電氣絕緣性、耐濕熱性、耐焊劑(flux)性等，尤其是兼顧接著性和電氣絕緣性、兼顧屈曲性和耐熱性這點來看非常優異。因此，可提供適宜用於以印刷配線板為首之電子材料週邊所用之接著劑及塗佈劑之熱硬化性樹脂組成物。The thermosetting resin composition of the present invention is excellent in adhesion, heat resistance, flexibility, flexibility, adhesion, electrical insulating properties, moist heat resistance, flux resistance, and the like, and particularly, adhesion and It is excellent in electrical insulation, buckling resistance and heat resistance. Therefore, it is possible to provide a thermosetting resin composition suitable for use as an adhesive and a coating agent for the periphery of an electronic material including a printed wiring board.

本發明之(A)含有羧基之改質酯樹脂係可藉由下述方式而得到：使(a)多元醇化合物與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物(b)[以下亦僅記載為「(b)含有酸酐基之化合物」]進行反應而生成(c)含有羧基之酯樹脂；使前述(c)含有羧基之酯樹脂與(d)於1分子中具有至少2個環氧基之環氧化合物進行反應而生成(e)含有側鏈羥基之改質酯樹脂；再來，使(e)含有側鏈羥基之改質酯樹脂與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應。The (A) carboxyl group-containing modified ester resin of the present invention can be obtained by: (a) a polyol compound and (b) at least one selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. The acid anhydride group-containing compound (b) (hereinafter also referred to as "(b) acid anhydride group-containing compound") is reacted to produce (c) a carboxyl group-containing ester resin; (c) the carboxyl group-containing ester resin and (d) An epoxy compound having at least two epoxy groups in one molecule is reacted to form (e) a modified ester resin containing a side chain hydroxyl group; and further, (e) a modified ester resin containing a side chain hydroxyl group and (b) at least one compound containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride.

藉由使用(A)含有羧基之改質酯樹脂，可顯著改善例如硬化前的保存安定性、硬化後的可撓性、絕緣信賴性、銲錫耐熱性、加濕後的銲錫耐熱性等。該等之物性，在以印刷配線板為首之電子材料週邊所用之接著劑及塗佈劑中皆為非常重要的物性。By using (A) a modified ester resin containing a carboxyl group, for example, storage stability before curing, flexibility after curing, insulation reliability, solder heat resistance, solder heat resistance after humidification, and the like can be remarkably improved. These physical properties are very important physical properties in the adhesives and coating agents used in the periphery of electronic materials such as printed wiring boards.

上述物性之顯著改善係因起始原料中使用(a)多元醇化合物和(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物。亦即，相較於以往使用以二元酸為原料之聚酯骨架作為主鏈之樹脂，可賦予源自(a)多元醇化合物之可撓性和加工性等。又，由(a)多元醇化合物與(b)含有酸酐基之化合物而生成(c)含有羧基之酯樹脂時，因絕緣信賴性差的酯鍵基經由(b)含有酸酐基之化合物所具有之大量取代基保護，相較於以往使用聚酯骨架作為主鏈之樹脂，可顯著提昇絕緣信賴性、銲錫耐熱性等。A significant improvement in the above physical properties is due to the use of (a) a polyol compound and (b) at least one compound containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. In other words, the flexibility and workability derived from the (a) polyol compound can be imparted as compared with the conventional resin using a polyester skeleton using a dibasic acid as a main chain. Further, when (a) a polyol compound and (b) an acid anhydride group-containing compound are used to form (c) a carboxyl group-containing ester resin, an ester bond group having poor insulation reliability is provided by (b) an acid anhydride group-containing compound. A large amount of substituent protection can significantly improve insulation reliability and solder heat resistance as compared with conventional resins using a polyester skeleton as a main chain.

例如，使用不屬於(b)含有酸酐基之化合物的含有酸酐基之化合物取代(b)含有酸酐基之化合物時，一般而言由源自酯鍵之極性所致之基材密著性和耐熱性，可得一定程度的接著強度和銲錫耐熱性。然而，在如高溫加濕的嚴格條件下，絕緣信賴性差，並且銲錫耐熱性無法滿足高溫的銲錫試驗或加濕狀態的銲錫試驗這類高度銲錫耐熱性。為了解決此等課題，一般係添加高Tg(Tg：玻璃轉化溫度)骨架之樹脂或高Tg骨架之硬化劑，添加此種硬化劑，則接著層整體高Tg化，對基材的密著性降低而接著強度顯著降低。For example, when an acid anhydride group-containing compound which does not belong to (b) an acid anhydride group-containing compound is substituted for (b) an acid anhydride group-containing compound, the substrate is generally adhered to heat and resistance due to the polarity of the ester bond. Sex, a certain degree of adhesion strength and solder heat resistance can be obtained. However, under severe conditions such as high-temperature humidification, insulation reliability is poor, and solder heat resistance cannot satisfy high solder heat resistance such as a high-temperature solder test or a wet solder test. In order to solve these problems, a resin having a high Tg (Tg: glass transition temperature) skeleton or a hardener having a high Tg skeleton is generally added, and when such a curing agent is added, the entire layer is high in Tg and the adhesion to the substrate is high. Decrease and then the strength is significantly reduced.

另一方面，(A)含有羧基之改質酯樹脂在由(a)多元醇化合物與(b)含有酸酐基之化合物(b)而生成(c)含有羧基之酯樹脂時，酯鍵基經由大量取代基保護。因此，同時滿足良好的絕緣信賴性和銲錫耐熱性，並且不須提昇Tg，可在保持高接著強度之下顯示高度耐熱性。On the other hand, when (A) a modified ester resin containing a carboxyl group produces (c) an ester resin containing a carboxyl group from (a) a polyol compound and (b) an acid anhydride group-containing compound (b), the ester bond group is passed through A large number of substituent protection. Therefore, both good insulation reliability and solder heat resistance are satisfied, and high heat resistance can be exhibited while maintaining high adhesion strength without raising the Tg.

又，(A)含有羧基之改質酯樹脂，尤其是作為(a)多元醇化合物而使用聚碳酸酯多元醇、脂環式聚酯多元醇等聚酯多元醇，聚丁二烯多元醇(包含氫化者)、聚醚多元醇及/或聚矽氧烷多元醇，可發揮更高的電氣絕緣性和耐熱性。並且，藉由適宜地選擇(d)於1分子中至少具有2個環氧基之環氧化合物，雖使用一般而言對基材的接著困難之聚碳酸酯骨架或聚矽氧烷骨架，卻可顯示高接著強度。Further, (A) a modified ester resin containing a carboxyl group, in particular, a polyester polyol such as a polycarbonate polyol or an alicyclic polyester polyol, or a polybutadiene polyol (a) (a) a polyol compound ( Containing hydrogenated), polyether polyols and/or polyoxyalkylene polyols, exhibits higher electrical insulation and heat resistance. Further, by appropriately selecting (d) an epoxy compound having at least two epoxy groups in one molecule, although a polycarbonate skeleton or a polyoxyalkylene skeleton which is generally difficult to adhere to a substrate is used, Can display high adhesion strength.

例如，通常為了確保電氣絕緣性而使用聚碳酸酯或聚矽氧烷等耐熱性優異之骨架時，因對基材的密著性降低，而無法確保接著強度。另一方面，本發明藉上述理由，可解決高電氣絕緣性與接著強度之矛盾。For example, when a skeleton having excellent heat resistance such as polycarbonate or polysiloxane is used in order to ensure electrical insulation, the adhesion to the substrate is lowered, and the bonding strength cannot be ensured. On the other hand, the present invention solves the contradiction between high electrical insulation and adhesion strength for the above reasons.

又，因(A)含有羧基之改質酯樹脂不需使用過多的高Tg原料，而顯示優異屈曲性。一般而言，屈曲性高的樹脂有缺乏耐熱性之傾向。然而，(A)含有羧基之改質酯樹脂因為分子內的酯鍵基經由大量取代基保護，而顯示比一般聚酯樹脂有更高的耐熱性。再者，使(e)含有側鏈羥基之改質酯樹脂與(b)含有酸酐基之化合物進行反應，而於主鏈中導入熱交聯點，因交聯而可進一步提昇其耐熱性。Further, since (A) the modified ester resin containing a carboxyl group does not require the use of an excessively high Tg raw material, it exhibits excellent buckling property. In general, resins having high buckling tend to have a lack of heat resistance. However, (A) the modified ester resin containing a carboxyl group exhibits higher heat resistance than a general polyester resin because the ester bond group in the molecule is protected by a large number of substituents. Further, by reacting (e) a modified ester resin containing a side chain hydroxyl group with (b) a compound containing an acid anhydride group, a thermal crosslinking point is introduced into the main chain, and the heat resistance can be further improved by crosslinking.

通常為了確保屈曲性而導入低Tg骨架或胺甲酸酯鍵，該等缺乏耐熱性而無法確保高耐熱性。又，為了確保耐熱性而導入高Tg骨架或高耐熱性鍵結，由於該等一般缺乏屈曲性，無法兼顧耐熱性和屈曲性。Usually, in order to ensure the buckling property, a low Tg skeleton or a urethane bond is introduced, and such heat resistance is insufficient to ensure high heat resistance. Moreover, in order to ensure heat resistance, a high Tg skeleton or a high heat-resistant bond is introduced, and since these generally lack buckling property, heat resistance and buckling property cannot be achieved.

另一方面，本發明藉上述理由，可解決高屈曲性與高耐熱性之矛盾。作為(a)多元醇化合物適宜使用低Tg之聚碳酸酯多元醇、聚丁二烯多元醇、氫化聚丁二烯多元醇、聚醚多元醇及/或聚矽氧烷多元醇，可更加提昇屈曲性。在此，低Tg意指0℃以下。On the other hand, the present invention solves the contradiction between high buckling property and high heat resistance by the above reasons. As the (a) polyol compound, it is preferable to use a low Tg polycarbonate polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a polyether polyol, and/or a polyoxyalkylene polyol. Flexibility. Here, the low Tg means 0 ° C or less.

又，本發明之含有羧基之改質酯樹脂(A)中，適宜地導入3官能的多元醇作為多元醇化合物(a)，而可更加提昇該等效果。具體而言，導入分支結構而使樹脂層的凝集力增大，結果完全沒有對保存安定性、加工安定性、屈曲性、電氣絕緣性造成不良影響，而可提昇接著強度和耐熱性。Further, in the carboxyl group-containing modified ester resin (A) of the present invention, a trifunctional polyol is appropriately introduced as the polyol compound (a), and these effects can be further enhanced. Specifically, the branching structure is introduced to increase the cohesive force of the resin layer, and as a result, the storage stability, the process stability, the buckling property, and the electrical insulating property are not adversely affected at all, and the bonding strength and heat resistance can be improved.

以下，詳細說明本發明之包含含有羧基之改質酯樹脂(A)的熱硬化性樹脂組成物。Hereinafter, the thermosetting resin composition containing the carboxyl group-containing modified ester resin (A) of the present invention will be described in detail.

本發明之含有羧基之改質酯樹脂(A)係藉由下述方式而得到：首先，使(a)多元醇化合物與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應而生成(c)含有羧基之酯樹脂，然後，使前述(c)含有羧基之酯樹脂與(d)於1分子中至少具有2個環氧基的環氧化合物進行反應而生成(e)含有側鏈羥基之改質酯樹脂，再來，使(e)含有側鏈羥基之改質酯樹脂與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應。The carboxyl group-containing modified ester resin (A) of the present invention is obtained by first (a) a polyol compound and (b) at least one selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. The acid anhydride group-containing compound is reacted to form (c) a carboxyl group-containing ester resin, and then (c) the carboxyl group-containing ester resin and (d) an epoxy compound having at least two epoxy groups in one molecule. The reaction produces (e) a modified ester resin containing a side chain hydroxyl group, and further, (e) a modified ester resin containing a side chain hydroxyl group and (b) at least one selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. A compound containing an acid anhydride group is reacted.

本發明中使用的多元醇化合物(a)較佳係具有2個以上的羥基並且具有其結構中之聚合度為2以上的重複單位。又，從可調節分子量為預期值這點來看，多元醇化合物(a)較佳係使用含有2個羥基之化合物。從可呈現硬化塗膜的耐熱性和屈曲性、密著性之間有良好平衡這點來看，藉膠透層析(以下亦稱為「GPC」)測定之換算成聚苯乙烯之重量平均分子量較佳係500至50000。多元醇化合物(a)不受限於以下例子，可例舉聚酯多元醇類、聚碳酸酯多元醇類、聚醚多元醇類、聚丁二烯多元醇類及聚矽氧烷多元醇類等。再者，本申請案中在無特別限定時，重量平均分子量意指藉GPC測定之換算成聚苯乙烯之重量平均分子量。The polyol compound (a) used in the present invention preferably has two or more hydroxyl groups and has a repeating unit having a degree of polymerization of 2 or more in the structure. Further, from the viewpoint that the adjustable molecular weight is an intended value, the polyol compound (a) is preferably a compound containing two hydroxyl groups. From the point of view that there is a good balance between the heat resistance of the cured coating film and the buckling property and the adhesion, the weight average converted into polystyrene by gel permeation chromatography (hereinafter also referred to as "GPC") The molecular weight is preferably from 500 to 50,000. The polyol compound (a) is not limited to the following examples, and examples thereof include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polyoxyalkylene polyols. Wait. Further, in the present application, when it is not particularly limited, the weight average molecular weight means a weight average molecular weight converted into polystyrene by GPC.

本發明中使用的聚酯多元醇類，例如多官能醇成分與二元酸成分進行縮合反應之聚酯多元醇。多官能醇成分中，二元醇可例舉乙二醇、丙二醇、二丙二醇、二乙二醇、三乙二醇、丁二醇、1,6-己二醇、3-甲基-1,5-戊二醇、3,3’-二羥甲基庚烷、聚氧基乙二醇、聚氧基丙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、辛二醇、丁基乙基戊二醇、2-乙基-1,3-己二醇、環己二醇、雙酚A等，具有3個以上的羥基之多官能醇成分可例舉三羥甲基乙烷、聚三羥甲基乙烷、三羥甲基丙烷、聚三羥甲基丙烷、新戊四醇、聚新戊四醇、山梨醇、甘露糖醇、***糖醇、木糖醇、半乳糖醇、甘油等。The polyester polyol used in the present invention, for example, a polyester polyol in which a polyfunctional alcohol component and a dibasic acid component are subjected to a condensation reaction. Among the polyfunctional alcohol components, the glycol may, for example, be ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol or 3-methyl-1. 5-pentanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol , octyl glycol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, etc., and a polyfunctional alcohol component having three or more hydroxyl groups can be exemplified Trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, neopentylol, polyneopentaerythritol, sorbitol, mannitol, arabitol, Xylitol, galactitol, glycerin, etc.

二元酸成分可例舉對酞酸、已二酸、壬二酸、癸二酸、酞酸酐、異酞酸、偏苯三甲酸等脂肪族、芳香族二元酸及該等之酸酐。The dibasic acid component may, for example, be an aliphatic or aromatic dibasic acid such as capric acid, adipic acid, sebacic acid, sebacic acid, phthalic anhydride, isophthalic acid or trimellitic acid, or the like.

又，可使用β-丁內酯、β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯、ε-己內酯、γ-己內酯、γ-庚內酯、α-甲基-β-丙內酯等內酯類等環狀酯化合物之開環聚合而得到之聚酯多元醇。Further, β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-gyne can be used. A polyester polyol obtained by ring-opening polymerization of a cyclic ester compound such as an ester or an α-methyl-β-propiolactone.

可使用具有磷原子之聚酯多元醇，具體上可例舉2-(9,10-二氫-9-氧雜-10-磷雜菲-10-基)甲基丁二酸或其酸酐與乙二醇之聚縮合物，或者2-(9,10-二氫-9-氧雜-10-氧離子基-10-磷雜菲-10-基)甲基丁二酸-雙-(2-羥基乙基)-酯或其聚縮合而得到之聚酯多元醇。A polyester polyol having a phosphorus atom may be used, and specifically, 2-(9,10-dihydro-9-oxa-10-phosphaphenanyl)methylsuccinic acid or an anhydride thereof may be exemplified. Polycondensate of ethylene glycol, or 2-(9,10-dihydro-9-oxa-10-oxo-10-phenylphosphino-10-yl)methylsuccinic acid-bis-(2) -Hydroxyethyl)-ester or a polyester polyol obtained by polycondensation thereof.

聚酯多元醇具體上可使用Kuraray股份有限公司之Kuraray多元醇P系列。其中P-1041、P-2041、P-2010、P-2020、P-1030、P-2030有絕緣信賴性和耐熱性而較佳。As the polyester polyol, Kuraray Polyol P series of Kuraray Co., Ltd. can be specifically used. Among them, P-1041, P-2041, P-2010, P-2020, P-1030, and P-2030 are preferred in terms of insulation reliability and heat resistance.

本發明中使用的聚碳酸酯多元醇類係於其分子內具有下記通式(1)所示之構造者。The polycarbonate polyol used in the present invention has a structure represented by the following formula (1) in its molecule.

-[-R8 -O-CO-]m -　通式(1)-[-R 8 -O-CO-] m - general formula (1)

(式中，R8 表示2價有機殘基，m表示1以上的整數)。(wherein R 8 represents a divalent organic residue, and m represents an integer of 1 or more).

聚碳酸酯多元醇可藉由例如(1)二醇或雙酚與碳酸酯反應、(2)二醇或雙酚在鹼存在下與光氣作用之反應等而得到。The polycarbonate polyol can be obtained, for example, by reacting (1) a diol or a bisphenol with a carbonate, (2) a reaction of a diol or a bisphenol with a phosgene in the presence of a base, and the like.

製法(1)中使用的碳酸酯具體上可例舉碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸伸乙酯、碳酸伸丙酯等。Specific examples of the carbonate used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethyl carbonate, and propyl carbonate.

製法(1)及(2)中使用的二醇或雙酚具體上可使用乙二醇、丙二醇(propylenglycol)、二丙二醇、二乙二醇、三乙二醇、丁二醇、3-甲基-1,5-戊二醇、2-甲基-1,8-辛二醇、3,3’-二羥甲基庚烷、聚氧基乙二醇、聚氧基丙二醇、丙烷二醇(propanediol)、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,9-壬二醇、新戊二醇、辛二醇、丁基乙基戊二醇、2-乙基-1,3-己二醇、環己二醇或者雙酚A或雙酚F等雙酚類，前述雙酚類與環氧乙烷、環氧丙烷等環氧烷加成之雙酚類等。該等化合物可使用1種或2種以上的混合物。The diol or bisphenol used in the processes (1) and (2) may specifically be ethylene glycol, propylenglycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol or 3-methyl. -1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol ( Propanediol), 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, Xinji Alcohol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol or bisphenols such as bisphenol A or bisphenol F, the aforementioned bisphenols and ethylene oxide, A bisphenol or the like which is added to an alkylene oxide such as propylene oxide. These compounds may be used alone or in combination of two or more.

聚碳酸酯多元醇具體上可使用Kuraray股份有限公司之Kuraray多元醇C系列。其中PMHC-1050、PMHC-2050、C-1090、C-2090、C-1065N、C-2065N、C-1015N、C-2015N有柔軟性而較佳。又，宇部興產股份有限公司之ETERNACOLL UC-100、UM-90(1/3)、UM-90(1/1)、UM-90(3/1)之耐熱性優異而較佳。As the polycarbonate polyol, Kuraray Polyol C series of Kuraray Co., Ltd. can be specifically used. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are soft and preferable. Further, ETERNACOLL UC-100, UM-90 (1/3), UM-90 (1/1), and UM-90 (3/1) of Ube Industries Co., Ltd. are excellent in heat resistance.

本發明中使用的聚醚多元醇類例如可使用四氫呋喃、環氧乙烷、環氧丙烷、環氧丁烷等環氧烷之聚合物、共聚物及接枝共聚物；己二醇、甲基己二醇、庚二醇、辛二醇或該等之混合物的縮合而得到的聚醚多元醇類；雙酚A或雙酚F等與環氧乙烷、環氧丙烷等環氧烷加成而成之雙酚類等芳香族二醇類；使用三羥甲基乙烷、聚三羥甲基乙烷、三羥甲基丙烷、聚三羥甲基丙烷、新戊四醇、聚新戊四醇、山梨醇、甘露糖醇、***糖醇、木糖醇、半乳糖醇、甘油等多元醇作為原料的一部份而合成之聚環氧乙烷、聚環氧丙烷、環氧乙烷/環氧丙烷之嵌段共聚物或隨機共聚物、聚伸丁二醇、伸丁二醇與新戊二醇之嵌段共聚物或隨機共聚物等聚醚多元醇類等羥基為2個以上者。The polyether polyol used in the present invention may, for example, be a polymer, a copolymer or a graft copolymer of an alkylene oxide such as tetrahydrofuran, ethylene oxide, propylene oxide or butylene oxide; hexanediol or methyl group; Polyether polyol obtained by condensation of hexanediol, heptanediol, octanediol or a mixture thereof; addition of bisphenol A or bisphenol F to an alkylene oxide such as ethylene oxide or propylene oxide An aromatic diol such as bisphenol; using trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentane Polyethylene oxide, polypropylene oxide, ethylene oxide synthesized as a part of raw materials by polyols such as tetraol, sorbitol, mannitol, arabitol, xylitol, galactitol, and glycerin a polyether polyol such as a block copolymer or a propylene oxide block copolymer or a random copolymer, a polybutane diol, a block copolymer of a butane diol and a neopentyl glycol, or a random copolymer; By.

本發明中使用的聚丁二烯多元醇類，例如可例舉包含將其分子內不飽和鍵氫化者，聚乙烯系多元醇、聚丙烯系多元醇、聚丁二烯系多元醇、氫化聚丁二烯多元醇、聚異戊二烯多元醇、氫化聚異戊二烯多元醇等。The polybutadiene polyol used in the present invention may, for example, be a hydrogenated polymer having a molecularly unsaturated bond, a polyvinyl polyol, a polypropylene polyol, a polybutadiene polyol, or a hydrogenated polymer. Butadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like.

聚丁二烯多元醇的市售品可例舉日本曹達股份有限公司之NISSSO PB(G系列)、出光石油化學股份有限公司之Poly-Pd等兩末端具有羥基之液狀聚丁二烯；日本曹達股份有限公司之NISSSO PB(GI系列)、三菱化學股份有限公司之Polytail H、Polytail HA等兩末端具有羥基之氫化聚丁二烯；出光石油化學股份有限公司製之Poly-iP等兩末端具有羥基之液狀C5系聚合物；出光石油化學股份有限公司製之Epole，Kuraray股份有限公司製之TH-1、TH-2、TH-3等兩末端具有羥基之氫化聚異戊二烯等，但不受限於此。The commercially available product of the polybutadiene polyol may, for example, be NSSSO PB (G series) of Japan Soda Co., Ltd., Poly-Pd of Idemitsu Petrochemical Co., Ltd., and liquid polybutadiene having hydroxyl groups at both ends; Caesar Co., Ltd.'s NISSSO PB (GI series), Mitsubishi Chemical Co., Ltd.'s Polytail H, Polytail HA, etc., hydrogenated polybutadiene with hydroxyl groups at both ends; Poly-iP, manufactured by Idemitsu Petrochemical Co., Ltd. a liquid C5-based polymer of a hydroxyl group; Epole manufactured by Idemitsu Petrochemical Co., Ltd., a hydrogenated polyisoprene having a hydroxyl group at both ends, such as TH-1, TH-2, and TH-3 manufactured by Kuraray Co., Ltd., But it is not limited to this.

本發明中使用的聚矽氧烷多元醇類可例舉通式(2)及(3)所示之化合物。The polyoxane polyols used in the present invention may, for example, be compounds represented by the general formulae (2) and (3).

(X表示羥基，R1 、R2 分別表示碳數1至6的伸烷基，n表示5以上的整數)。(X represents a hydroxyl group, R 1 and R 2 each represent an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 5 or more).

(Y表示羥基，R3 表示碳數1至6的烷基，R4 、R5 、R6 分別表示碳數1至6的伸烷基，R7 表示氫原子或碳數1至6的烷基，n表示5以上的整數)。(Y represents a hydroxyl group, R 3 represents an alkyl group having 1 to 6 carbon atoms, R 4 , R 5 and R 6 each represent an alkylene group having 1 to 6 carbon atoms, and R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Base, n represents an integer of 5 or more).

該等多元醇化合物(a)中，特佳係由1,4-環己烷二羧酸與3-甲基-1,5-戊二醇所成之聚酯二醇、僅使用1,6-己二醇作為二醇所成之聚碳酸酯多元醇、使用1,6-己二醇與3-甲基-1,5-戊二醇作為二醇所成之聚碳酸酯二醇、使用1,9-壬二醇與2-甲基-1,8-辛二醇作為二醇所成之聚碳酸酯二醇、聚伸丁二醇、聚丙二醇或伸丁二醇與新戊二醇之共聚合聚醚多元醇、聚丁二烯多元醇、氫化聚丁二烯多元醇、聚矽氧烷多元醇等。該等多元醇化合物(a)因骨架的柔軟性、耐熱性、耐水解性優異，而用於含有羧基之改質酯樹脂(A)時，電氣絕緣性、屈曲性、耐熱性、耐濕性等特別優異。Among these polyol compounds (a), a polyester diol composed of 1,4-cyclohexanedicarboxylic acid and 3-methyl-1,5-pentanediol is used, and only 1,6 is used. a polycarbonate polyol formed by using hexanediol as a diol, a polycarbonate diol formed using 1,6-hexanediol and 3-methyl-1,5-pentanediol as a diol, and used 1,8-nonanediol and 2-methyl-1,8-octanediol as a diol to form a polycarbonate diol, a polybutane diol, a polypropylene glycol or a butane diol and neopentyl glycol The copolymerized polyether polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyoxyalkylene polyol, and the like. These polyol compounds (a) are excellent in flexibility, heat resistance, and hydrolysis resistance of the skeleton, and are used for electrical insulating properties, buckling properties, heat resistance, and moisture resistance when used in a modified ester resin (A) containing a carboxyl group. Especially excellent.

本發明中，該等多元醇化合物(a)可單獨使用，亦可併用複數個。In the present invention, the polyol compounds (a) may be used singly or in combination of plural kinds.

本發明的最大特徵係前述多元醇化合物(a)與選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物(b)進行反應而得到之含有羧基之酯樹脂(c)中的酯鍵基經由大量取代基保護。The most characteristic feature of the present invention is a carboxyl group-containing ester resin obtained by reacting the polyol compound (a) with at least one acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride (c) The ester bond group is protected by a large number of substituents.

本發明中使用的選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物(b)，可例舉如甲基四氫酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、納迪克酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、苯乙烯基內苯乙烯四氫酞酸酐、3,6-內亞甲基四氫酞酸酐、甲基內亞甲基四氫酞酸酐、三烷基四氫酞酸酐等脂環式二元酸酐；氫化偏苯三甲酸酐、氫化焦蜜石酸酐等三元酸以上的脂環式多元酸酐；酞酸酐、四溴酞酸酐、偏苯三羧酸酐等芳香族二元酸酐；聯苯四羧酸二酐、二苯基醚四羧酸二酐、焦蜜石酸酐、二苯基酮四羧酸二酐等三元酸以上的芳香族多元酸酐。The at least one acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride used in the present invention may, for example, be methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. Methyl hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, styrylstyrene tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl An alicyclic dibasic acid anhydride such as an endo-methylenetetrahydrophthalic anhydride or a trialkyltetrahydrophthalic anhydride; an alicyclic polybasic acid anhydride such as a tribasic acid such as a hydrogenated trimellitic anhydride or a hydrogenated pyrogallic anhydride; An aromatic dibasic acid anhydride such as tetrabromophthalic anhydride or trimellitic anhydride; biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, pyrogallic anhydride, diphenylketone tetracarboxylic dianhydride, etc. An aromatic polybasic acid anhydride having a tribasic acid or higher.

該等含有酸酐基之化合物(b)中較佳係甲基四氫酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、納迪克酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐等。與多元醇化合物(a)反應生成含有羧基之酯樹脂(c)時，絕緣信賴性差的酯鍵基以大量取代基保護，以經由大量取代基保護之酯鍵基構成主鏈，相較於以往使用聚酯骨架作為主鏈的樹脂，可保持高接著性並且顯著提昇絕緣信賴性、銲錫耐熱性等。Preferred among the acid anhydride group-containing compound (b) are methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated nail Kinadic anhydride and the like. When the polyol compound (a) is reacted with the polyol compound (a) to form a carboxyl group-containing ester resin (c), the ester bond group having poor insulation reliability is protected by a large number of substituents, and the ester bond group protected by a large number of substituents constitutes a main chain, compared with the conventional one. A resin using a polyester skeleton as a main chain can maintain high adhesion and remarkably improve insulation reliability, solder heat resistance, and the like.

又，含有酸酐基之化合物(b)較佳亦為偏苯三羧酸酐或焦蜜石酸酐等。可增加與多元醇化合物(a)反應而含有羧基之酯樹脂(c)的末端羧基數量，接著，在與於1分子中具有至少2個環氧基的環氧化合物(d)的反應中，可高分子量化。然後，高分子量化而樹脂的凝集力增大，因此可保持可撓性並且塗膜形成後可形成耐性更優異而強韌的塗膜。Further, the acid anhydride group-containing compound (b) is preferably trimellitic anhydride or pyrogallic anhydride. The number of terminal carboxyl groups of the ester resin (c) having a carboxyl group which is reacted with the polyol compound (a) can be increased, and then, in the reaction with the epoxy compound (d) having at least two epoxy groups in one molecule, It can be polymerized. Then, since the polymer is increased in molecular weight and the cohesive force of the resin is increased, flexibility can be maintained and a coating film which is more excellent in resistance and tough can be formed after the formation of the coating film.

本發明中，可任意地使用含有羥基之化合物(a-1)。含有羥基之化合物(a-1)係含有1個以上的羥基之化合物，除了屬於前述「多元醇化合物(a)」化合物以外的化合物，其代表例，可例舉如於分子中具有1個羥基之單醇化合物(a-1-1)、於分子中具有2個羥基之二醇化合物(a-1-2)、於分子中具有3個以上羥基之化合物(a-1-3)。該等亦可於分子中併有羥基、羥基以外的官能基。又，可單獨使用，亦可複數併用。In the present invention, the compound (a-1) having a hydroxyl group can be optionally used. The compound (a-1) having a hydroxyl group is a compound containing one or more hydroxyl groups, and a compound other than the compound of the above-mentioned "polyol compound (a)", and a representative example thereof may have one hydroxyl group in the molecule. The monool compound (a-1-1), a diol compound (a-1-2) having two hydroxyl groups in the molecule, and a compound (a-1-3) having three or more hydroxyl groups in the molecule. These may also have a functional group other than a hydroxyl group or a hydroxyl group in the molecule. Further, they may be used singly or in combination.

於分子中具有1個羥基之單醇化合物(a-1-1)可例舉如甲醇、乙醇、正丙醇、異丙醇、正丁二醇、異丁二醇、三級丁二醇、月桂醇、硬脂醇等脂肪族單醇；環己醇等脂環族單醇；苯甲醇、茀醇等芳香族單醇；酚、甲氧苯酚等酚類；併有羥基以外的官能基之單醇化合物可例舉12-羥基硬脂酸等含有羥基之羧酸化合物、環氧丙醇等含有羥基之環氧化合物、氧雜環丁醇(oxetane alcohol)等含有羥基之氧雜環丁烷化合物。其他，可例舉單一末端甲氧化聚乙二醇、單一末端甲氧化聚丙二醇、以單醇為開始劑之己內酯加成聚合物等寡聚物型單醇。The monool compound (a-1-1) having one hydroxyl group in the molecule may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butylene glycol, isobutylene glycol or tertiary butanediol. An aliphatic monoalcohol such as lauryl alcohol or stearyl alcohol; an alicyclic monoalcohol such as cyclohexanol; an aromatic monoalcohol such as benzyl alcohol or decyl alcohol; a phenol such as phenol or methoxyphenol; and a functional group other than a hydroxyl group. The monool compound may, for example, be a hydroxyl group-containing carboxylic acid compound such as 12-hydroxystearic acid, a hydroxyl group-containing epoxy compound such as glycidyl alcohol, or a hydroxy-containing oxetane such as oxetane alcohol. Compound. Other examples include oligomeric monoalcohols such as a single-end methoxypolyethylene glycol, a single-end methoxypolypropylene glycol, and a caprolactone addition polymer using a monool as a starting agent.

本發明中，使用該等於分子內具有1個羥基之單醇化合物(a-1-1)時，可封裝得到之含有羧基之酯樹脂(c)的末端。因此，有意地於合成低分子量的含有羧基之改質酯樹脂(A)時等，需要調整分子量時可適宜的使用。又，使用併有羥基以外的官能基之含有羥基之化合物時，可於含有羧基之酯樹脂(c)的末端導入羧基以外的官能基，需要含有羧基之酯樹脂(c)之末端改質時，可適宜的使用。考慮到羥基的反應性和聚合調控，單醇化合物(a-1-1)較佳係用月桂醇、硬脂醇、環己醇、12-羥基硬脂酸、環氧丙醇、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁酯等。In the present invention, when the monool compound (a-1-1) having one hydroxyl group in the molecule is used, the terminal of the carboxyl group-containing ester resin (c) can be encapsulated. Therefore, when a low molecular weight carboxylate-containing modified ester resin (A) is intentionally synthesized, it is necessary to suitably adjust the molecular weight. When a hydroxyl group-containing compound having a functional group other than a hydroxyl group is used, a functional group other than a carboxyl group may be introduced at the terminal of the carboxyl group-containing ester resin (c), and when the terminal resin of the carboxyl group-containing ester resin (c) is required to be modified , can be used as appropriate. The monool compound (a-1-1) is preferably a lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidyl alcohol, (methyl) in view of reactivity of a hydroxyl group and polymerization regulation. 2-hydroxyethyl acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

又，於分子內具有2個基之二醇化合物(a-1-2)可例舉如乙二醇、丙二醇、2-甲基-1,3-丙二醇、2-甲基-2-乙基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-丁基-2-甲基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-甲基-2,4-戊二醇、1,3,5-三甲基-1,3-戊二醇、2-甲基-1,8-辛二醇、3,3’-二羥甲基庚烷、丙烷二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,9-壬二醇、新戊二醇、辛二醇、3-丁基-3-乙基-1,5-戊二醇、2-乙基-1,6-己二醇、環己二醇、環己二甲醇、三環癸二甲醇、環戊二烯二甲醇、二聚物二醇、氫化雙酚A、螺二醇(spiroglycol)等脂肪族或脂環族二醇類；可例舉1,3-雙(2-羥基乙氧基)苯、1,2-雙(2-羥基乙氧基)苯、1,4-雙(2-羥基乙氧基)苯、4,4’-亞甲基二酚、4,4’-(2-亞降莰基)二酚(4,4’-(2-norbornylidene)diphenol)、4,4’-二羥基聯酚，鄰-、間-及對-二羥基苯，4,4’-亞異丙基酚、1,2-茚二醇、1,3-萘二醇、1,5-萘二醇、1,7-萘二醇、9,9’-雙(4-羥基苯基)茀、9,9’-雙(3-甲基-4-羥基苯基)茀等芳香族二醇類等。其他，含磷原子之二醇、含硫原子之二醇、含溴原子之二醇等。Further, the diol compound (a-1-2) having two groups in the molecule may, for example, be ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol or 2-methyl-2-ethyl group. -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl-1,3 -propylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2- Methyl-2,4-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dihydroxyl Heptane, propane diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl Glycol, octanediol, 3-butyl-3-ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclic An aliphatic or alicyclic diol such as hydrazine dimethanol, cyclopentadiene dimethanol, dimer diol, hydrogenated bisphenol A, spiroglycol; 1,3-bis(2- Hydroxyethoxy)benzene, 1,2-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediphenol, 4, 4'-(2-norbornylidene) diphenol (4,4'-(2-norbornylidene) diphenol), 4,4 -Dihydroxybiphenol, o-, m- and p-dihydroxybenzene, 4,4'-isopropylidene phenol, 1,2-decanediol, 1,3-naphthalenediol, 1,5-naphthalene Aromatic diols such as diol, 1,7-naphthalenediol, 9,9'-bis(4-hydroxyphenyl)anthracene, 9,9'-bis(3-methyl-4-hydroxyphenyl)anthracene Classes, etc. Other, a diol containing a phosphorus atom, a diol containing a sulfur atom, a diol containing a bromine atom, or the like.

又，可例舉具有羥基以外的官能基之化合物。羥基以外可例舉如含有3級胺基之化合物之N,N-雙(2-羥基丙基)苯胺、N,N-雙(2-羥基乙基)苯胺、N,N-雙(2-羥基乙基)甲基胺、N,N-雙(2-羥基乙基)丙基胺、N,N-雙(2-羥基乙基)丁基胺、N,N-雙(2-羥基乙基)己基胺、N,N-雙(2-羥基乙基)辛基胺、N,N-雙(2-羥基乙基)苯甲基胺、N,N-雙(2-羥基乙基)環己基胺等含有3級胺基之二醇化合物，又，含有羧基之化合物可例舉如二羥甲基丁酸、二羥甲基丙酸、3-羥基柳酸、4-羥基柳酸、5-羥基柳酸、2-羧基-1,4-環己烷二甲醇等。Further, a compound having a functional group other than a hydroxyl group can be exemplified. The N,N-bis(2-hydroxypropyl)aniline, N,N-bis(2-hydroxyethyl)aniline, N,N-bis(2-) may be exemplified by a compound containing a tertiary amino group. Hydroxyethyl)methylamine, N,N-bis(2-hydroxyethyl)propylamine, N,N-bis(2-hydroxyethyl)butylamine, N,N-bis(2-hydroxyethyl) Hexylamine, N,N-bis(2-hydroxyethyl)octylamine, N,N-bis(2-hydroxyethyl)benzylamine, N,N-bis(2-hydroxyethyl) a diol compound containing a tertiary amino group such as cyclohexylamine, and a compound having a carboxyl group may, for example, be dimethylolbutanoic acid, dimethylolpropionic acid, 3-hydroxysalic acid, 4-hydroxysalic acid, 5-hydroxysalic acid, 2-carboxy-1,4-cyclohexanedimethanol, and the like.

其中，二羥甲基丁酸、二羥甲基丙酸與含有酸酐基之化合物(b)反應而得到，可增加含有羧基之酯樹脂(c)的末端羧基數目，接著，與於1分子中具有至少2個環氧基之環氧化合物(d)的反應中，以可高分子量化這點來看，本發明中為較佳。又，使用N,N-雙(2-羥基丙基)苯胺等含有3級胺基之二醇化合物時，最終所得之塗膜凝集力增大，從可形成保持可撓性並且耐性更優異而強韌的塗膜這點來看為較佳。Wherein, dimethylol butyric acid and dimethylolpropionic acid are reacted with the acid anhydride group-containing compound (b) to increase the number of terminal carboxyl groups of the carboxyl group-containing ester resin (c), and then, in one molecule In the reaction of the epoxy compound (d) having at least two epoxy groups, it is preferred in the present invention from the viewpoint of high molecular weight. Further, when a diol compound containing a tertiary amino group such as N,N-bis(2-hydroxypropyl)aniline is used, the finally obtained coating film cohesive force is increased, and the flexibility can be maintained and the resistance is further improved. A strong coating film is preferred in this respect.

又，於分子中具有3個以上羥基之化合物(a-1-3)可例舉如三羥甲基乙烷、三羥甲基丙烷、新戊四醇、山梨醇、甘露糖醇、***糖醇、木糖醇、半乳糖醇、甘油等多元醇化合物。Further, the compound (a-1-3) having three or more hydroxyl groups in the molecule may, for example, be trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, mannitol or arabinose. A polyol compound such as an alcohol, xylitol, galactitol or glycerin.

本發明中，使用該等於分子中具有3個以上羥基之化合物(a-1-3)時，因可增加得到之含有羧基之酯樹脂(c)的末端羧基數目，而最終生成物可高分子量化，可提昇硬化塗膜耐性。因而，本發明中以進一步提昇硬化塗膜耐性為目的，而因應需要使用即可。由反應調控的層面來看，該等於分子中具有3個以上羥基之化合物(a-1-3)中較佳係使用三羥甲基丙烷或新戊四醇。In the present invention, when the compound (a-1-3) having three or more hydroxyl groups in the molecule is used, the number of terminal carboxyl groups of the obtained carboxyl group-containing ester resin (c) can be increased, and the final product can have a high molecular weight. It can improve the resistance of hardened coating film. Therefore, in the present invention, it is intended to further improve the resistance of the cured coating film, and it may be used as needed. From the viewpoint of reaction regulation, trimethylolpropane or neopentylol is preferably used in the compound (a-1-3) having three or more hydroxyl groups in the molecule.

在此，在本發明中多元醇化合物(a)和含有羥基之化合物(a-1)係可因應目的而以任意的比例使用，相對於多元醇化合物(a)中的羥基1.0莫耳，含有羥基之化合物(a-1)中的羥基較佳係以0.01莫耳至1.00莫耳，更佳係以0.05莫耳至0.50莫耳的比例使用。相對於多元醇化合物(a)中的羥基1.0莫耳，含有羥基之化合物(a-1)中的羥基以0.01莫耳以上的比例使用時，可得優異耐熱性。又，1.00莫耳以下時，最終得到之塗膜的凝集力成為適宜的範圍，接著強度優異。Here, in the present invention, the polyol compound (a) and the hydroxyl group-containing compound (a-1) can be used in an arbitrary ratio depending on the purpose, and are contained in an amount of 1.0 mol per hydroxy group in the polyol compound (a). The hydroxyl group in the hydroxy compound (a-1) is preferably used in an amount of from 0.01 mol to 1.00 mol, more preferably from 0.05 mol to 0.50 mol. When the hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a ratio of 0.01 mol or more to 1.0 mol of the hydroxyl group in the polyol compound (a), excellent heat resistance can be obtained. Further, when it is 1.00 mol or less, the cohesive force of the finally obtained coating film is in an appropriate range, and then the strength is excellent.

又，合成含有羧基之酯樹脂(c)時，使其起始材料反應的比例，對於多元醇化合物(a)及依照情況而添加之含有羥基之化合物(a-1)，該等所含有之羥基的合計作為1莫耳時，含有酸酐基之化合物(b)所含之酸酐基合計較佳係以0.70莫耳至1.30莫耳的比例反應，更佳係以0.90莫耳至1.10莫耳的比例反應。酸酐基合計為0.70莫耳以上時，得到之含有羧基之酯樹脂(c)的羧基量多，接下來的與於1分子中具有至少2個環氧基之環氧化合物(d)之反應步驟中發生充分的反應，最終所得之含有羧基之改質酯樹脂(A)的重量平均分子量變的足夠大。又，酸酐基合計為1.30莫耳以下時，接下來的與於1分子中具有至少2個環氧基之環氧化合物(d)反應時非常少發生副反應，不會在反應中途膠凝化。Further, when the carboxyl group-containing ester resin (c) is synthesized, the ratio of the reaction of the starting material to the polyol compound (a) and the hydroxyl group-containing compound (a-1) added as the case may be included. When the total of the hydroxyl groups is 1 mol, the acid anhydride group contained in the acid anhydride group-containing compound (b) is preferably reacted in a ratio of 0.70 mol to 1.30 mol, more preferably 0.90 mol to 1.10 mol. Proportional reaction. When the total of the acid anhydride groups is 0.70 mol or more, the carboxyl group-containing ester resin (c) has a large amount of carboxyl groups, and the subsequent reaction step with the epoxy compound (d) having at least two epoxy groups in one molecule A sufficient reaction occurs, and the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A) becomes sufficiently large. When the total amount of the acid anhydride groups is 1.30 mol or less, the next reaction occurs very little when reacting with the epoxy compound (d) having at least two epoxy groups in one molecule, and gelation does not occur in the middle of the reaction. .

又，0.90莫耳至1.10莫耳的範圍內，以接近1.00莫耳的比例(即0.95莫耳至1.05莫耳)反應時，接下來的與於1分子中具有至少2個環氧基之環氧化合物(d)的反應步驟的途中，進一步發生充分的反應。藉此，使最終所得之含有羧基之改質酯樹脂(A)的重量平均分子量更足夠大，可更提昇硬化塗膜的耐熱性和屈曲性、密著性。Further, in the range of 0.90 mol to 1.10 mol, when reacted at a ratio close to 1.00 mol (ie, 0.95 mol to 1.05 mol), the next ring having at least 2 epoxy groups in one molecule In the middle of the reaction step of the oxygen compound (d), a sufficient reaction further occurs. Thereby, the weight average molecular weight of the carboxyl group-containing modified ester resin (A) finally obtained is more sufficiently large, and the heat resistance, buckling property, and adhesion of the cured coating film can be further enhanced.

本發明中，含有羧基之酯樹脂(c)的合成條件無特別限定者，可依公知條件進行。例如於燒瓶中置入多元醇化合物(a)及溶劑[因應需要之含有羥基之化合物(a-1)]，在氮氣氣流下，於20至120℃加熱/攪拌而均勻地溶解後，投入含有酸酐基之化合物(b)，邊攪拌邊以50至150℃加熱而可得到含有羧基之酯樹脂(c)。In the present invention, the synthesis conditions of the carboxyl group-containing ester resin (c) are not particularly limited, and can be carried out under known conditions. For example, a polyol compound (a) and a solvent [a compound (a-1) having a hydroxyl group as required] are placed in a flask, and are uniformly dissolved by heating/stirring at 20 to 120 ° C under a nitrogen gas stream, and then charged. The acid anhydride group-containing compound (b) is heated at 50 to 150 ° C with stirring to obtain a carboxyl group-containing ester resin (c).

反應時，亦可因應需要而使用含有3級胺基之化合物等。又，亦可在投入含有酸酐基之化合物(b)前，將預先置入燒瓶中之多元醇化合物(a)及溶劑於100℃以上加熱/攪拌，使溶劑的一部份脫溶劑。此操作通常係為了去除系內水分(脫水處理)而施行，藉由此操作，選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)進行反應時，可抑制水所致之酸酐基的開環反應。In the reaction, a compound containing a tertiary amino group or the like may be used as needed. Further, before the addition of the acid anhydride group-containing compound (b), the polyol compound (a) and the solvent previously placed in the flask may be heated/stirred at 100 ° C or higher to remove a part of the solvent. This operation is usually carried out in order to remove moisture (dehydration treatment) in the system, and by this operation, when at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride is reacted, it can be suppressed. A ring opening reaction of an acid anhydride group due to water.

接著說明本發明之於1分子中具有至少2個環氧基之環氧化合物(d)[以下，亦簡稱為「環氧化合物(d)」]。從可調控分子量成為預期值這點來看，本發明中使用之環氧化合物(d)較佳係於分子內含有2個環氧基之化合物即可，無特別限定者。具體上可例舉如乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、雙酚A-表氯醇(epichlorohydrin)型環氧樹脂、雙酚F-表氯醇型環氧樹脂、聯酚-表氯醇型環氧樹脂、甘油-表氯醇加成物之聚環氧丙基醚、間苯二酚二環氧丙基醚、聚丁二烯二環氧丙基醚、氫醌二環氧丙基醚、二溴新戊二醇二環氧丙基醚、新戊二醇二環氧丙基醚、六氫酞酸二環氧丙酯、氫化雙酚A型二環氧丙基醚、二羥基蒽型環氧樹脂、聚丙二醇二環氧丙基醚、二苯基碸二環氧丙基醚、二羥基二苯基酮二環氧丙基醚、聯酚二環氧丙基醚、二苯基甲烷二環氧丙基醚、雙酚茀二環氧丙基醚、雙甲酚茀二環氧丙基醚、雙苯氧基乙醇茀二環氧丙基醚、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N-二環氧丙基苯胺、N,N-二環氧丙基甲苯胺，日本特開2004-156024號公報、日本特開2004-315595號公報、日本特開2004-323777號公報中所揭示之柔軟性優異之環氧化合物，和下述式(1)至(3)所示之結構的環氧化合物等。Next, an epoxy compound (d) having at least two epoxy groups in one molecule of the present invention (hereinafter also referred to simply as "epoxy compound (d)") will be described. The epoxy compound (d) used in the present invention is preferably a compound containing two epoxy groups in the molecule, and is not particularly limited. Specifically, for example, ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, 1,6-hexanediol diepoxypropyl ether, bisphenol A-epichlorohydrin (epichlorohydrin) Type epoxy resin, bisphenol F-epichlorohydrin type epoxy resin, biphenol-epichlorohydrin type epoxy resin, polyepoxypropyl ether of glycerol-epichlorohydrin adduct, resorcinol II Glycidyl ether, polybutadiene diepoxypropyl ether, hydroquinone diepoxypropyl ether, dibromo neopentyl glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, Di-glycidyl hexahydrophthalate, hydrogenated bisphenol A type di-epoxypropyl ether, dihydroxyindole type epoxy resin, polypropylene glycol diepoxypropyl ether, diphenylphosphonium diepoxypropyl ether, Dihydroxydiphenyl ketone diepoxypropyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol quinone diepoxypropyl ether, biscresol quinone epoxide Propyl ether, bisphenoxyethanol hydrazine diepoxypropyl ether, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N-diepoxypropyl Aniline, N,N-diepoxypropyltoluamide, JP-A-2004-156024, and JP-A-2004-315595 Reported, Japanese Laid-Open Patent Publication No. 2004-323777 disclosed the excellent flexibility of an epoxy compound, an epoxy compound, etc., and the following structural formula (1) to (3).

其中，1,6-己二醇二環氧丙基醚較佳係賦予柔軟性給最終所得之含有羧基之改質酯樹脂(A)之情況。雙酚A-表氯醇型環氧樹脂較佳係賦予耐熱性給最終所得之含有羧基之改質酯樹脂(A)之情況。藉此本發明中，可因應目的而選擇環氧化合物(d)，該等可單獨使用，亦可複數併用個。Among them, the 1,6-hexanediol diepoxypropyl ether is preferably one which imparts flexibility to the finally obtained carboxyl group-containing modified ester resin (A). The bisphenol A-epichlorohydrin type epoxy resin is preferably a case where heat resistance is imparted to the finally obtained carboxyl group-containing modified ester resin (A). Accordingly, in the present invention, the epoxy compound (d) can be selected depending on the purpose, and these may be used singly or in combination.

在此，將含有羧基之酯樹脂(c)的羧基作為1.0莫耳時，含有羧基之酯樹脂(c)與環氧化合物(d)進行反應的比例較佳係環氧化合物(d)中的環氧基以0.50莫耳至1.50莫耳的比例進行反應，更佳係以0.70莫耳至1.30莫耳的比例進行反應。相對於含有羧基之酯樹脂(c)的羧基1.0莫耳，於1分子中具有至少2個環氧基之環氧化合物(d)中的環氧基的比例為0.50莫耳以上時，最終所得之含有羧基之改質酯樹脂(A)的分子量足夠高且可得優異塗膜耐性和成膜性。又，相對於含有羧基之酯樹脂(c)的羧基1.0莫耳，環氧化合物(d)中的環氧基的比例為1.50莫耳以下時，末端環氧基的量成為適宜的範圍，於最終合成段階，含有酸酐基之化合物(b)進行反應時不發生副反應，不會在反應中途發生膠凝化。Here, when the carboxyl group of the carboxyl group-containing ester resin (c) is 1.0 mol, the ratio of the carboxyl group-containing ester resin (c) to the epoxy compound (d) is preferably in the epoxy compound (d). The epoxy group is reacted at a ratio of from 0.50 mol to 1.50 mol, more preferably from 0.70 mol to 1.30 mol. When the ratio of the epoxy group in the epoxy compound (d) having at least two epoxy groups in one molecule is 1.00 mol or more with respect to 1.0 mol of the carboxyl group of the carboxyl group-containing ester resin (c), the final result is obtained. The molecular weight of the modified ester resin (A) having a carboxyl group is sufficiently high and excellent coating film resistance and film formability can be obtained. Further, when the ratio of the epoxy group in the epoxy compound (d) is 1.50 mol or less with respect to 1.0 mol of the carboxyl group of the carboxyl group-containing ester resin (c), the amount of the terminal epoxy group is in an appropriate range. In the final synthesis step, the acid anhydride group-containing compound (b) does not undergo side reactions during the reaction, and gelation does not occur in the middle of the reaction.

本發明中，含有側鏈羥基之改質酯樹脂(e)的合成條件無特別限定者，可依公知條件施行。例如，於燒瓶中置入含有羧基之酯樹脂(c)、環氧化合物(d)、及溶劑，邊攪拌邊於100至150℃加熱，而可得到含有側鏈羥基之改質酯樹脂(e)。此時，可因應需要使用三苯基膦、含有3級胺基之化合物等觸媒。In the present invention, the synthesis conditions of the modified ester resin (e) containing a side chain hydroxyl group are not particularly limited, and can be carried out under known conditions. For example, an ester resin (c) containing a carboxyl group, an epoxy compound (d), and a solvent are placed in a flask, and heated at 100 to 150 ° C with stirring to obtain a modified ester resin containing a side chain hydroxyl group (e) ). At this time, a catalyst such as triphenylphosphine or a compound containing a tertiary amino group may be used as needed.

接著說明本發明之含有羧基之改質酯樹脂(A)。本發明之含有羧基之改質酯樹脂(A)可藉由含有側鏈羥基之改質酯樹脂(e)與含有酸酐基之化合物(b)進行反應而得到。Next, the carboxyl group-containing modified ester resin (A) of the present invention will be described. The carboxyl group-containing modified ester resin (A) of the present invention can be obtained by reacting a modified ester resin (e) having a side chain hydroxyl group with a compound (b) containing an acid anhydride group.

在此，合成含有羧基之改質酯樹脂(A)時，將含有側鏈羥基之改質酯樹脂(e)中的羥基作為1.0莫耳時，含有酸酐基之化合物(b)進行反應的比例較佳係含有酸酐基之化合物(b)中的酸酐基以0.05莫耳至1.0莫耳的比例進行反應，更佳係以0.10莫耳至0.90莫耳的比例進行反應。相對於含有側鏈羥基之改質酯樹脂(e)中的羥基1.0莫耳，選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)中的酸酐基的比例為0.05莫耳以上時，改質的比例充分且導入主鏈中的交聯性官能基的效果高。又，1.0莫耳以下時，剩餘的含有酸酐基之化合物不易殘存，最終塗膜的可撓性、銲錫耐熱性、絕緣信賴性優異。Here, when the modified ester resin (A) having a carboxyl group is synthesized, when the hydroxyl group in the modified ester resin (e) containing a side chain hydroxyl group is 1.0 mol, the ratio of the acid anhydride group-containing compound (b) is reacted. It is preferred that the acid anhydride group in the acid anhydride group-containing compound (b) is reacted at a ratio of from 0.05 mol to 1.0 mol, more preferably from 0.10 mol to 0.90 mol. The ratio of the acid anhydride group in the acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride with respect to 1.0 hydroxy group of the hydroxyl group in the modified ester resin (e) having a side chain hydroxyl group When it is 0.05 mol or more, the ratio of reforming is sufficient and the effect of introducing a crosslinkable functional group in the main chain is high. Further, when it is 1.0 mol or less, the remaining acid anhydride group-containing compound is less likely to remain, and the final coating film is excellent in flexibility, solder heat resistance, and insulation reliability.

本發明中，含有羧基之改質酯樹脂(A)的合成條件無特別限定者，可依公知條件施行。例如，於燒瓶中置入含有側鏈羥基之改質酯樹脂(e)、含有酸酐基之化合物(b)、及溶劑，邊攪拌邊於50至100℃加熱，而可得到含有羧基之改質酯樹脂(A)。此反應在無觸媒下進行，但因應需要亦可使用含有3級胺基之化合物等觸媒。In the present invention, the synthesis conditions of the carboxyl group-containing modified ester resin (A) are not particularly limited, and can be carried out under known conditions. For example, a modified ester resin (e) containing a side chain hydroxyl group, a compound (b) containing an acid anhydride group, and a solvent are placed in a flask, and heated at 50 to 100 ° C with stirring to obtain a carboxyl group-containing modification. Ester resin (A). This reaction is carried out without a catalyst, but a catalyst such as a compound having a tertiary amino group may also be used as needed.

本發明之含有羧基之改質酯樹脂(A)的酸價較佳係1至100mgKOH/g，更佳係5至90mgKOH/g。酸價在1mgKOH/g以上時，羧基作為硬化性基的功能足夠，硬化後的塗膜耐性非常優異。又，酸價在100mgKOH/g以下時，塗膜的硬度成為適宜的範圍，接著強度非常優異。又，酸價在1至100mgKOH/g的範圍內，以接近1mgKOH/g的範圍設計時(具體而言為1mgKOH/g至10mgKOH/g)，所得之塗膜的屈曲性和密著性提升。另一方面，以接近100mgKOH/g的範圍設計時(具體而言為80mgKOH/g至100mgKOH/g)，交聯點多而最終所得之塗膜的耐熱性提昇。如此，本發明中，含有羧基之改質酯樹脂(A)的酸價可在1至100mgKOH/g的範圍內，因應目的而作調整。The acid value of the carboxyl group-containing modified ester resin (A) of the present invention is preferably from 1 to 100 mgKOH/g, more preferably from 5 to 90 mgKOH/g. When the acid value is 1 mgKOH/g or more, the function of the carboxyl group as a curable group is sufficient, and the coating film resistance after curing is extremely excellent. Further, when the acid value is 100 mgKOH/g or less, the hardness of the coating film is in an appropriate range, and the strength is extremely excellent. Further, when the acid value is in the range of 1 to 100 mgKOH/g and the design is in the range of approximately 1 mgKOH/g (specifically, 1 mgKOH/g to 10 mgKOH/g), the resulting coating film is improved in the buckling property and the adhesion. On the other hand, when designing in the range of approximately 100 mgKOH/g (specifically, 80 mgKOH/g to 100 mgKOH/g), the crosslinking point is increased and the heat resistance of the finally obtained coating film is improved. As described above, in the present invention, the acid value of the carboxyl group-containing modified ester resin (A) may be in the range of 1 to 100 mgKOH/g, which is adjusted depending on the purpose.

本發明之含有羧基之改質酯樹脂(A)的重量平均分子量較佳係5000至500000，更佳係10000至300000。重量平均分子量在5000以上時，可得非常優異的銲錫耐熱性及可撓性。又，重量平均分子量在500000以下時，塗裝時的黏度成為適宜的範圍，容易操作(handling)。又，重量平均分子量在5000至500000的範圍內，以接近5000的值設計時(具體而言為5000至10000)，所得之樹脂的末端(即羧基)多，而得到富有交聯性的樹脂，可提昇最終所得之塗膜的耐熱性。另一方面，以接近500000的值設計時(具體而言為300000至500000)，最終所得之塗膜的密著性和屈曲性優異。如此，本發明中，含有羧基之改質酯樹脂(A)的重量平均分子量可在5000至500000的範圍內，因應目的而作調整。The weight average molecular weight of the carboxyl group-containing modified ester resin (A) of the present invention is preferably from 5,000 to 500,000, more preferably from 10,000 to 300,000. When the weight average molecular weight is 5,000 or more, extremely excellent solder heat resistance and flexibility can be obtained. Further, when the weight average molecular weight is 500,000 or less, the viscosity at the time of coating is in an appropriate range, and handling is easy. Further, the weight average molecular weight is in the range of 5,000 to 500,000, and when designed at a value close to 5,000 (specifically, 5,000 to 10,000), the end of the obtained resin (that is, a carboxyl group) is increased to obtain a crosslinkable resin. The heat resistance of the finally obtained coating film can be improved. On the other hand, when designing at a value close to 500,000 (specifically, 300,000 to 500,000), the coating film finally obtained is excellent in adhesion and buckling property. As described above, in the present invention, the weight average molecular weight of the carboxyl group-containing modified ester resin (A) may be in the range of 5,000 to 500,000, and is adjusted depending on the purpose.

本發明之熱硬化性樹脂組成物包含：前述(A)含有羧基之改質酯樹脂，和(B)選自含有環氧基之化合物、含有異氰酸酯基之化合物及含有封端化異氰酸酯基之化合物所成之群組之至少一種化合物，和(C)熱硬化助劑。在此說明，選自含有環氧基之化合物、含有異氰酸酯基之化合物及含有封端化異氰酸酯基之化合物所成之群組之至少一種化合物(B)[以下亦簡稱為「化合物(B)」]。本發明之熱硬化性樹脂組成物之特徵係使用化合物(B)作為上述含有羧基之改質酯樹脂(A)的硬化劑。The thermosetting resin composition of the present invention comprises the above (A) a carboxyl group-containing modified ester resin, and (B) a compound selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound. At least one compound of the group formed, and (C) a thermal hardening aid. Here, at least one compound (B) selected from the group consisting of a compound containing an epoxy group, a compound containing an isocyanate group, and a compound having a blocked isocyanate group (hereinafter also referred to simply as "compound (B)" ]. The thermosetting resin composition of the present invention is characterized in that the compound (B) is used as a curing agent for the carboxyl group-containing modified ester resin (A).

本發明之含有環氧基之化合物，只要為於分子內含有環氧基之化合物即可，無特別限定者。例如，於分子內具有1個環氧基之化合物可例舉N-環氧丙基酞醯亞胺、環氧丙醇、(甲基)丙烯酸環氧丙酯等化合物。該等藉由因應需要而併用後述所例示之於分子內具有2個以上環氧基之化合物，以調控硬化物的交聯密度為目的而可適宜的使用。又，於分子內具有2個以上環氧基之化合物，可例舉乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、雙酚A-表氯醇型環氧樹脂、雙酚F-表氯醇型環氧樹脂、雙酚S-表氯醇型環氧樹脂、雙酚AD-表氯醇型環氧樹脂、聯酚-表氯醇型環氧樹脂、雙酚A的環氧乙烷加成物或環氧丙烷加成物之表氯醇型環氧樹脂，甘油-表氯醇加成物之聚環氧丙基醚、萘二醇二環氧丙基醚、間苯二酚二環氧丙基醚、聚丁二烯二環氧丙基醚、氫醌二環氧丙基醚、二溴新戊二醇二環氧丙基醚、新戊二醇二環氧丙基醚、六氫酞酸二環氧丙酯、氫化雙酚A型二環氧丙基醚、聚丙二醇二環氧丙基醚、二苯基碸二環氧丙基醚、二羥基二苯基酮二環氧丙基醚、聯酚二環氧丙基醚、二苯基甲烷二環氧丙基醚、雙酚茀二環氧丙基醚、雙甲酚茀二環氧丙基醚、雙苯氧基乙醇茀二環氧丙基醚、1,3-雙(N,N-二環氧丙基胺基甲基)環己烷、N,N-二環氧丙基苯胺、N,N-二環氧丙基甲苯胺，日本特開2004-156024號公報、日本特開2004-315595號公報、日本特開2004-323777號公報所揭示之柔軟性優異的環氧化合物，下述式(4)至(6)所示之結構的環氧化合物等。The epoxy group-containing compound of the present invention is not particularly limited as long as it is a compound containing an epoxy group in the molecule. For example, a compound having one epoxy group in the molecule may, for example, be a compound such as N-epoxypropyl quinone imine, glycidyl alcohol or glycidyl (meth)acrylate. These compounds can be suitably used for the purpose of controlling the crosslinking density of the cured product by using a compound having two or more epoxy groups in the molecule as exemplified below. Further, the compound having two or more epoxy groups in the molecule may, for example, be ethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether or 1,6-hexanediol diepoxypropyl chloride. Ether, bisphenol A-epichlorohydrin epoxy resin, bisphenol F-epichlorohydrin epoxy resin, bisphenol S-epichlorohydrin epoxy resin, bisphenol AD-epichlorohydrin epoxy resin , a biphenol-epichlorohydrin type epoxy resin, an ethylene oxide adduct of bisphenol A or an epichlorohydrin type epoxy resin of a propylene oxide adduct, a poly ring of a glycerol-epichlorohydrin adduct Oxypropyl propyl ether, naphthalenediol diepoxypropyl ether, resorcinol diepoxypropyl ether, polybutadiene diepoxypropyl ether, hydroquinone diepoxypropyl ether, dibromo neopentyl Diol diglycidyl ether, neopentyl glycol diepoxypropyl ether, diglycidyl hexahydrophthalate, hydrogenated bisphenol A diepoxypropyl ether, polypropylene glycol diepoxypropyl ether , diphenylphosphonium diepoxypropyl ether, dihydroxydiphenyl ketone diepoxypropyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol quinone ring Oxypropyl propyl ether, biscresol quinone diepoxypropyl ether, bisphenoxyethanol oxime epoxide Ether, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, N,N-diepoxypropylaniline, N,N-diepoxypropyltoluamide, An epoxy compound excellent in flexibility disclosed in JP-A-2004-315777, and JP-A-2004-323777, which is represented by the following formulas (4) to (6). Structure of epoxy compounds, etc.

再者，可例舉三(羥基乙基)三聚異氰酸酯三環氧丙基醚、三聚異氰酸三環氧丙酯，三菱化學股份有限公司製「EPIKOTE 1031S」、「EPIKOTE 1032H60」、「EPIKOTE 604」、「EPIKOTE 630」，還有酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂，日本特開2001-240654號公報所揭示之二環戊二烯型環氧樹脂、萘型環氧樹脂，乙二醇-表氯醇加成物之聚環氧丙基醚、新戊四醇聚環氧丙基醚、三羥甲基丙烷聚環氧丙基醚、N,N,N’,N’-四環氧丙基-m-二甲苯二胺等。又，可使用併有環氧基以外的其他熱硬化性基之化合物。例如，可例舉日本特開2001-59011號公報、2003-48953號公報所揭示之矽烷改質環氧樹脂。Further, tris(hydroxyethyl)trimeric isocyanate triepoxypropyl ether or triglycidyl isocyanate, "EPIKOTE 1031S" and "EPIKOTE 1032H60" manufactured by Mitsubishi Chemical Corporation can be exemplified. EPIKOTE 604", "EPIKOTE 630", and a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, naphthalene disclosed in JP-A-2001-240654 Epoxy resin, polyepoxypropyl ether of ethylene glycol-epichlorohydrin adduct, neopentyl alcohol polyepoxypropyl ether, trimethylolpropane polyepoxypropyl ether, N, N, N', N'-tetraepoxypropyl-m-xylenediamine, and the like. Further, a compound having a thermosetting group other than the epoxy group may be used. For example, a decane-modified epoxy resin disclosed in JP-A-2001-59011 and JP-A-2003-48953 can be exemplified.

尤其是三(羥基乙基)三聚異氰酸酯三環氧丙基醚、三聚異氰酸三環氧丙酯等含有三聚異氰酸酯環之環氧化合物使用於本發明時，有對聚醯亞胺和銅的接著強度提昇的傾向而較佳。又，三菱化學股份有限公司製「EPIKOTE 1031S」、「EPIKOTE 1032H60」、「EPIKOTE 604」、「EPIKOTE 630」因多官能且耐熱性優異而在本發明中非常佳，又，脂肪族系的環氧化合物以及日本特開2004-156024號公報、日本特開2004-315595號公報、日本特開2004-323777號公報所記載之環氧化合物因硬化塗膜的柔軟性優異而較佳。又，日本特開2001-240654號公報所記載之二環戊二烯型環氧化合物以及酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯酚-表氯醇型環氧樹脂等在本發明中，熱硬化性及吸濕性和以耐熱性為首之硬化塗膜的耐久性層面優異而較佳。In particular, an epoxy compound containing a trimeric isocyanate ring such as tris(hydroxyethyl)trimeric isocyanate triepoxypropyl ether or triglycidyl isocyanate is used in the present invention, and has a polyimine. It is preferable to have a tendency to increase the strength of copper. In addition, "EPIKOTE 1031S", "EPIKOTE 1032H60", "EPIKOTE 604", and "EPIKOTE 630" manufactured by Mitsubishi Chemical Corporation are excellent in multi-functionality and heat resistance, and are excellent in the present invention, and are also aliphatic epoxy. The epoxy compound described in the Japanese Patent Publication No. 2004-315777, and the above-mentioned JP-A-2004-323777 is preferably excellent in flexibility of the cured coating film. Further, a dicyclopentadiene type epoxy compound, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a bisphenol-epichlorohydrin type epoxy resin described in JP-A-2001-240654 In the present invention, the thermosetting property and the hygroscopic property and the heat-resistant coating film including heat resistance are excellent in durability and are preferable.

含有異氰酸酯基之化合物只要是於分子內具有異氰酸酯基之化合物即可，無特別限定者。具體而言，二異氰酸酯化合物可例舉如碳數4至50的芳香族二異氰酸酯、脂肪族二異氰酸酯、芳香脂肪族二異氰酸酯、脂環族二異氰酸酯等。The compound containing an isocyanate group is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specifically, the diisocyanate compound may, for example, be an aromatic diisocyanate having 4 to 50 carbon atoms, an aliphatic diisocyanate, an aromatic aliphatic diisocyanate or an alicyclic diisocyanate.

芳香族二異氰酸酯可例舉如二異氰酸1,3-伸苯基酯、二異氰酸4,4’-二苯基酯、二異氰酸1,4-伸苯基酯、二異氰酸4,4’-二苯基甲烷酯、二異氰酸2,4-伸甲苯基酯、二異氰酸2,6-伸甲苯基酯、二異氰酸4,4’-甲苯胺酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、二異氰酸聯大茴香胺酯(dianisidine triisocyanate)、二異氰酸4,4’-二苯基醚酯、三異氰酸4,4’,4”-三苯基甲烷酯等。The aromatic diisocyanate may, for example, be 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, or diisomeric. 4,4'-diphenylmethane cyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 4,4'-toluidine diisocyanate Ester, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, diisocyanate diisocyanate, 4,4'-diphenyl ether diisocyanate And 4,4',4"-triphenylmethane triisocyanate.

脂肪族二異氰酸酯可例舉如二異氰酸三亞甲基酯、二異氰酸四亞甲基酯、二異氰酸六亞甲基酯、二異氰酸五亞甲基酯、二異氰酸1,2-伸丙基酯、二異氰酸2,3-伸丁基酯、二異氰酸1,3-伸丁基酯、二異氰酸伸十二烷基酯、二異氰酸2,4,4-三甲基六亞甲基酯等。The aliphatic diisocyanate may, for example, be trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate or diisocyanate. Acid 1,2-propyl ester, 2,3-butyl butyl diisocyanate, 1,3-butyl butyl diisocyanate, dodecyl diisocyanate, diisocyanate Acid 2,4,4-trimethylhexamethylene ester and the like.

芳香脂肪族二異氰酸酯可例舉如ω,ω’-二異氰酸酯-1,3-二甲基苯、ω,ω’-二異氰酸酯-1,4-二甲基苯、ω,ω’-二異氰酸酯-1,4-二乙基苯、二異氰酸1,4-四甲基伸茬基酯、二異氰酸1,3-四甲基伸茬基酯等。The aromatic aliphatic diisocyanate may, for example, be ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate. - 1,4-diethylbenzene, 1,4-tetramethyl decyl diisocyanate, 1,3-tetramethyl decyl diisocyanate, and the like.

脂環族二異氰酸酯可例舉如3-異氰酸酯甲基-3,5,5-三甲基環己基異氰酸酯[別名：二異氰酸異佛酮酯]、二異氰酸1,3-環戊烷酯、二異氰酸1,3-環己烷酯、二異氰酸1,4-環己烷酯、二異氰酸甲基-2,4-環己烷酯、二異氰酸甲基-2,6-環己烷酯、4,4’-亞甲基雙(環己基異氰酸酯)、1,3-雙(異氰酸酯甲基)環己烷、1,4-雙(異氰酸酯甲基)環己烷等。The alicyclic diisocyanate may, for example, be 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], 1,3-cyclopentyl diisocyanate Alkyl ester, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, diisocyanate Base-2,6-cyclohexane ester, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanate methyl) Cyclohexane and the like.

於分子中具有1個或3個以上異氰酸酯基之含有異氰酸酯基之化合物，具體上，於1分子中具有1個異氰酸酯基之單官能異氰酸酯，可例舉異氰酸(甲基)丙烯醯氧基乙基酯、異氰酸1,1-雙[(甲基)丙烯醯氧基甲基]乙基酯、異氰酸乙烯酯、異氰酸烯丙酯、異氰酸(甲基)丙烯醯基酯、異氰酸異丙烯基-α,α-二甲基苯甲酯等。又，1,6-二異氰酸基己烷、二異氰酸異佛酮酯、二異氰酸4,4’-二苯基甲烷酯、高分子型二異氰酸二苯基甲烷酯、二異氰酸伸茬基酯、2,4-二異氰酸亞甲苯基酯、二異氰酸甲苯、2,4-二異氰酸甲苯酯、二異氰酸六亞甲基酯、二異氰酸4-甲基-m-伸苯基酯、二異氰酸萘酯、二異氰酸對伸苯基酯、二異氰酸四甲基伸茬基酯、二異氰酸環己基甲烷酯、二異氰酸氫化伸茬基酯、二異氰酸環己基酯、二異氰酸聯甲苯胺酯、二異氰酸2,2,4-三甲基六亞甲基酯、二異氰酸2,4,4-三甲基六亞甲基酯、二異氰酸間四甲基伸茬基酯、二異氰酸對四甲基伸茬基酯、二聚酸二異氰酸酯等二異氰酸酯化合物，其與含有羥基、羧基、醯胺基之乙烯基單體以相等莫耳進行反應之化合物亦可使用作為異氰酸酯化合物。The isocyanate group-containing compound having one or three or more isocyanate groups in the molecule, specifically, a monofunctional isocyanate having one isocyanate group in one molecule, and an isocyanate (meth) propylene oxy group is exemplified. Ethyl ester, 1,1-bis[(meth)acryloxymethyl]ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) propylene isocyanate A base ester, isopropenyl isocyanate-α, α-dimethylbenzyl ester or the like. Further, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polymer diphenylmethane diisocyanate , diisocyanate dialkyl phthalate, 2,4-diisocyanate toluene, toluene diisocyanate, 2,4-diisocyanate, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthyl diisocyanate, p-phenylene diisocyanate, tetramethyl decyl diisocyanate, diisocyanate ring Hexyl methane ester, hydrogenated dithiocyanate, cyclohexyl diisocyanate, toluidine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, tetramethyl decyl diisocyanate, tetramethyl decyl diisocyanate, dimer acid diisocyanate As the diisocyanate compound, a compound which reacts with a vinyl monomer having a hydroxyl group, a carboxyl group or a guanamine group in an equivalent molar amount can also be used as the isocyanate compound.

又,於1分子中具有3個以上異氰酸酯基之多官能異氰酸酯可例舉如芳香族聚異氰酸酯、離胺酸三異氰酸酯等脂肪族聚異氰酸酯、芳香脂肪族聚異氰酸酯、脂環族聚異氰酸酯等，可例舉前述之二異氰酸酯的三羥甲基丙烷加成物、與水反應之縮二脲(biuret)體、具有三聚異氰酸酯環之三聚物。Further, the polyfunctional isocyanate having three or more isocyanate groups in one molecule may, for example, be an aliphatic polyisocyanate such as an aromatic polyisocyanate or an isocyanuric acid triisocyanate, an aromatic aliphatic polyisocyanate or an alicyclic polyisocyanate. A trimethylolpropane adduct of the above-mentioned diisocyanate, a biuret body which reacts with water, and a terpolymer having a trimerized isocyanate ring are exemplified.

含有封端化異氰酸酯基之化合物可例舉只要含有異氰酸酯基經ε-己內醯胺、MEK肟(MEK oxime)等保護之異氰酸酯基之化合物即可，無特別限定者。具體上可例舉上述含有異氰酸酯基之化合物的異氰酸酯基經ε-己內醯胺、MEK肟、環己酮肟、吡唑、酚等而封端者等。The compound containing a blocked isocyanate group is not particularly limited as long as it contains a compound having an isocyanate group which is protected by ε-caprolactam, MEK oxime or the like. Specifically, the isocyanate group of the above-mentioned isocyanate group-containing compound may be blocked by ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol or the like.

本發明中，化合物(B)可單獨使用一種，亦可複數併用。化合物(B)的使用量可在考慮本發明之硬化性樹脂組成物的用途等之後決定即可，無特別限定者，相對於含有羧基之改質酯樹脂(A)100重量份，使用量較佳係以0.5重量份至100重量份之比例添加，更佳係以1重量份至80重量份之比例添加。藉由使用化合物(B)，而可調整本發明之硬化性樹脂組成物的交聯密度成為適宜的值，可進一步提昇硬化後的塗膜的各種物性。化合物(B)的使用量在0.5重量份以上時，加熱硬化後的塗膜的交聯密度成為適宜的範圍，接著強度和耐熱性皆非常優異。又，該使用量在100重量份以下時，加熱硬化後的交聯密度成為適宜的範圍，其結果，塗膜的屈曲性、可撓性、接著強度皆非常優異。In the present invention, the compound (B) may be used singly or in combination of plural kinds. The amount of the compound (B) to be used may be determined in consideration of the use of the curable resin composition of the present invention, etc., and is not particularly limited, and is used in an amount of 100 parts by weight based on 100 parts by weight of the modified ester resin (A) containing a carboxyl group. It is preferably added in a proportion of from 0.5 part by weight to 100 parts by weight, more preferably from 1 part by weight to 80 parts by weight. By using the compound (B), the crosslinking density of the curable resin composition of the present invention can be adjusted to a suitable value, and various physical properties of the coating film after curing can be further improved. When the amount of the compound (B) is 0.5 parts by weight or more, the crosslinking density of the coating film after heat curing is in an appropriate range, and the strength and heat resistance are both excellent. In addition, when the amount is 100 parts by weight or less, the crosslinking density after heat curing is in an appropriate range, and as a result, the buckling property, flexibility, and adhesion strength of the coating film are extremely excellent.

接著，說明本發明之熱硬化助劑(C)。本發明之熱硬化助劑(C)係在上述化合物(B)與含有羧基之改質酯樹脂(A)進行硬化反應時，直接協助硬化反應之化合物或者以觸媒的方式協助之化合物。Next, the thermal curing aid (C) of the present invention will be described. The thermosetting assistant (C) of the present invention is a compound which directly assists the compound of the curing reaction or a catalyst-assisted compound when the compound (B) and the modified ester resin (A) having a carboxyl group are subjected to a curing reaction.

熱硬化助劑(C)表示直接協助硬化反應之化合物，係具有可與羥基、胺基、環氧基、羧基等進行反應之官能基之化合物，或者以觸媒的方式協助硬化反應之化合物，除了屬於上述化合物(B)者以外者，本發明之熱硬化性樹脂組成物中皆可適宜的使用。具體上可例舉如氰酸酯化合物、氮雜環丙烷化合物、含有酸酐基之化合物、含有羧基之化合物、含有碳二亞胺基之化合物、含有氧雜環丁烷基之化合物、苯并化合物、順丁烯二醯亞胺化合物、甲基順丁烯二醯亞胺化合物、納迪克醯亞胺化合物、烯丙基納迪克醯亞胺化合物、乙烯基醚化合物、乙烯基苯甲基醚樹脂、硫醇化合物、三聚氰胺化合物、胍胺(guanamine)化合物、胺基樹脂、酚樹脂、醇酸樹脂、丙烯酸系樹脂、不飽和聚酯樹脂、酞酸二烯丙基酯樹脂、矽氧樹脂、二甲苯樹脂、呋喃樹脂、酮樹脂、三聚氰酸三烯丙基酯樹脂、含有三聚異氰酸三(2-羥基乙基)酯之樹脂、含有偏苯三甲酸三烯丙基酯之樹脂、二環戊二烯樹脂、芳香族二氰胺之三聚合化而成之熱硬化性樹脂等。The thermosetting assistant (C) represents a compound which directly assists the hardening reaction, a compound having a functional group reactive with a hydroxyl group, an amine group, an epoxy group, a carboxyl group, or the like, or a compound which assists the hardening reaction by a catalyst. Other than the above-mentioned compound (B), the thermosetting resin composition of the present invention can be suitably used. Specific examples thereof include a cyanate compound, an aziridine compound, an acid anhydride group-containing compound, a carboxyl group-containing compound, a carbodiimide group-containing compound, an oxetanyl group-containing compound, and a benzo compound. Compound, maleimide compound, methyl maleimide compound, nadic quinone compound, allyl nadic ylide compound, vinyl ether compound, vinyl benz ether Resin, thiol compound, melamine compound, guanamine compound, amine based resin, phenol resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl citrate resin, oxime resin, Xylene resin, furan resin, ketone resin, triallyl cyanurate resin, resin containing tris(2-hydroxyethyl) isocyanate, and triallyl trimellitate A thermosetting resin obtained by polymerizing a resin, a dicyclopentadiene resin, or an aromatic dicyanamide.

氰酸酯化合物可例舉雙(4-氰酸基苯基)乙烷、2,2-雙(4-氰酸基苯基)丙烷、2,2-雙(3,5-二甲基-4-氰酸基苯基)甲烷、2,2-雙(4-氰酸基苯基)-1,1,1,3,3,3-六氟丙烷、α,α’-雙(4-氰酸基苯基)-m-二異丙基苯、酚加成二環戊二烯聚合物之氰酸酯化合物等，其預聚合物(prepolymer)等可單獨或混合使用。其中，2,2-雙(4-氰酸基苯基)丙烷及2,2-雙(3,5-二甲基-4-氰酸基苯基)等因硬化物的介電特性特別良好而較佳。使用氰酸酯化合物時，因應需要可用金屬系反應觸媒類，可用錳、鐵、鈷、鎳、銅、鋅等金屬觸媒類。具體而言，可用作為2-乙基己烷酸鹽或環烷酸鹽等有機金屬鹽化合物及乙醯丙酮錯合物等有機金屬錯合物。相對於氰酸酯化合物，金屬系反應觸媒的調配量較佳係1至3000ppm，更佳係1至1000ppm，再更佳係2至300ppm。金屬系反應觸媒的調配量為1ppm以上時，可充分得到添加的效果，3000ppm以下時，容易調控反應，硬化速度成為較佳範圍。The cyanate compound may, for example, be bis(4-cyanylphenyl)ethane, 2,2-bis(4-cyanylphenyl)propane or 2,2-bis(3,5-dimethyl- 4-cyanate phenyl)methane, 2,2-bis(4-cyanylphenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4- Cyanate phenyl)-m-diisopropylbenzene, a phenol-added dicyclopentadiene polymer cyanate compound, etc., and a prepolymer or the like may be used singly or in combination. Among them, 2,2-bis(4-cyanylphenyl)propane and 2,2-bis(3,5-dimethyl-4-c-cyanophenyl) have good dielectric properties due to hardening properties. Better. When a cyanate compound is used, a metal-based reaction catalyst may be used as needed, and a metal catalyst such as manganese, iron, cobalt, nickel, copper or zinc may be used. Specifically, it can be used as an organic metal salt compound such as 2-ethylhexane salt or a naphthenate or an organic metal complex such as an acetamidineacetate complex. The compounding amount of the metal-based reaction catalyst is preferably from 1 to 3,000 ppm, more preferably from 1 to 1,000 ppm, still more preferably from 2 to 300 ppm, based on the cyanate ester compound. When the amount of the metal-based reaction catalyst is 1 ppm or more, the effect of addition can be sufficiently obtained, and when it is 3,000 ppm or less, the reaction is easily regulated, and the curing rate is preferably in a preferred range.

氮雜環丙烷化合物可例舉如N,N’-二苯基甲烷-4,4’-雙(1-氮雜環丙烷羰基化物)、N,N’-甲苯-2,4-雙(1-氮雜環丙烷羰基化物)、雙異酞醯基-1-(2-甲基氮雜環丙烷)、三-1-氮雜環丙基氧化膦(tris(1-aziridinyl)phosphine oxide)、N,N’-六亞甲基-1,6-雙(1-氮雜環丙烷羰基化物)、丙酸三羥甲基丙烷-三-β-氮雜環丙基酯、丙酸四羥甲基甲烷-三-β-氮雜環丙基酯、三-2,4,6-(1-氮雜環丙基)-1、3、5-三、三羥甲基丙烷三[3-(1-氮雜環丙基)丙酸酯]、三羥甲基丙烷三[3-(1-氮雜環丙基)丁酸酯]、三羥甲基丙烷三[3-(1-(2-甲基)氮雜環丙基)丙酸酯]、三羥甲基丙烷三[3-(1-氮雜環丙基)-2-甲基丙酸酯]、2,2’-雙羥基甲基丁醇三[3-(1-氮雜環丙基)丙酸酯]、新戊四醇四[3-(1-氮雜環丙基)丙酸酯]、二苯基甲烷-4,4-雙-N,N’-伸乙基脲、1,6-六亞甲基雙-N,N’-伸乙基脲、2,4,6-(三伸乙基亞胺基)-Syn-三、雙[1-(2-乙基)氮雜環丙基]苯-1,3-羧酸醯胺等。The aziridine compound may, for example, be N,N'-diphenylmethane-4,4'-bis(1-azetidinylcarbonyl), N,N'-toluene-2,4-bis (1) - azacyclopropane carbonyl), diisodecyl-1-(2-methylaziridine), tri-1-(1-aziridinyl)phosphine oxide, N,N'-hexamethylene-1,6-bis(1-azetidinylcarbonyl), trimethylolpropane propionate-tri-beta-azacyclopropyl ester, tetrahydroxyl propionate Methane-tris-β-azacyclopropyl ester, tris-2,4,6-(1-azacyclopropyl)-1,3,5-three , trimethylolpropane tris[3-(1-azetidinyl)propionate], trimethylolpropane tris[3-(1-azacyclopropyl)butyrate], trishydroxyl Propane tris[3-(1-(2-methyl)azirudyl)propionate], trimethylolpropane tris[3-(1-azetidinyl)-2-methylpropane Acid ester], 2,2'-bishydroxymethylbutanol tris[3-(1-azetidinyl)propionate], pentaerythritol tetrakis[3-(1-azacyclopropyl) Propionate], diphenylmethane-4,4-bis-N,N'-extended ethylurea, 1,6-hexamethylenebis-N,N'-extended ethylurea, 2,4, 6-(tris-ethylethylamino)-Syn-three , bis[1-(2-ethyl)azirridinyl]benzene-1,3-carboxylic acid decylamine, and the like.

含有酸酐基之化合物只要為以含有酸酐基之化合物(b)為首之於分子內含有酸酐基之化合物即可，無特別限定者。含有酸酐基之化合物(b)以外的含有酸酐基之化合物，具體上可例舉二羧酸酐、六羧酸三酐、六羧酸二酐、順丁烯二酸酐共聚合樹脂等多元羧酸酐類等。進一步詳細例示含有酸酐基之化合物，則除了酞酸酐、四氫酞酸酐等之外，順丁烯二酸酐共聚合樹脂可例舉Sartomer Company製SMA樹脂系列，股份有限公司岐阜Shellac製造所製GSM系列等苯乙烯-順丁烯二酸酐共聚合樹脂、對苯基苯乙烯-順丁烯二酸酐共聚合樹脂、聚乙烯-順丁烯二酸酐等α-烯烴-順丁烯二酸酐共聚合樹脂、Daicel化學工業股份有限公司製「VEMA」(甲基乙烯基醚與順丁烯二酸酐之共聚物)、順丁烯二酸酐丙烯酸系改質聚烯烴(「AUROREN系列」：日本製紙Chemicals股份有限公司製)、順丁烯二酸酐共聚合丙烯酸系樹脂等。The compound containing an acid anhydride group is not particularly limited as long as it is a compound containing an acid anhydride group (b) and an acid anhydride group in the molecule. The acid anhydride group-containing compound other than the acid anhydride group-containing compound (b) may, for example, be a polycarboxylic acid anhydride such as a dicarboxylic anhydride, a hexacarboxylic acid trihydride, a hexacarboxylic dianhydride or a maleic anhydride copolymer resin. Wait. Further, the compound containing an acid anhydride group is exemplified by a SMA resin series manufactured by Sartomer Company, and a GSM series manufactured by Shellac Co., Ltd., in addition to phthalic anhydride, tetrahydrophthalic anhydride, and the like. a styrene-maleic anhydride copolymerized resin, a p-phenylstyrene-maleic anhydride copolymerized resin, an α-olefin-maleic anhydride copolymerized resin such as polyethylene-maleic anhydride, Daicel Chemical Industry Co., Ltd. "VEMA" (copolymer of methyl vinyl ether and maleic anhydride), maleic anhydride acrylic modified polyolefin ("AUROREN series": Nippon Paper Chemicals Co., Ltd. And maleic anhydride copolymerized acrylic resin or the like.

含有羧基之化合物可例舉如鄰酞酸、異酞酸、對酞酸、1,4-二甲基對酞酸、1,3-二甲基異酞酸、5-磺酸基-1,3-二甲基異酞酸、4,4-聯苯基二羧酸、1,4-萘二羧酸、2,6-萘二羧酸、降莰烯二羧酸、二苯基甲烷-4,4’-二羧酸、苯基茚二羧酸等芳香族二羧酸類；六氫對酞酸、六氫異酞酸、六氫酞酸、四氫酞酸等脂環族二羧酸類；乙二酸、丙二酸、丁二酸、已二酸、癸二酸、壬二酸、辛二酸、順丁烯二酸、氯順丁烯二酸、反丁烯二酸、十二烷二酸、庚二酸、甲基順丁烯二酸、戊二酸、伊康酸等脂肪族二羧酸類等。The compound having a carboxyl group may, for example, be ortho-decanoic acid, isophthalic acid, p-citric acid, 1,4-dimethyl-p-decanoic acid, 1,3-dimethylisodecanoic acid or 5-sulfonic acid group-1. 3-dimethylisodecanoic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornene dicarboxylic acid, diphenylmethane- An aromatic dicarboxylic acid such as 4,4'-dicarboxylic acid or phenylphosphonium dicarboxylic acid; or an alicyclic dicarboxylic acid such as hexahydropyridinic acid, hexahydroisodecanoic acid, hexahydrononanoic acid or tetrahydrofurfuric acid Oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, suberic acid, maleic acid, chloro-maleic acid, fumaric acid, twelve An aliphatic dicarboxylic acid such as alkanoic acid, pimelic acid, methyl maleic acid, glutaric acid or itaconic acid.

含有碳二亞胺基之化合物可例舉日清紡績股份有限公司的CARBODILITE系列。其中CARBODILITEV-01、03、05、07、09因與有機溶劑的相溶性優異而較佳。The compound containing a carbodiimide group can be exemplified by the CARBODILITE series of Nissin Textile Co., Ltd. Among them, CARBODILITEV-01, 03, 05, 07, and 09 are preferred because they are excellent in compatibility with an organic solvent.

含有氧雜環丁烷基之化合物可例舉如1,4-雙{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}苯[東亞合成公司製，商品名；Aronoxetane OXT-121等]、3-乙基-3-{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷[東亞合成公司製，商品名；Aronoxetane OXT-221等]、1,3-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、4,4’-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]聯苯、(2-乙基-2-氧雜環丁基)乙醇與對酞酸之酯化物、(2-乙基-2-氧雜環丁基)乙醇與酚酚醛清漆樹脂之醚化物、(2-乙基-2-氧雜環丁基)乙醇與多元羧酸化合物之酯化物等。The oxetane group-containing compound may, for example, be 1,4-bis{[(3-ethyloxetan-3-yl)methoxy]methyl}benzene [manufactured by Toagosei Co., Ltd., a product Name; Aronoxetane OXT-121, etc.], 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane [manufactured by Toagosei Co., Ltd. , trade name; Aronoxetane OXT-221, etc.], 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyl 3-(oxetanyl)methoxymethyl]biphenyl, (2-ethyl-2-oxetanyl)ethanol and esterified with citric acid, (2-ethyl-2-oxo An etherified product of a heterocyclic butyl)ethanol and a phenol novolak resin, an esterified product of (2-ethyl-2-oxetanyl)ethanol and a polyvalent carboxylic acid compound, or the like.

苯并化合物可例舉Macromolecules,36,6010(2003)所記載之「P-a」、「P-alp」、「P-ala」、「B-ala」，Macromolecules,34,7257(2001)所記載之「P-appe」、「Bappe」，四國化成股份有限公司製「B-a型苯并」、「F-a型苯并」、「B-m型苯并」等。Benzo The compound can be exemplified by "Pa", "P-alp", "P-ala", "B-ala" as described in Macromolecules, 36, 6010 (2003), "P-ala", Macromolecules, 34, 7257 (2001). -appe", "Bappe", "Ba-type benzo" made by Shikoku Chemicals Co., Ltd. "Fa type benzophenone "Bm type benzophenone "Wait.

乙烯基苯甲基醚樹脂可例舉V-1000X(昭和高分子股份有限公司製)、美國專利第4116936號公報、美國專利第4170711號公報、美國專利第4278708號公報、日本特開平9-31006號公報、日本特開2001-181383號公報、日本特開2001-253992號公報、日本特開2003-277440號公報、日本特開2003-283076號公報、國際公開第02/083610號冊子等記載之乙烯基苯甲基醚樹脂等。The vinyl benzyl ether resin may, for example, be V-1000X (manufactured by Showa Polymer Co., Ltd.), U.S. Patent No. 4,116,936, U.S. Patent No. 4,170, 711, U.S. Patent No. 4,278,708, and Japanese Patent Laid-Open No. Hei 9-31006 Japanese Laid-Open Patent Publication No. 2001-181383, JP-A-2001-253992, JP-A-2003-277440, JP-A-2003-283076, and International Publication No. 02/083610 Vinyl benzyl ether resin and the like.

順丁烯二醯亞胺化合物，於分子內具有至少1個順丁烯二醯亞胺基，可例舉如苯基順丁烯二醯亞胺、1-甲基-2,4-雙順丁烯二醯亞胺基苯、N,N’-間-伸苯基雙順丁烯二醯亞胺、N,N’-對-伸苯基雙順丁烯二醯亞胺、N,N’-4,4-聯伸苯基雙順丁烯二醯亞胺、N,N’-4,4-(3,3-二甲基聯伸苯基)雙順丁烯二醯亞胺、N,N’-4,4-(3,3-二甲基二苯基甲烷)雙順丁烯二醯亞胺、N,N’-4,4-(3,3-二乙基二苯基甲烷)雙順丁烯二醯亞胺、N,N’-4,4-二苯基甲烷雙順丁烯二醯亞胺、N,N’-4,4-二苯基丙烷雙順丁烯二醯亞胺、N,N’-4,4-二苯基醚雙順丁烯二醯亞胺、N,N’-4,4-二苯基碸雙順丁烯二醯亞胺、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷、2,2-雙[3-第二丁基-3,4-(4-順丁烯二醯亞胺苯氧基)苯基]丙烷、1,1-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]癸烷、4,4’-亞環己基-雙[1-(4-順丁烯二醯亞胺苯氧基)苯氧基]-2-環己基苯、2,2-雙[4-(4-順丁烯二醯亞胺苯氧基)苯基]六氟丙烷等，可單獨使用亦可混合2種類以上使用。The maleimide compound has at least one maleimide group in the molecule, and may, for example, be phenyl maleimide or 1-methyl-2,4-bis Butylenediimide benzene, N,N'-m-phenylenebissuccinimide, N,N'-p-phenylenebissuccinimide, N,N '-4,4-linked phenylbis-s-butylene diimide, N,N'-4,4-(3,3-dimethyl-linked phenyl)bis-non-butylene diimide, N,N'-4,4-(3,3-dimethyldiphenylmethane)bis-n-butylenediamine, N,N'-4,4-(3,3-diethyldiphenyl Methane) bis-n-butylene diimide, N,N'-4,4-diphenylmethane bis-s-butylene diimide, N,N'-4,4-diphenylpropane bis-butane Equinone imine, N,N'-4,4-diphenyl ether bis-n-butylene imide, N,N'-4,4-diphenylfluorene bis-n-butylene diimide, 2,2-bis[4-(4-methylene-2-imide phenoxy)phenyl]propane, 2,2-bis[3-t-butyl-3,4-(4-thinene) Dimethyleneimine phenoxy)phenyl]propane, 1,1-bis[4-(4-maleoximine phenoxy)phenyl]decane, 4,4'-cyclohexylene- Bis[1-(4-methyleneimine)phenoxy)phenoxy]-2-cyclo Hexylbenzene, 2,2-bis[4-(4-methyleneimine phenoxy)phenyl]hexafluoropropane, etc. may be used alone or in combination of two or more.

甲基順丁烯二醯亞胺化合物，於分子內具有至少1個甲基順丁烯二醯亞胺基之化合物或其聚合物，例如苯基甲基順丁烯二醯亞胺、1-甲基-2,4-雙甲基順丁烯二醯亞胺苯、N,N’-間-伸苯基雙甲基順丁烯二醯亞胺、N,N’-對伸苯基雙甲基順丁烯二醯亞胺、N,N’-4,4-聯伸苯基雙甲基順丁烯二醯亞胺、N,N’-4,4-(3,3-二甲基聯伸苯基)雙甲基順丁烯二醯亞胺、N,N’-4,4-(3,3-二甲基二苯基甲烷)雙甲基順丁烯二醯亞胺、N,N’-4,4-(3,3-二乙基二苯基甲烷)雙甲基順丁烯二醯亞胺、N,N’-4,4-二苯基甲烷雙甲基順丁烯二醯亞胺、N,N’-4,4-二苯基丙烷雙甲基順丁烯二醯亞胺、N,N’-4,4-二苯基醚雙甲基順丁烯二醯亞胺、N,N’-4,4-二苯基碸雙甲基順丁烯二醯亞胺、2,2-雙[4-(4-甲基順丁烯二醯亞胺苯氧基)苯基]丙烷、2,2-雙[3-第二丁基-3,4-(4-甲基順丁烯二醯亞胺苯氧基)苯基]丙烷、1,1-雙[4-(4-甲基順丁烯二醯亞胺苯氧基)苯基]癸烷、4,4’-亞環己基-雙[1-(4-甲基順丁烯二醯亞胺苯氧基)苯氧基]-2-環己基苯、2,2-雙[4-(4-甲基順丁烯二醯亞胺苯氧基)苯基]六氟丙烷等，可單獨使用亦可混合2種類以上使用。a methyl maleimide compound, a compound having at least one methyl maleimide group in a molecule or a polymer thereof, such as phenylmethyl maleimide, 1- Methyl-2,4-bismethylbutyleneimine benzene, N,N'-m-phenylene bismethyl maleimide, N,N'-p-phenylene Methyl maleimide, N,N'-4,4-linked phenyl bismethyl succinimide, N,N'-4,4-(3,3-dimethyl Base phenyl) bismethyl succinimide, N, N'-4, 4-(3,3-dimethyldiphenylmethane) bismethyl succinimide, N,N'-4,4-(3,3-diethyldiphenylmethane) bismethyl maleimide, N,N'-4,4-diphenylmethane bismethyl cis Butylene diimide, N,N'-4,4-diphenylpropane bismethyl maleimide, N,N'-4,4-diphenyl ether bismethylbutene Dimethyleneimine, N,N'-4,4-diphenylfluorene bismethylsuccinimide, 2,2-bis[4-(4-methyls-butyleneimine benzene) Oxy)phenyl]propane, 2,2-bis[3-t-butyl-3,4-(4-methylbutyleneimine phenoxy)phenyl]propane, 1,1- Double [4-(4-methyl cis) Acetylimine phenoxy)phenyl]decane, 4,4'-cyclohexylene-bis[1-(4-methylsuccinimide phenoxy)phenoxy]-2 -cyclohexylbenzene, 2,2-bis[4-(4-methylsuccinimide phenoxy)phenyl]hexafluoropropane, etc., may be used alone or in combination of two or more.

納迪克醯亞胺化合物，於分子中具有至少1個納迪克醯亞胺基之化合物或該聚合物，例如苯基納迪克醯亞胺、1-甲基-2,4-雙納迪克醯亞胺苯、N,N’-間-伸苯基雙納迪克醯亞胺、N,N’-對-伸苯基雙納迪克醯亞胺、N,N’-4,4-聯伸苯基雙納迪克醯亞胺、N,N’-4,4-(3,3-二甲基聯伸苯基)雙納迪克醯亞胺、N,N’-4,4-(3,3-二甲基二苯基甲烷)雙納迪克醯亞胺、N,N’-4,4-二苯基甲烷雙納迪克醯亞胺、N,N’-4,4-二苯基丙烷雙納迪克醯亞胺、N,N’-4,4-二苯基醚雙納迪克醯亞胺、N,N’-4,4-二苯基碸雙納迪克醯亞胺、2,2-雙[4-(4-納迪克醯亞胺苯氧基)苯基]丙烷、2,2-雙[3-第二丁基-3,4-(4-納迪克醯亞胺苯氧基)苯基]丙烷、1,1-雙[4-(4-納迪克醯亞胺苯氧基)苯基]癸烷、4,4’-亞環己基-雙[1-(4-納迪克醯亞胺苯氧基)苯氧基]-2-環己基苯、2,2-雙[4-(4-納迪克醯亞胺苯氧基)苯基]六氟丙烷等，可單獨使用亦可混合2種類以上使用。a nadic ylidene compound having at least one nadic amide group in the molecule or a polymer such as phenyl nadic ylide, 1-methyl-2,4-double Nadickia Amine benzene, N,N'-m-phenylene dipyridinium imine, N,N'-p-phenylene dipyridinium imine, N,N'-4,4-linked phenyl Double nadic ylidene imine, N,N'-4,4-(3,3-dimethyllinked phenyl) double nadic quinone imine, N,N'-4,4-(3,3- Dimethyldiphenylmethane) bis nadic ylidene imine, N,N'-4,4-diphenylmethane double nadic quinone imine, N,N'-4,4-diphenylpropane double Dickimide, N,N'-4,4-diphenyl ether double nadic quinone imine, N,N'-4,4-diphenylfluorene double nadic quinone imine, 2,2-double [4-(4-Nadickimine phenoxy)phenyl]propane, 2,2-bis[3-t-butyl-3,4-(4-nadylimidazoline phenoxy)benzene Propane, 1,1-bis[4-(4-nadickylimidinophenoxy)phenyl]decane, 4,4'-cyclohexylene-bis[1-(4-nadicia Amine phenoxy)phenoxy]-2-cyclohexylbenzene, 2,2-bis[4-(4-nadicryleneiminephenoxy)phenyl]hexafluoropropane, etc., may be used alone or Using two kinds or more combined.

就烯丙基納迪克醯亞胺化合物而言，有雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二甲醯亞胺)苯基}甲烷、1,6-己烷-雙-烯丙基納迪克醯亞胺、間伸茬基-雙-烯丙基納迪克醯亞胺等，可單獨使用亦可混合2種類以上使用。In the case of the allyl nadic quinone imine compound, there are bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dimethylimine)phenyl}methane, 1 6-hexane-bis-allyl nadicylimine, m-decyl-bis-allyl n-didecimide, etc., may be used alone or in combination of two or more.

就乙烯基醚化合物而言，有2-羥基乙基乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚、環己烷二甲醇二乙烯基醚、環己烷二甲醇單乙烯基醚、環己基乙烯基醚、環己烷甲醇乙烯基醚、乙基環已醇乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、羥基丙基乙烯基醚、羥基戊基乙烯基醚、二乙基胺基乙基乙烯基醚、三環癸烷環氧基乙烯基醚、乙二醇二乙烯基醚、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、四乙二醇二乙烯基醚、新戊四醇二乙烯基醚、丙二醇二乙烯基醚、二丙二醇二乙烯基醚、三丙二醇二乙烯基醚、新戊二醇二乙烯基醚、1,4-丁二醇二乙烯基醚、1,6-己二醇二乙烯基醚、甘油二乙烯基醚、三羥甲基丙烷二乙烯基醚、1,4-二羥基環己烷二乙烯基醚、1,4-二羥基甲基環己烷二乙烯基醚、氫醌二乙烯基醚、環氧乙烷改質氫醌二乙烯基醚、環氧乙烷改質間苯二酚二乙烯基醚、環氧乙烷改質雙酚A二乙烯基醚、環氧乙烷改質雙酚S二乙烯基醚、甘油三乙烯基醚、山梨醇四乙烯基醚、三羥甲基丙烷三乙烯基醚、新戊四醇三乙烯基醚、新戊四醇四乙烯基醚、二新戊四醇六乙烯基醚、二新戊四醇聚乙烯基醚、二(三羥甲基)丙烷四乙烯基醚、二(三羥甲基)丙烷聚乙烯基醚等，可單獨使用亦可混合2種類以上使用。In the case of the vinyl ether compound, there are 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane II. Methanol monovinyl ether, cyclohexyl vinyl ether, cyclohexane methanol vinyl ether, ethyl cyclohexanyl vinyl ether, methoxy ethyl vinyl ether, ethoxyethyl vinyl ether, hydroxypropyl Vinyl ether, hydroxypentyl vinyl ether, diethylaminoethyl vinyl ether, tricyclodecane epoxy vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, Triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl Alcohol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4- Dihydroxycyclohexanedivinyl ether, 1,4-dihydroxymethylcyclohexanedivinyl ether, hydroquinone divinyl ether, ethylene oxide modified hydroquinone divinyl Ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerol trivinyl ether, Sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, neopentyl alcohol trivinyl ether, neopentyl alcohol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol Polyvinyl ether, bis(trimethylol)propane tetravinyl ether, bis(trimethylol)propane polyvinyl ether, etc. may be used alone or in combination of two or more.

就硫醇化合物而言，有2,4,6-三巰基-s-***、2-二丁基胺基-4,6-二巰基-s-三、2-苯胺基-4,6-二巰基-S-三、四乙二醇雙-3-巰基丙酸酯、三羥甲基丙烷三-3-巰基丙酸酯、三-(乙基-3-巰基丙酸酯)三聚異氰酸酯、新戊四醇四-3-巰基丙酸酯、二新戊四醇六-3-巰基丙酸酯等，可單獨使用亦可混合2種類以上使用。In the case of thiol compounds, there are 2,4,6-trimethyl-s-triazole, 2-dibutylamino-4,6-dimercapto-s-three 2-anilino-4,6-dimercapto-S-three , tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tri-3-mercaptopropionate, tris-(ethyl-3-mercaptopropionate) trimeric isocyanate, neopentyl alcohol -3-mercaptopropionate, dipentaerythritol hexa-3-mercaptopropionate, etc. may be used alone or in combination of two or more.

胺基樹脂，可例舉尿素、三聚氰胺、苯并胍胺及乙胍胺等與甲醛之加成化合物或者其部分縮合物。The amine-based resin may, for example, be an addition compound with urea or a partial condensate thereof such as urea, melamine, benzoguanamine or acetamide.

又，酚樹脂可例舉酚、甲酚類及雙酚類等化合物與甲醛之加成化合物或者其部分縮合物。具體上可例舉酚樹脂、甲酚樹脂、第三丁基酚樹脂、二環戊二烯甲酚樹脂、二環戊二烯酚樹脂、伸茬基改質酚樹脂、四酚樹脂、雙酚A樹脂、聚對乙烯基酚樹脂之可溶酚醛型(resol)樹脂或酚醛清漆型樹脂。其他，可例舉萘酚系化合物、三酚系化合物、酚芳烷基樹脂。其中，因酚樹脂之可溶酚醛型樹脂在耐熱性及硬化性的方面非常優異，可適宜用於本發明中。Further, the phenol resin may, for example, be an addition compound of a compound such as phenol, cresol or bisphenol with formaldehyde or a partial condensate thereof. Specific examples thereof include a phenol resin, a cresol resin, a third butyl phenol resin, a dicyclopentadiene cresol resin, a dicyclopentadiene phenol resin, a hydrazine-modified phenol resin, a tetraphenol resin, and a bisphenol. A resin, a resol resin of a poly-p-vinylphenol resin or a novolac type resin. Other examples include a naphthol compound, a trisphenol compound, and a phenol aralkyl resin. Among them, the novolac type resin of the phenol resin is excellent in heat resistance and hardenability, and can be suitably used in the present invention.

熱硬化助劑(C)，觸媒的方式協助硬化反應之化合物，可例舉3級胺及其鹽類、二氰二胺、羧醯肼、咪唑類、氮雜雙環化合物類、膦類、鏻鹽類，使用該等使熱硬化反應更有效率地進行且塗膜耐性優異而較佳。The thermosetting assistant (C), a catalyst-assisted compound for assisting the hardening reaction, may be a tertiary amine and a salt thereof, a dicyandiamide, a carboxy hydrazine, an imidazole, an azabicyclic compound, or a phosphine. The onium salt is preferably used because the thermosetting reaction proceeds more efficiently and the coating film resistance is excellent.

具體上可例舉三乙基胺、三丁基胺、苯甲基二甲基胺、2,4,6-三(二甲基胺基甲基)酚、N-甲基哌等3級胺類、及其鹽類；2-甲基咪唑、2-苯基咪唑、2-十一基咪唑、2-乙基-4-甲基咪唑、1-氰基乙基-2-甲基咪唑、2,4-二氰基-6-[2-甲基咪唑基-1]-乙基-S-三、硼酸2-乙基-4-甲基咪唑四苯基酯等咪唑類、及其鹽類；1,5-二氮雜雙環[5,4,0]-7-十一烷、1,5-二氮雜雙環[4,3,0]-5-壬烷、1,4-二氮雜雙環[2,2,2,]辛烷、硼酸1,8-二氮雜雙環[5.4.0]十一烯-7-四苯基酯等二氮雜雙環化合物類；三丁基膦、三苯基膦、三(二甲氧基苯基)膦、三(羥基丙基)膦、三(氰基乙基)膦等膦類；四苯基鏻四苯基硼鹽、甲基三丁基鏻四苯基硼鹽、甲基三氰基乙基鏻四苯基硼鹽等鏻鹽類；其他，觸媒的方式且自身亦直接協助硬化反應之化合物，可例舉二氰二胺、羧醯肼等。羧醯肼，可例舉丁二醯肼、已二醯肼等。Specifically, triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methylpiperidyl can be exemplified. Grade 3 amines, and salts thereof; 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Methylimidazole, 2,4-dicyano-6-[2-methylimidazolyl-1]-ethyl-S-three Imidazoles such as 2-ethyl-4-methylimidazolium tetraphenyl borate, and salts thereof; 1,5-diazabicyclo[5,4,0]-7-undecane, 1,5 -diazabicyclo[4,3,0]-5-nonane, 1,4-diazabicyclo[2,2,2,]octane, boric acid 1,8-diazabicyclo[5.4.0 a diazabicyclo compound such as undecene-7-tetraphenyl ester; tributylphosphine, triphenylphosphine, tris(dimethoxyphenyl)phosphine, tris(hydroxypropyl)phosphine, tri ( a phosphine such as cyanoethyl)phosphine; a phosphonium salt such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate or methyltricyanoethylphosphonium tetraphenylborate; Other compounds which are in a manner of a catalyst and which directly assist the hardening reaction by themselves may, for example, be dicyandiamide or carboxyindole. The carboxy hydrazine may, for example, be diterpene or diterpene.

該等熱硬化助劑(C)可僅一種類使用，又，亦可併用二種類以上。These thermosetting assistants (C) may be used in only one type, or two or more types may be used in combination.

熱硬化助劑(C)使用量只要考慮硬化性樹脂組成物的硬化物性而決定即可，無特別限定者，相對於本發明之含有羧基之改質酯樹脂(A)100重量份，使用量較佳係0.05重量份至20重量份的範圍內，更佳係0.1重量份至10重量份的範圍內。藉此可調控本發明之熱硬化性樹脂組成物的交聯速度和交聯密度、凝集力，可進一步提昇各種物性。熱硬化助劑(C)的使用量在0.05重量份以上時，可充分得到其添加效果，又，該使用量在20重量份以下時，電氣絕緣性、接著強度、銲錫耐熱性優異。The amount of use of the thermosetting auxiliary (C) is determined in consideration of the cured physical properties of the curable resin composition, and is not particularly limited, and is used in an amount of 100 parts by weight based on 100 parts by weight of the carboxyl group-containing modified ester resin (A) of the present invention. It is preferably in the range of from 0.05 part by weight to 20 parts by weight, more preferably from 0.1 part by weight to 10 parts by weight. Thereby, the crosslinking rate, the crosslinking density, and the cohesive force of the thermosetting resin composition of the present invention can be adjusted, and various physical properties can be further improved. When the amount of the heat-curing auxiliary (C) is 0.05 parts by weight or more, the effect of addition can be sufficiently obtained, and when the amount is 20 parts by weight or less, electrical insulating properties, adhesion strength, and solder heat resistance are excellent.

其他，本發明之熱硬化性樹脂組成物在不損害其目的之範圍內，可進一步添加下述之任意成分，溶劑、染料、顏料、阻燃劑、抗氧化劑、聚合禁止劑、消泡劑、調平劑、離子捕集劑、保濕劑、黏度調整劑、防腐劑、抗菌劑、抗靜電劑、防阻塞劑、紫外線吸收劑、紅外線吸收劑、電磁波屏蔽劑、填充劑等。尤其是電子材料用途而使用於直接接觸電路之絕緣部材(例如電路保護膜、覆蓋層、層間絕緣材料等)、電路週邊之可能呈高熱之部材(印刷配線板接著劑、支持基板等)時，較佳係併用阻燃劑。In addition, the thermosetting resin composition of the present invention may further contain any of the following components, solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, antifoaming agents, and the like, without impairing the purpose thereof. Leveling agent, ion trapping agent, moisturizing agent, viscosity adjusting agent, preservative, antibacterial agent, antistatic agent, anti-blocking agent, ultraviolet absorber, infrared absorber, electromagnetic wave shielding agent, filler, and the like. In particular, when it is used for an electronic material, it is used for an insulating member (for example, a circuit protective film, a cover layer, an interlayer insulating material, etc.) that directly contacts a circuit, and a component (a printed wiring board adhesive, a supporting substrate, etc.) that may be high in heat around the circuit. It is preferred to use a flame retardant in combination.

阻燃劑可例舉如磷酸三聚氰胺、聚磷酸三聚氰胺、磷酸胍、聚磷酸胍、磷酸銨、聚磷酸銨、磷酸醯胺銨、聚磷酸醯胺銨、磷酸胺甲酸酯、聚磷酸胺甲酸酯等磷酸鹽系化合物和聚磷酸鹽系化合物，紅磷、有機磷酸酯化合物、磷氮基化合物(phosphazene compound)、亞磷酸(phosphonic acid)化合物、二乙基膦酸(phosphinic acid)鋁、甲基乙基膦酸鋁、二苯基膦酸鋁、乙基丁基膦酸鋁、甲基丁基膦酸鋁、聚乙烯膦酸鋁等磷酸化合物，氧化膦化合物、磷烷化合物、磷醯胺化合物等磷系阻燃劑；三聚氰胺、蜜白胺(melam)、蜜勒胺(melem)、氰尿醯胺(melon)、三聚氰胺三聚氰酸酯等三系化合物，三聚氰酸化合物、異三聚氰酸化合物、***系化合物、四唑化合物、重氮化合物、尿素等氮系阻燃劑；矽氧化合物、矽烷化合物等矽系阻燃劑；鹵化雙酚A、鹵化環氧化合物、鹵化苯氧基化合物等低分子含鹵化合物、經鹵化之寡聚物或聚合物等鹵系阻燃劑；氫氧化鋁、氫氧化鎂、氫氧化鋯、氫氧化鋇、氫氧化鈣等金屬氫氧化物，氧化錫、氧化鋁、氧化鎂、氧化鋯、氧化鋅、氧化鉬、氧化銻、氧化鎳、碳酸鋅、碳酸鎂、碳酸鈣、碳酸鋇、硼酸鋅、水合玻璃等無機系阻燃劑等。本發明中，顧慮近年受到輿論之對環境的影響，最好係使用磷系阻燃劑和氮系阻燃劑等非鹵系阻燃劑，其中與本發明之熱硬化性樹脂組成物的併用，較佳係使用阻燃性有效果之磷氮基化合物、膦化合物、聚磷酸三聚氰胺、聚磷酸銨、三聚氰胺三聚氰酸酯等。本發明中，該等阻燃劑可單獨使用或複數併用。The flame retardant may, for example, be melamine phosphate, melamine polyphosphate, strontium phosphate, strontium polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amide ammonium phosphate, ammonium polyphosphate ammonium phosphate, urethane phosphate, polyphosphoric acid Phosphate-based compounds such as esters and polyphosphate-based compounds, red phosphorus, organic phosphate compounds, phosphazene compounds, phosphoric acid compounds, phosphinic acid aluminum, and Phosphate compound such as aluminum bisphosphonate, aluminum diphenylphosphinate, aluminum ethyl butylphosphinate, aluminum methyl butylphosphinate, aluminum polyphosphinate, phosphine oxide compound, phosphine compound, phosphoniumamine Phosphorus-based flame retardants such as compounds; melamine, melam, melem, melon, melamine cyanurate, etc. a compound, a cyanuric acid compound, a tricyanuric acid compound, a triazole compound, a tetrazole compound, a diazo compound, a nitrogen-based flame retardant such as urea; an antimony-based flame retardant such as an anthracene compound or a decane compound; Halogenated halogen-containing compounds such as halogenated bisphenol A, halogenated epoxy compounds, halogenated phenoxy compounds, halogenated flame retardants such as halogenated oligomers or polymers; aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, Metal hydroxide such as barium hydroxide or calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cerium oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, boric acid Inorganic flame retardants such as zinc and hydrated glass. In the present invention, it is preferable to use a non-halogen flame retardant such as a phosphorus-based flame retardant or a nitrogen-based flame retardant, which is in combination with the thermosetting resin composition of the present invention. Preferably, a flame retardant phosphorus-nitrogen-based compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate or the like is used. In the present invention, the flame retardants may be used singly or in combination.

消泡劑、調平劑可例舉矽氧系、烴系、丙烯酸系樹脂系之化合物等。Examples of the antifoaming agent and the leveling agent include a compound of an anthracene oxygen type, a hydrocarbon type, and an acrylic resin type.

離子捕集劑可適用無機或有機的離子交換體。詳細而言可用東亞合成股份有限公司之無機離子交換體IXE、三菱化學股份有限公司之離子交換樹脂DIAION，但只要有離子捕集能者即可，不限於該等。The ion trapping agent can be applied to an inorganic or organic ion exchanger. In detail, the inorganic ion exchanger IXE of the East Asia Synthetic Co., Ltd. and the ion exchange resin DIAION of Mitsubishi Chemical Corporation may be used, but the ion trapping energy is not limited thereto.

本申請案發明之熱硬化性樹脂組成物可藉由混合上述(A)含有羧基之改質酯樹脂、(B)化合物、(C)熱硬化助劑、及因應需要之上述任意成分而得到。The thermosetting resin composition of the invention of the present application can be obtained by mixing the above (A) a carboxyl group-containing modified ester resin, (B) a compound, (C) a thermosetting auxiliary agent, and the above optional components.

本申請案發明之硬化物係藉由用以往公知方法例如逗號塗佈(comma coating)、刮刀式塗佈(knife coating)、模具塗佈(die coating)、唇嘴塗佈(lip coating)、輥塗佈(roll coating)、淋幕式塗佈(curtain coating)、棒塗佈(bar coating)、凹版印刷、彈性印刷(flexography)、浸泡塗佈(dip coating)、噴霧塗佈(Spray coating)、旋轉塗佈等方法，將熱硬化性樹脂組成物塗佈於剝離基材的至少一面後，通常於40至150℃乾燥而製造。又，接著劑層的乾燥膜厚為了發揮充分的接著性、焊錫耐熱性，而且從容易處理這點來看，較佳係5μm至500μm，更佳係10μm至100μm。The cured product of the present invention is obtained by a conventionally known method such as comma coating, knife coating, die coating, lip coating, and roll. Roll coating, curtain coating, bar coating, gravure printing, flexography, dip coating, spray coating, After the method of spin coating or the like, the thermosetting resin composition is applied to at least one surface of the release substrate, and then dried at 40 to 150 ° C, usually. Further, the dry film thickness of the adhesive layer is preferably from 5 μm to 500 μm, more preferably from 10 μm to 100 μm, in order to exhibit sufficient adhesion and solder heat resistance.

又，接著說明使用熱硬化性樹脂組成物之印刷配線板的製造方法。於聚酯或聚醯亞胺等有可撓性、絕緣性之塑膠薄膜上，將導體圖案用印刷技術而形成之撓性印刷配線板的導體圖案以覆蓋的方式與本發明之熱硬化性樹脂組成物重疊，加熱/加壓而使熱硬化性樹脂組成物硬化，而可得到設置保護層之撓性印刷配線板。Moreover, the method of manufacturing a printed wiring board using a thermosetting resin composition will be described next. The conductive pattern of the flexible printed wiring board formed by the printing technique of the conductive pattern on the flexible or insulating plastic film such as polyester or polyimide, and the thermosetting resin of the present invention The composition is superposed, heated and pressurized to cure the thermosetting resin composition, and a flexible printed wiring board provided with a protective layer can be obtained.

設置導電性電路之方法，例如經由或不經由接著劑層於基膜(base film)上設置銅箔而成之可撓性敷銅板的銅箔上形成感光性蝕刻光阻層，經過具備電路圖案之遮罩膜而曝光，僅硬化曝光部，然後將未曝光部的銅箔藉由蝕刻而去除後，剝離殘留的光阻層等，可由銅箔形成導電性電路。或者，可為用濺鍍、電鍍等手段而僅設置需要的電路於基膜上者。A method of providing a conductive circuit, for example, forming a photosensitive etch photoresist layer on a copper foil of a flexible copper-clad plate formed by providing a copper foil on a base film without or via an adhesive layer, and having a circuit pattern The mask film is exposed to light, and only the exposed portion is cured, and then the copper foil of the unexposed portion is removed by etching, and then the remaining photoresist layer or the like is peeled off, and a conductive circuit can be formed from the copper foil. Alternatively, it may be a method in which only a necessary circuit is provided on the base film by means of sputtering, plating, or the like.

又，在複數撓性印刷配線之間夾著從本發明之熱硬化性樹脂組成物剝除剝離性基材而成之硬化性接著劑層，藉由加熱/加壓而使熱硬化性樹脂組成物硬化，可得到多層撓性印刷配線板。可使用本發明之熱硬化性樹脂組成物，而積層銅箔和耐熱性絕緣性可撓性基材。In addition, a curable adhesive layer obtained by removing a peelable base material from the thermosetting resin composition of the present invention is interposed between the plurality of flexible printed wirings, and is composed of a thermosetting resin by heating/pressurization. The material is hardened to obtain a multilayer flexible printed wiring board. The thermosetting resin composition of the present invention can be used to laminate a copper foil and a heat-resistant insulating flexible substrate.

再者，使用本發明之熱硬化性樹脂組成物，可得附有補強材之撓性印刷配線板。附有補強材之撓性印刷配線板係撓性印刷配線板與玻璃環氧物、金屬、聚醯亞胺等補強材之間夾著從本發明之熱硬化性樹脂組成物剝除剝離性基材而成之硬化性接著劑層，藉由加熱/加壓而使熱硬化性樹脂組成物硬化，於撓性印刷配線板附上補強材者。Further, by using the thermosetting resin composition of the present invention, a flexible printed wiring board with a reinforcing material can be obtained. A flexible printed wiring board with a reinforcing material is a flexible printed wiring board, and a reinforcing material such as glass epoxy, metal, or polyimide is peeled off from the thermosetting resin composition of the present invention. The hardenable adhesive layer made of the material is cured by heating/pressurization, and the reinforcing material is attached to the flexible printed wiring board.

根據本發明可得接著強度、電氣絕緣性、耐熱性、屈曲性、加工性、耐焊劑性優異，尤其是同時滿足保存安定性與加工安定性，並進一步保持高接著強度的同時顯示高度耐熱性，再更進一步可兼顧接著強度與電氣絕緣性、耐熱性與屈曲性，含有羧基之改質酯樹脂及熱硬化性樹脂組成物。該等可適用於以撓性印刷配線板週邊為首之電子材料用接著劑和接著片、塗佈劑、電路被覆用焊錫光阻、覆蓋層薄膜、電磁波屏蔽用接著劑、電鍍光阻、印刷配線板用層間電氣絕緣材料、光導波路等。本發明之熱硬化性樹脂組成物尤其適用於接著劑組成物。According to the present invention, it is excellent in adhesive strength, electrical insulating properties, heat resistance, buckling property, workability, and solder resist resistance, and in particular, it satisfies both storage stability and processing stability, and further maintains high adhesion strength while exhibiting high heat resistance. Furthermore, it is possible to combine the strength and electrical insulation properties, the heat resistance and the buckling property, and the carboxylate-containing modified ester resin and the thermosetting resin composition. These can be applied to an adhesive for an electronic material, a bonding sheet, a coating agent, a solder resist for a circuit coating, a cover film, an adhesive for electromagnetic wave shielding, a plating resist, and a printed wiring, which are mainly used for the periphery of a flexible printed wiring board. Interlayer electrical insulation materials, optical waveguides, etc. The thermosetting resin composition of the present invention is particularly suitable for use as an adhesive composition.

(實施例)(Example)

以下，藉實施例進一步具體說明本發明，本發明之權利範圍不限於以下實施例。再者，實施例之「份」及「%」分別表示「重量份」及「重量%」，Mw意指重量平均分子量。Hereinafter, the present invention will be further specifically described by the examples, and the scope of the present invention is not limited to the following examples. In addition, "parts" and "%" of the examples mean "parts by weight" and "% by weight", respectively, and Mw means a weight average molecular weight.

＜重量平均分子量(Mw)之測定＞<Measurement of Weight Average Molecular Weight (Mw)>

Mw之測定係用TOSOH股份有限公司製GPC(凝膠滲透層析)「HPC-8020」。GPC係溶解於溶劑(THF；四氫呋喃)的物質依其分子大小的差而分離定量之液相層析法。本發明之測定係將管柱「LF-604」(昭和電工股份有限公司製：迅速分析用GPC管柱：6mmID×150mm大小)串聯而連接2管使用，流量0.6ml/分鐘、管柱溫度40℃之條件進行，重量平均分子量(Mw)係以換算成聚苯乙烯而決定。For the measurement of Mw, GPC (gel permeation chromatography) "HPC-8020" manufactured by TOSOH Co., Ltd. was used. GPC is a liquid chromatography method in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified depending on the difference in molecular size. In the measurement system of the present invention, the column "LF-604" (manufactured by Showa Denko Co., Ltd.: GPC column for rapid analysis: 6 mm ID × 150 mm size) was connected in series and connected to 2 tubes, and the flow rate was 0.6 ml/min, and the column temperature was 40. The conditions of °C were carried out, and the weight average molecular weight (Mw) was determined by conversion into polystyrene.

[製造例1][Manufacturing Example 1]

於具備攪拌機、回流冷卻管、氮氣導入管、導入管、溫度計之4口燒瓶中，置入聚碳酸酯二醇(Kuraray多元醇C-2090：Kuraray股份有限公司製：3-甲基-1,5-戊二醇/1,6-己二醇=9/1(莫耳比)共聚合聚碳酸酯二醇：羥基價=56mgKOH/g，Mw=2000)292.1份、四氫酞酸酐(RIKACID TH：新日本理化股份有限公司製)44.9份、溶劑之甲苯350份，於氮氣氣流下，邊攪拌邊升溫至60℃，使其均勻溶解。然後將該燒瓶升溫至110℃，反應3小時。其後，冷卻到40℃後，添加雙酚A型環氧樹脂(YD-8125：東都化成股份有限公司製：環氧當量=175g/eq)62.9份、觸媒之三苯基膦4份，升溫至110℃，反應8小時。冷卻到室溫後，添加四氫酞酸酐11.8份，於110℃反應3小時。冷卻到室溫後，用甲苯將固形分調整成35%，得到本發明之含有羧基之改質酯樹脂(A)溶液。由本製造例所得之含有羧基之改質酯樹脂(A)的重量平均分子量為12600，根據實測之樹脂固形分的酸價為15.3mgKOH/g。A polycarbonate diol (Kuraray polyol C-2090: manufactured by Kuraray Co., Ltd.: 3-methyl-1) was placed in a 4-neck flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer. 5-pentanediol/1,6-hexanediol = 9/1 (mole ratio) copolymerized polycarbonate diol: hydroxyl value = 56 mgKOH/g, Mw = 2000) 292.1 parts, tetrahydrophthalic anhydride (RIKACID) TH: 44.9 parts of a Nippon Chemical and Chemical Co., Ltd. product, and 350 parts of a solvent of toluene were heated to 60 ° C under a nitrogen gas stream to be uniformly dissolved. The flask was then warmed to 110 ° C and allowed to react for 3 hours. Thereafter, after cooling to 40 ° C, 62.9 parts of a bisphenol A type epoxy resin (YD-8125: manufactured by Tohto Kasei Co., Ltd.: epoxy equivalent = 175 g/eq) and 4 parts of a catalyst triphenylphosphine were added. The temperature was raised to 110 ° C and the reaction was carried out for 8 hours. After cooling to room temperature, 11.8 parts of tetrahydrophthalic anhydride was added, and the mixture was reacted at 110 ° C for 3 hours. After cooling to room temperature, the solid content was adjusted to 35% with toluene to obtain a carboxyl group-containing modified ester resin (A) solution of the present invention. The weight average molecular weight of the carboxyl group-containing modified ester resin (A) obtained in the present production example was 12,600, and the acid value of the resin solid content measured was 15.3 mgKOH/g.

[製造例2至36、比較製造例1至9][Manufacturing Examples 2 to 36, Comparative Manufacturing Examples 1 to 9]

除了換成表1至3所示之材料以外，進行與製造例1相同操作，得到本發明之含有羧基之改質酯樹脂(A)溶液。The carboxyl group-containing modified ester resin (A) solution of the present invention was obtained in the same manner as in Production Example 1, except that the materials shown in Tables 1 to 3 were replaced.

C-2090：Kuraray股份有限公司製，3-甲基-1,5-戊二醇/1,6-己二醇=9/1(莫耳比)共聚合聚碳酸酯二醇C-2090: Kuraray Co., Ltd., 3-methyl-1,5-pentanediol/1,6-hexanediol = 9/1 (mole ratio) copolymerized polycarbonate diol

T-5652：旭化成Chemicals股份有限公司製，C5C6共聚合聚碳酸酯二醇T-5652: Asahi Kasei Chemicals Co., Ltd., C5C6 copolymerized polycarbonate diol

UHC50-200：宇部興產股份有限公司製，1,6-己二醇/己內酯=5/5共聚合聚碳酸酯二醇UHC50-200: manufactured by Ube Industries, Ltd., 1,6-hexanediol/caprolactone=5/5 copolymerized polycarbonate diol

UC-100：宇部興產股份有限公司製，以1,4-環己烷二甲醇為基礎之聚碳酸酯二醇UC-100: manufactured by Ube Hiroshi Co., Ltd., based on 1,4-cyclohexanedimethanol

UM90(1/3)：宇部興產股份有限公司製，1,4-環己烷二甲醇/1,6-己二醇=1/3共聚合聚碳酸酯二醇UM90 (1/3): manufactured by Ube Industries, Ltd., 1,4-cyclohexanedimethanol/1,6-hexanediol = 1/3 copolymerized polycarbonate diol

UM90(1/1)：宇部興產股份有限公司製，1,4-環己烷二甲醇/1,6-己二醇=1/1共聚合聚碳酸酯二醇UM90(1/1): 1,4-cyclohexanedimethanol/1,6-hexanediol = 1/1 copolymerized polycarbonate diol, manufactured by Ube Industries, Ltd.

UM90(3/1)：宇部興產股份有限公司製，1,4-環己烷二甲醇/1,6-己二醇=3/1共聚合聚碳酸酯二醇UM90(3/1): manufactured by Ube Industries, Ltd., 1,4-cyclohexanedimethanol/1,6-hexanediol = 3/1 copolymerized polycarbonate diol

PTG-2000SN：保土谷化學股份有限公司製，聚四亞甲基二醇PTG-L2000：保土谷化學股份有限公司製，聚四亞甲基二醇(重量平均分子量約2000)PTG-2000SN: manufactured by Hodogaya Chemical Co., Ltd., polytetramethylene glycol PTG-L2000: manufactured by Hodogaya Chemical Co., Ltd., polytetramethylene glycol (weight average molecular weight about 2000)

GI-2000：日本曹達股份有限公司製，氫化型聚丁二烯二醇(重量平均分子量約2100)GI-2000: Hydrogenated polybutadiene diol (weight average molecular weight of about 2100) manufactured by Japan Soda Co., Ltd.

G-2000：日本曹達股份有限公司製，α,ω-聚丁二烯二醇(重量平均分子量約1800)G-2000: manufactured by Japan Soda Co., Ltd., α,ω-polybutadiene diol (weight average molecular weight about 1800)

Poly-ip：出光興產股份有限公司製，羥基末端液狀異戊二烯(重量平均分子量約2500)Poly-ip: manufactured by Idemitsu Kosan Co., Ltd., hydroxyl terminated liquid isoprene (weight average molecular weight about 2500)

KF-6002：信越化學工業股份有限公司製，兩末端甲醇改質型聚矽氧油(重量平均分子量約3000)KF-6002: Shin-Etsu Chemical Co., Ltd., two-terminal methanol-modified polyfluorene-oxygen oil (weight average molecular weight of about 3000)

P-1041：Kuraray股份有限公司製，3-甲基-1,5-戊二醇/1,4-環己烷二羧酸共聚合聚酯多元醇(重量平均分子量約1000)P-1041: 3-methyl-1,5-pentanediol/1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol (weight average molecular weight about 1000) manufactured by Kuraray Co., Ltd.

P-2041：Kuraray股份有限公司製，3-甲基-1,5-戊二醇/1,4-環己烷二羧酸共聚合聚酯多元醇(重量平均分子量約2000)P-2041: 3-methyl-1,5-pentanediol/1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol (weight average molecular weight about 2000) manufactured by Kuraray Co., Ltd.

P-2010：Kuraray股份有限公司製，脂肪族聚酯多元醇(重量平均分子量約2000)P-2010: manufactured by Kuraray Co., Ltd., an aliphatic polyester polyol (weight average molecular weight of about 2000)

C-590：Kuraray股份有限公司製，3-甲基-1,5-戊二醇/1,6-己二醇=9/1(莫耳比)共聚合聚碳酸酯二醇(重量平均分子量約600)C-590: Kuraray Co., Ltd., 3-methyl-1,5-pentanediol/1,6-hexanediol = 9/1 (mole ratio) copolymerized polycarbonate diol (weight average molecular weight) About 600)

C-1090：Kuraray股份有限公司製，3-甲基-1,5-戊二醇/1,6-己二醇=9/1(莫耳比)共聚合聚碳酸酯二醇(重量平均分子量約1000)C-1090: 3-methyl-1,5-pentanediol/1,6-hexanediol=9/1 (mole ratio) copolymerized polycarbonate diol (weight average molecular weight) manufactured by Kuraray Co., Ltd. About 1000)

TH：新日本理化股份有限公司製，四氫酞酸酐TH: New Japan Physicochemical Co., Ltd., tetrahydrophthalic anhydride

HNA-100：新日本理化股份有限公司製，甲基雙環[2.2.1]庚烷-2,3-二羧酸酐HNA-100: New Japan Physicochemical Co., Ltd., methyl bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride

TMA酐：偏苯三甲酸酐TMA anhydride: trimellitic anhydride

SA：新日本理化股份有限公司製，丁二酸酐SA: New Japan Physicochemical Co., Ltd., succinic anhydride

YD-8125：東都化成股份有限公司製，雙酚A型環氧樹脂YD-8125: Dongdu Chemical Co., Ltd., bisphenol A epoxy resin

EX-216L：Nagase ChemteX股份有限公司製，環己烷二甲醇二環氧丙基醚EX-216L: Nagase ChemteX Co., Ltd., cyclohexane dimethanol diepoxypropyl ether

EX-214L：Nagase ChemteX股份有限公司製，1,4-丁二醇二環氧丙基醚EX-214L: Nagase ChemteX Co., Ltd., 1,4-butanediol diepoxypropyl ether

EX-212L：Nagase ChemteX股份有限公司製，1,6-己二醇二環氧丙基醚EX-212L: 1,6-hexanediol diepoxypropyl ether, manufactured by Nagase ChemteX Co., Ltd.

YX-8800：三菱化學股份有限公司製，二羥基蒽型環氧樹脂YX-8800: manufactured by Mitsubishi Chemical Corporation, dihydroxy oxime epoxy resin

YDF-8170C：東都化成股份有限公司製，雙酚F型環氧樹脂YDF-8170C: Dongdu Chemical Co., Ltd., bisphenol F epoxy resin

ZX-1059：東都化成股份有限公司製，雙酚型環氧樹脂ZX-1059: Dongdu Chemical Co., Ltd., bisphenol epoxy resin

BHPA：N,N-雙(2-羥基丙基)苯胺BHPA: N,N-bis(2-hydroxypropyl)aniline

DMBA：二羥甲基丁酸DMBA: dimethylolbutanoic acid

TMP：三羥甲基丙烷TMP: Trimethylolpropane

1、6-HD：1,6-己二醇1,6-HD: 1,6-hexanediol

(實施例1)(Example 1)

混合相對於製造例1所得之含有羧基之改質酯樹脂(A)溶液的固形分100份、化合物(B)之多官能環氧丙基醚型環氧樹脂(三菱化學社製「EPIKOTE 1031S」)20份、及熱硬化助劑(C)之CHEMITITE PZ(日本觸媒股份有限公司製，多官能氮雜環丙烷化合物)1份，得到熱硬化性樹脂組成物。將該熱硬化性樹脂組成物以乾燥後的膜厚成為30μm的方式均勻地塗裝於經過剝離處理之聚酯薄膜上後乾燥，設置接著劑層。然後，將經過剝離處理之另一個聚酯薄膜積層於接著劑層側，得到附雙面保護膜之接著片。100 parts of the solid content of the carboxyl group-containing modified ester resin (A) solution obtained in Production Example 1 and the polyfunctional epoxy propyl ether type epoxy resin of the compound (B) ("EPIKOTE 1031S" manufactured by Mitsubishi Chemical Corporation" 20 parts of CHEMITITE PZ (manufactured by Nippon Shokubai Co., Ltd., polyfunctional aziridine compound) of 20 parts of heat curing aid (C), and a thermosetting resin composition was obtained. The thermosetting resin composition was uniformly coated on the release-treated polyester film so that the film thickness after drying was 30 μm, and dried, and an adhesive layer was provided. Then, another polyester film which was subjected to the release treatment was laminated on the side of the adhesive layer to obtain a back sheet having a double-sided protective film.

(實施例2至27)(Examples 2 to 27)

除了將實施例1所使用之製造例1的含有羧基之改質酯樹脂(A)溶液分別換成由製造例2至27所得之含有羧基之改質酯樹脂(A)溶液以外，皆進行與實施例1相同操作，作成附雙面保護膜之接著片。Except that the carboxyl group-containing modified ester resin (A) solution of Production Example 1 used in Example 1 was replaced with the carboxyl group-containing modified ester resin (A) solution obtained in Production Examples 2 to 27, In the same manner as in Example 1, a back sheet having a double-sided protective film was formed.

(實施例28)(Embodiment 28)

混合相對於由製造例28所得之含有羧基之改質酯樹脂(A)溶液的固形分100份、化合物(B)之多官能環氧丙基醚型環氧樹脂(三菱化學社製「EPIKOTE 1031S」)18份、及熱硬化助劑(C)之二氰二胺1份，得到熱硬化性樹脂組成物。將該熱硬化性樹脂組成物以乾燥後的膜厚成為30μm的方式均勻地塗裝於經過剝離處理之聚酯薄膜上後乾燥，設置接著劑層。然後，將經過剝離處理之另一個聚酯薄膜積層於接著劑層側，得到附雙面保護膜之接著片。100 parts of a solid content of the solution containing the carboxyl group-containing modified ester resin (A) obtained in Production Example 28, and a polyfunctional epoxy propyl ether type epoxy resin of the compound (B) (EPIKOTE 1031S, manufactured by Mitsubishi Chemical Corporation) ” 18 parts and 1 part of dicyandiamide of the thermosetting assistant (C), and a thermosetting resin composition was obtained. The thermosetting resin composition was uniformly coated on the release-treated polyester film so that the film thickness after drying was 30 μm, and dried, and an adhesive layer was provided. Then, another polyester film which was subjected to the release treatment was laminated on the side of the adhesive layer to obtain a back sheet having a double-sided protective film.

(實施例29至36)(Examples 29 to 36)

除了將實施例28所使用之製造例28的含有羧基之改質酯樹脂(A)溶液分別換成由製造例29至36所得之含有羧基之改質酯樹脂(A)溶液以外，皆進行與實施例1相同操作，作成附雙面保護膜之接著片。The solution of the carboxyl group-containing modified ester resin (A) of Production Example 28 used in Example 28 was replaced with the carboxyl group-containing modified ester resin (A) solution obtained in Production Examples 29 to 36, respectively. In the same manner as in Example 1, a back sheet having a double-sided protective film was formed.

(實施例37至64)(Examples 37 to 64)

除了以表4所示之組成得到熱硬化性樹脂組成物以外，皆進行與實施例1相同操作，作成附雙面保護膜之接著片。A laminate having a double-sided protective film was prepared in the same manner as in Example 1 except that the thermosetting resin composition was obtained in the composition shown in Table 4.

828：三菱化學股份有限公司製，雙酚A型環氧化合物828: bisphenol A epoxy compound manufactured by Mitsubishi Chemical Corporation

EOCN-102S：日本化藥股份有限公司製，甲酚酚醛清漆型環氧樹脂EOCN-102S: Made from Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin

EPPN-201L：日本化藥股份有限公司製，酚酚醛清漆型環氧樹脂EPPN-201L: Made by Nippon Kayaku Co., Ltd., phenol novolak type epoxy resin

YH434L：東都化成股份有限公司製，四官能聚環氧丙基胺YH434L: manufactured by Dongdu Chemical Co., Ltd., tetrafunctional polyepoxypropylamine

ONCOAT 1040：Nagase ChemteX股份有限公司製，茀型多官能環氧樹脂ONCOAT 1040: Nagase ChemteX, Inc., 茀-type multifunctional epoxy resin

BL3175：住化Bayer Urethane股份有限公司製，三聚異氰酸酯型封端異氰酸酯BL3175: Made from Bayer Urethane Co., Ltd., a trimeric isocyanate blocked isocyanate

B80T：旭化成Chemicals股份有限公司製，封端異氰酸酯B80T: Asahi Kasei Chemicals Co., Ltd., blocked isocyanate

DICY：二氰二胺DICY: dicyandiamide

CHEMITITE PZ：日本觸媒股份有限公司製，多官能氮雜環丙烷化合物CHEMITITE PZ: Japan Catalyst Co., Ltd., a polyfunctional azacyclopropane compound

RIKACID TMTA-C：新日本理化股份有限公司製，多官能酸酐RIKACID TMTA-C: New Japan Physicochemical Co., Ltd., polyfunctional anhydride

Aronoxetane OXT-121：東亞合成股份有限公司製，1,4-雙{[(3-乙基氧雜環丁烷-3-基)甲氧基]甲基}氧雜環丁烷Aronoxetane OXT-121: manufactured by Toagosei Co., Ltd., 1,4-bis{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane

B-a：四國化成股份有限公司製，苯并化合物Ba: Siguo Huacheng Co., Ltd., benzo Compound

CARBODILITE V-07：日清紡股份有限公司製，聚碳二亞胺化合物CARBODILITE V-07: Made from Nisshinbo Co., Ltd., polycarbodiimide compound

ZISNET DB：三協化成股份有限公司製，2-二丁基胺基-4,6-二巰基-s-三 ZISNET DB: manufactured by Sanxie Chemical Co., Ltd., 2-dibutylamino-4,6-dimercapto-s-three

TD-2131：DIC股份有限公司製，酚酚醛清漆樹脂TD-2131: DIC Co., Ltd., phenol novolac resin

BMI-2300：大和化成工業股份有限公司製，聚苯基甲烷順丁烯二醯亞胺化合物BMI-2300: Dahehua Chemical Industry Co., Ltd., polyphenylmethane maleimide compound

(比較例1至9)(Comparative Examples 1 to 9)

除了將實施例1之含有羧基之改質酯樹脂(A)溶液分別換成比較製造例1至9所得之樹脂溶液以外，皆進行與實施例1相同操作，作成附雙面保護膜之接著片。The same operation as in Example 1 was carried out except that the carboxyl group-containing modified ester resin (A) solution of Example 1 was replaced with the resin solutions obtained in Comparative Production Examples 1 to 9, respectively, to form a double-sided protective film. .

用以下方法評價實施例及比較例所得之接著片的保存安定性、加工安定性、接著強度、銲錫浴耐性、銲錫後接著強度、加濕銲錫浴耐性、絕緣信賴性、耐焊劑性。The storage stability, processing stability, adhesion strength, solder bath resistance, solder adhesion strength, wet solder bath resistance, insulation reliability, and solder resist resistance of the back sheets obtained in the examples and the comparative examples were evaluated by the following methods.

(1)加工安定性(1) Processing stability

將去除保護膜之65mm×65mm大小的接著片夾在厚度為75μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 300H」]與厚度為45μm之敷銅積層板之間，於80℃積層，然後以160℃、1.0MPa的條件進行捲邊(crimping)處理1小時。再來，將此試驗片於160℃熱硬化2小時，作成評價用試驗片。測定此試驗片的捲邊處理前與熱硬化後的接著劑層的面積差，將其作為超出面積而評價加工安定性。該加工安定性係評價捲邊處理時接著層因熱而軟化，引起電路基板位置偏移、配線間的接觸之程度者，以後述基準判斷結果。The 65 mm × 65 mm-sized adhesive sheet with the protective film removed was sandwiched between a polyimide film (DUPNT-TORAY Kapton 300H) having a thickness of 75 μm and a copper-clad laminate having a thickness of 45 μm. The layer was laminated at 80 ° C, and then subjected to crimping treatment at 160 ° C and 1.0 MPa for 1 hour. Then, this test piece was thermally hardened at 160 ° C for 2 hours to prepare a test piece for evaluation. The area difference between the edge of the test piece before the curling treatment and the adhesive layer after the heat curing was measured, and the processing stability was evaluated as the excess area. This processing stability is a result of evaluating the degree of contact between the circuit board position and the contact between the wirings when the bonding layer is softened by heat during the curling process, and the result of the reference determination will be described later.

◎……「超出面積≦100mm2 」◎...... "Exceeding the area ≦100mm 2 "

○……「100mm2 ＜超出面積≦250mm2 」○......"100mm 2 <Out of area ≦250mm 2 ”

△……「250mm2 ＜超出面積≦500mm2 」△..."250mm 2 <Out of area ≦500mm 2 ”

×……「500mm2 ＜超出面積」×..."500mm 2 <out of area"

(2)接著強度(2) subsequent strength

將於加工安定性評價作成之試驗片切成寬度10mm、長度65mm，於23℃相對濕度50%的環境下，以拉伸速度300mm/分鐘進行T揭膜(peel)剝離試驗，測定接著強度(N/cm)。此試驗係評價常溫使用時之接著層的接著強度者，以後述基準判斷結果。The test piece prepared by the evaluation of the stability of the processing was cut into a width of 10 mm and a length of 65 mm, and subjected to a peel peeling test at a tensile speed of 300 mm/min in an environment of a relative humidity of 50% at 23 ° C, and the subsequent strength was measured. N/cm). This test is for evaluating the adhesion strength of the adhesive layer at the time of normal temperature use, and the results of the reference determination will be described later.

◎……「18(N/cm)＜接著強度」◎......"18(N/cm)<continued strength"

○……「12(N/cm)＜接著強度≦18(N/cm)」○..."12(N/cm)<then strength ≦18(N/cm)"

△……「8(N/cm)＜接著強度≦12(N/cm)」△ ... "8 (N / cm) < then strength ≦ 12 (N / cm)"

×……「接著強度≦8(N/cm)」×..."Continuous strength ≦8 (N/cm)"

(3)保存安定性(3) Preservation stability

將於實施例及比較例作成之附雙面保護膜之接著片，於40℃加熱保存3個月後，以上述(1)的條件施予積層、捲邊處理及熱硬化，以與上述(2)相同方法評價接著強度，與未加熱保存之接著片所得之接著強度比較。此試驗係以加熱保存的有無造成的接著強度的差異來評價未硬化狀態的接著層的經時安定性者，經時安定性越良好者未硬化的狀態越安定，施予加熱促進時接著強度降低的較少，經時安定性越差者未硬化的狀態越不安定，加熱促進使硬化反應進行，與不施予加熱促進時相較下接著強度大幅降低。以後述基準判斷該等評價結果。The adhesive sheet with the double-sided protective film prepared in the examples and the comparative examples was heated and stored at 40 ° C for 3 months, and then laminated, crimped, and thermally cured under the above condition (1) to 2) The same method was used to evaluate the subsequent strength, which was compared with the subsequent strength obtained from the unheated storage of the succeeding sheet. In this test, the time stability of the adhesive layer in the uncured state is evaluated by the difference in the strength of the adhesion due to the presence or absence of the heat storage. The more stable the stability is, the more stable the unhardened state is, and the heat is promoted. The decrease is less, and the worse the stability over time, the less stable the unhardened state, and the heating promotes the hardening reaction to proceed, and the strength is greatly lowered as compared with the case where the heating is not applied. The evaluation results are judged based on the criteria described later.

◎……「加熱促進使接著強度完全沒有變化」◎...... "The heating promotes the final strength without any change"

○……「加熱促進使接著強度幾乎沒有變化」○... "The heating promotes almost no change in the strength of the bonding"

△……「加熱促進使接著強度略為降低」△... "heating promotes a slight decrease in the strength of the joint"

×……「加熱促進使接著強度顯著降低」×... "heating promotes a significant decrease in the strength of the bond"

(4)銲錫浴耐性(4) solder bath resistance

將與上述(2)相同得方式切成寬度10mm、長度65mm之試驗片，於260℃的溶融銲錫中，使聚醯亞胺薄膜面與其接觸漂浮1分鐘。其後，以目視觀察試驗片外觀，評價接著劑層的發泡、浮起、剝離等接著異常的有無。此試驗係以外觀評價接觸銲錫時之接著層的熱安定性者，相對於耐熱性良好者在銲錫處理的前後外觀無變化，耐熱性差者在銲錫處理後產生發泡和剝離。以後述基準判斷該等評價結果。A test piece having a width of 10 mm and a length of 65 mm was cut into the same manner as in the above (2), and the polyimide film surface was floated in contact with the molten solder at 260 ° C for 1 minute. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of abnormality such as foaming, floating, peeling, and the like of the adhesive layer was evaluated. In this test, the thermal stability of the adhesive layer in the case of contact soldering was evaluated by the appearance, and the appearance was not changed before and after the soldering treatment with respect to the heat resistance, and the heat resistance was poor, and foaming and peeling occurred after the soldering treatment. The evaluation results are judged based on the criteria described later.

◎……「外觀無變化」◎...... "There is no change in appearance"

○……「觀察到略有微小的發泡」○... "A slight foaming was observed"

△……「觀察到發泡」△...... "Observation of foaming"

×……「觀察到激烈的發泡和剝離」×... "Experienced intense foaming and peeling"

(5)銲錫後接著強度(5) After soldering strength

對於上述(4)之銲錫浴耐性評價後的試驗片用與上述(2)相同方法測定接著強度，比較銲錫處理前的接著強度與銲錫處理後的接著強度。此試驗係以銲錫處理前後之接著強度的變化來評價銲錫接觸時接著層的熱安定性者，相對於耐熱性良好者在銲錫處理的前後接著強度無變化，耐熱性差者在銲錫處理後接著強度顯著降低。以後述基準判斷該等評價結果。The test piece after the evaluation of the solder bath resistance of the above (4) was measured for the adhesive strength in the same manner as in the above (2), and the adhesive strength before the soldering treatment and the bonding strength after the soldering treatment were compared. In this test, the thermal stability of the adhesive layer at the time of solder contact was evaluated by the change in the adhesive strength before and after the soldering treatment, and the strength was not changed before and after the soldering treatment with respect to the heat resistance, and the heat resistance was poor after the soldering treatment. Significantly lower. The evaluation results are judged based on the criteria described later.

◎……「接著強度完全沒有變化」◎...... "There is no change in strength at all."

○……「接著強度幾乎沒有變化」○... "There is almost no change in strength"

△……「接著強度略為降低」△... "The strength is slightly lower"

×……「接著強度顯著降低」×... "The strength is then significantly reduced"

(6)加濕銲錫浴耐性(6) Humidification solder bath resistance

將與上述(2)相同方式切成寬度10mm、長度65mm之試驗片，於40℃、相對濕度90%的環境下，放置96小時使其加濕後，於260℃的溶融銲錫中，使聚醯亞胺薄膜面與其接觸漂浮1分鐘。其後，以目視觀察試驗片外觀，評價接著劑層的發泡、浮起、剝離等接著異常的有無。此試驗係以外觀來評價加濕狀態下接觸銲錫時之接著層熱安定性者，相對於耐濕熱性良好者外觀無變化，耐濕熱性差者在銲錫處理後產生發泡和剝離。以後述基準判斷該等評價結果。The test piece having a width of 10 mm and a length of 65 mm was cut into the same manner as in the above (2), and placed in an environment of 40 ° C and a relative humidity of 90% for 96 hours to be humidified, and then melted in a molten solder at 260 ° C. The quinone imine film surface floated in contact with it for 1 minute. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of abnormality such as foaming, floating, peeling, and the like of the adhesive layer was evaluated. In this test, the thermal stability of the adhesive layer in the case of contact with the solder in the humidified state was evaluated by the appearance, and the appearance was not changed with respect to the heat and humidity resistance, and the heat and humidity resistance was poor, and foaming and peeling occurred after the soldering treatment. The evaluation results are judged based on the criteria described later.

◎……「完全沒有外觀變化」◎...... "There is no change in appearance"

○……「幾乎沒有外觀變化」○... "There is almost no change in appearance"

△……「觀察到發泡」△...... "Observation of foaming"

×……「觀察到激烈發泡和剝離」×... "Experienced intense foaming and peeling"

(7)絕緣信賴性(7) Insulation reliability

去除保護膜之65mm×65mm大小的接著片夾在厚度為25μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 100H」]與於聚醯亞胺上形成銅電路之梳型圖案(導體圖案寬度/間隔寬度=50μm/50μm)印刷電路基板之間，於80℃積層，然後以160℃、1.0MPa的條件進行1小時捲邊處理。再來，將此試驗片於160℃熱硬化2小時，作成評價用試驗片。在溫度130℃、相對濕度85%的環境下將直流電壓50V連續施加100小時於此試驗片的導體電路，測定100小時後的導體間的絕緣電阻值。評價基準同下。The 65 mm × 65 mm-sized back sheet from which the protective film was removed was sandwiched between a polyimide film having a thickness of 25 μm [Kapton 100H manufactured by DU PONT-TORAY Co., Ltd.] and a comb pattern of a copper circuit formed on polyimide. (Conductor pattern width/space width = 50 μm/50 μm) The printed circuit boards were laminated at 80 ° C, and then subjected to a hemming treatment at 160 ° C and 1.0 MPa for 1 hour. Then, this test piece was thermally hardened at 160 ° C for 2 hours to prepare a test piece for evaluation. The conductor circuit of this test piece was continuously applied to a conductor circuit of this test piece for 100 hours under a temperature of 130 ° C and a relative humidity of 85%, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are the same as below.

◎……絕緣電阻值108 Ω以上◎......Insulation resistance value of 10 8 Ω or more

○……絕緣電阻值107 以上未達108 Ω○......Insulation resistance value of 10 7 or more is less than 10 8 Ω

△……絕緣電阻值106 以上未達107 Ω△...Insulation resistance value of 10 6 or more is less than 10 7 Ω

×……絕緣電阻值未達106 Ω×...Insulation resistance value is less than 10 6 Ω

(8)耐焊劑性(8) solder resistance

以乾燥後的膜厚成為30μm的方式將熱硬化性樹脂組成物均勻塗裝於厚度為75μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 300H」]上後乾燥，再來，將此試驗片於160℃熱硬化1小時，作成評價用試驗片。滴下數滴弱活性松香(rosin)系焊劑(日本Alpha Metals股份有限公司製，商品名：RM-615)於此試驗片上後，於260℃的烘箱熱處理3分鐘。從烘箱取出試驗片，以異丙醇擦除焊劑後，由聚醯亞胺上之硬化膜的厚度進行如下述方式之判斷。實用上無問題者為○。The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75 μm [Kapton 300H manufactured by DU PONT-TORAY Co., Ltd.], and dried, and then dried. This test piece was heat-hardened at 160 ° C for 1 hour to prepare a test piece for evaluation. A few drops of weakly active rosin-based flux (manufactured by Alpha Metals Co., Ltd., trade name: RM-615) were dropped on the test piece, and then heat-treated in an oven at 260 ° C for 3 minutes. The test piece was taken out from the oven, and after the flux was wiped with isopropyl alcohol, the thickness of the cured film on the polyimide was judged as follows. Those who have no problem in practical use are ○.

○……膜厚變化未達5μm○......The film thickness change is less than 5μm

△……膜厚變化為5至10μm△... film thickness change is 5 to 10 μm

×……膜厚變化大於10μm×... film thickness variation is greater than 10μm

(9)可撓性(9) Flexibility

以乾燥後的膜厚成為30μm的方式將熱硬化性樹脂組成物均勻塗裝於厚度為75μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 300H」]上後乾燥，再來，將此試驗片於160℃熱硬化1小時，作成評價用試驗片。將評價用試驗片折彎成180度，相同部分往相反側折彎成180度。以下述基準判斷此時塗膜的狀態。The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75 μm [Kapton 300H manufactured by DU PONT-TORAY Co., Ltd.], and dried, and then dried. This test piece was heat-hardened at 160 ° C for 1 hour to prepare a test piece for evaluation. The test piece for evaluation was bent to 180 degrees, and the same portion was bent to 180 degrees on the opposite side. The state of the coating film at this time was judged based on the following criteria.

○……於膜面上沒有看到裂縫(crack)○......No cracks were seen on the film surface.

△……於膜面上看到些許裂縫△... see some cracks on the film surface

×……膜裂開，於膜面上清楚看到裂縫×......The film cracked and the crack was clearly seen on the film surface.

(10)屈曲性(10) Flexibility

以乾燥後的膜厚成為30μm的方式將熱硬化性樹脂組成物均勻塗裝於厚度為75μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 300H」]上後乾燥，再來，將此試驗片於160℃熱硬化1小時，作成評價用試驗片。將評價用試驗片使硬化塗膜面朝向外側折彎成180度，以下述基準評價此時塗膜的狀態。The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75 μm [Kapton 300H manufactured by DU PONT-TORAY Co., Ltd.], and dried, and then dried. This test piece was heat-hardened at 160 ° C for 1 hour to prepare a test piece for evaluation. The test piece for evaluation was bent to 180 degrees toward the outside, and the state of the film at this time was evaluated by the following criteria.

○……於膜面上沒有看到裂縫(crack)○......No cracks were seen on the film surface.

△……於膜面上看到些許裂縫△... see some cracks on the film surface

×……膜裂開，於膜面上清楚看到裂縫×......The film cracked and the crack was clearly seen on the film surface.

(11)密著性(11) Adhesion

以乾燥後的膜厚成為30μm的方式將熱硬化性樹脂組成物均勻塗裝於厚度為75μm之聚醯亞胺薄膜[DU PONT-TORAY(股)製「Kapton 300H」]上後乾燥，再來，將此試驗片於160℃熱硬化1小時，作成評價用試驗片。以JIS K5400為基準，於硬化塗膜上作出100個1mm×1mm大小的方格，藉由CELLOTAPE(註冊商標)進行揭膜試驗。觀察方格的剝離狀態，以下述基準評價。The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75 μm [Kapton 300H manufactured by DU PONT-TORAY Co., Ltd.], and dried, and then dried. This test piece was heat-hardened at 160 ° C for 1 hour to prepare a test piece for evaluation. Based on JIS K5400, 100 squares of 1 mm × 1 mm size were made on the hardened coating film, and a film peeling test was performed by CELLOTAPE (registered trademark). The peeling state of the square was observed and evaluated on the basis of the following criteria.

○……無剝離○......no peeling

△……20%以下的方格剝離△... 20% or less of the square peeling

×……21%以上的方格剝離×... 21% or more of the square peeling

評價結果表示於下述表5。The evaluation results are shown in Table 5 below.

關於表5，如同從實施例和比較例所得知，比較例1至4、7、9所用之樹脂，在生成含有羧基之酯樹脂(c)時未使用選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)，因此絕緣信賴性、銲錫後接著強度、加濕銲錫浴耐性顯著惡化。With respect to Table 5, as seen from the examples and the comparative examples, the resins used in Comparative Examples 1 to 4, 7, and 9 did not use an alicyclic polybasic acid anhydride and aromatics in the formation of the carboxyl group-containing ester resin (c). Since at least one of the polybasic acid anhydrides contains the acid anhydride group-containing compound (b), the insulating reliability, the solder post-external strength, and the humidifying solder bath resistance are remarkably deteriorated.

又，比較例5至7所用之樹脂，在生成含有羧基之改質酯樹脂(A)時未使用選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)，因此絕緣信賴性、銲錫後接著強度、加濕銲錫浴耐性顯著惡化。Further, in the resins used in Comparative Examples 5 to 7, when the modified ester resin (A) having a carboxyl group was produced, at least one acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride was not used. Therefore, the reliability of the insulation, the strength after soldering, and the resistance of the humidifying solder bath are remarkably deteriorated.

另一方面，實施例中使用選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)，因此不止改善這3種物性，並且全部的物性中亦保持平衡並得到良好的結果。認為此係因下述之本發明的特徵造成很大的影響：前述多元醇化合物(a)與選自脂環式多元酸酐及芳香族多元酸酐之含有酸酐基之至少一種化合物(b)進行反應而得到之含有羧基之酯樹脂(c)中的酯鍵基經由大量取代基保護，以及含有側鏈羥基之改質酯樹脂(e)與選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)進行反應而成之含有羧基之改質酯樹脂(A)中的酯鍵基經由大量取代基保護。On the other hand, in the examples, at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride is used, and therefore, the three physical properties are not only improved, but also the balance is obtained in all the physical properties. Good results. It is considered that this is greatly affected by the characteristics of the present invention described below: the polyol compound (a) is reacted with at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. And the ester bond group in the obtained carboxyl group-containing ester resin (c) is protected by a large number of substituents, and the modified ester resin (e) having a side chain hydroxyl group and at least one selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride The ester bond group in the carboxyl group-containing modified ester resin (A) obtained by reacting the acid anhydride group-containing compound (b) is protected by a large number of substituents.

再者，由製造例得到之含有羧基之改質酯樹脂(A)不僅保持銲錫浴耐性並且顯示高接著強度。此係因出發原料中使用多元醇化合物(a)與選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)，相較於以往的以二元酸為原料之聚酯骨架作為主鏈使用之樹脂，可賦予源自多元醇化合物(a)之可撓性和加工性等。又，認為此係因為即使酯鍵基經由大量取代基保護，源自酯骨架的極性仍有作用。Further, the carboxyl group-containing modified ester resin (A) obtained in the production example not only maintains solder bath resistance but also exhibits high adhesion strength. This is because the polyol compound (a) and the compound (b) containing at least one acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride are used as starting materials, and the dibasic acid is used as a raw material. The polyester skeleton is a resin used as a main chain, and can impart flexibility, workability, and the like derived from the polyol compound (a). Further, this is considered to be because the polarity derived from the ester skeleton still functions even if the ester bond group is protected by a large number of substituents.

如同實施例和比較例所得知，實施例中使用選自脂環式多元酸酐及芳香族多元酸酐之至少一種含有酸酐基之化合物(b)合成樹脂，全部的物性皆顯示良好的結果。再者，藉由添加熱硬化助劑(C)，可在不降低接著強度、絕緣信賴性等之下，並且提昇加工性和加濕銲錫耐性、銲錫後的接著強度。認為此係因酯鍵基經由大量取代基保護導致耐水解性和熱硬化助劑(C)的相乘效果。As is understood from the examples and the comparative examples, in the examples, at least one compound (b) containing an acid anhydride group-containing synthetic resin selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride was used, and all of the physical properties showed good results. Further, by adding the thermosetting assistant (C), it is possible to improve the workability, the wet solder resistance, and the adhesion strength after soldering without lowering the bonding strength, the insulating reliability, and the like. It is considered that this is caused by the hydrolysis resistance and the synergistic effect of the thermosetting assistant (C) due to the protection of the ester bond group via a large number of substituents.

Claims (7)

一種熱硬化性樹脂組成物，其包含：(A)含有羧基之改質酯樹脂；(B)選自含有環氧基之化合物、含有異氰酸酯基之化合物、及含有封端化異氰酸酯基之化合物所成之群組之至少一種化合物；以及(C)熱硬化助劑；(A)含有羧基之改質酯樹脂係由下述步驟製成者：使(a)多元醇化合物與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應而生成(c)含有羧基之酯樹脂；使前述(c)含有羧基之酯樹脂與(d)於1分子中具有至少2個環氧基之環氧化合物進行反應而生成(e)含有側鏈羥基之改質酯樹脂；再來，使(e)含有側鏈羥基之改質酯樹脂與(b)選自脂環式多元酸酐及芳香族多元酸酐的至少一種含有酸酐基之化合物進行反應；前述(C)熱硬化助劑係選自氮雜環丙烷化合物、含有碳二亞胺基之化合物、苯并化合物、酚樹脂、咪唑類及二氰二胺所成之群組之至少一種。A thermosetting resin composition comprising: (A) a modified ester resin containing a carboxyl group; (B) a compound selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound a group of at least one compound; and (C) a thermosetting assistant; (A) a carboxylate-containing modified ester resin produced by the steps of: (a) a polyol compound and (b) selected from The at least one acid anhydride group-containing compound of the alicyclic polybasic acid anhydride and the aromatic polybasic acid anhydride is reacted to form (c) a carboxyl group-containing ester resin; and the (c) carboxyl group-containing ester resin and (d) have one molecule At least two epoxy-based epoxy compounds are reacted to form (e) a modified ester resin containing a side chain hydroxyl group; and further, (e) a modified ester resin containing a side chain hydroxyl group and (b) is selected from the group consisting of The at least one compound containing an acid anhydride group of the cyclic polybasic acid anhydride and the aromatic polybasic acid anhydride is reacted; and the (C) thermal curing assistant is selected from the group consisting of an aziridine compound, a compound containing a carbodiimide group, and a benzo compound. At least one of the group consisting of a compound, a phenol resin, an imidazole, and a dicyandiamide. 如申請專利範圍第1項所述之熱硬化性樹脂組成物，其中，前述(a)多元醇化合物係選自聚酯多元醇、聚碳酸酯多元醇、聚醚多元醇、聚丁二烯多元醇及聚矽氧烷多元醇所成之群組之至少一種化合物。 The thermosetting resin composition according to claim 1, wherein the (a) polyol compound is selected from the group consisting of polyester polyols, polycarbonate polyols, polyether polyols, and polybutadiene polyols. At least one compound of the group formed by an alcohol and a polyoxyalkylene polyol. 如申請專利範圍第1項所述之熱硬化性樹脂組成物，其中，前述(b)含有酸酐基之化合物係選自甲基四氫酞酸酐、四氫酞酸酐、六氫酞酸酐、甲基六氫酞酸酐、納迪克酸酐、甲基納迪克酸酐、氫化甲基納迪克酸酐、苯乙烯基內苯乙烯四氫酞酸酐、3,6-內亞甲基四氫酞酸酐、甲基內亞甲基四氫酞酸酐、三烷基四氫酞酸酐、酞酸酐、四溴酞酸酐、苯偏三酸酐及焦蜜石酸二酐所成之群組之至少一種化合物。 The thermosetting resin composition according to claim 1, wherein the (b) acid anhydride group-containing compound is selected from the group consisting of methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl group. Hexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, styrylstyrene tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylene At least one compound of the group consisting of methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, and pyrogallate dianhydride. 如申請專利範圍第1項所述之熱硬化性樹脂組成物，其中，前述(A)含有羧基之改質酯樹脂的酸價係1至100mgKOH/g。 The thermosetting resin composition according to claim 1, wherein the (A) carboxyl group-containing modified ester resin has an acid value of from 1 to 100 mgKOH/g. 如申請專利範圍第1項所述之熱硬化性樹脂組成物，其中，前述(A)含有羧基之改質酯樹脂的重量平均分子量係5000至500000。 The thermosetting resin composition according to claim 1, wherein the (A) carboxyl group-containing modified ester resin has a weight average molecular weight of 5,000 to 500,000. 一種硬化物，其係藉由加熱使申請專利範圍第1項至第5項中任一項所述之熱硬化性樹脂組成物硬化而得到者。 A cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 5 by heating. 一種印刷配線板，其具有由申請專利範圍第6項所述之硬化物所成之層。A printed wiring board having a layer formed of the cured product described in claim 6 of the patent application.
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