TW201509988A - Carboxyl group-containing polyester and thermosetting resin composition containing the same - Google Patents

Carboxyl group-containing polyester and thermosetting resin composition containing the same Download PDF

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TW201509988A
TW201509988A TW103121135A TW103121135A TW201509988A TW 201509988 A TW201509988 A TW 201509988A TW 103121135 A TW103121135 A TW 103121135A TW 103121135 A TW103121135 A TW 103121135A TW 201509988 A TW201509988 A TW 201509988A
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resin composition
mass
carboxyl group
group
thermosetting resin
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TW103121135A
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Ryosuke Kanda
Tomohiro Aoyama
Tomoharu Kurita
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Toyo Boseki
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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
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate 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
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

Provided is a carboxyl group-containing polyester capable of forming a cured product having properties that can simultaneously satisfy thermal curability, long-term reliability, flexibility, plating resistance and copper foil coherency. The carboxyl group-containing polyester is characterized in that the number average molecular weight of which is more than 10,000 and less than 50,000, the acid value of resin is more than 1,200 equivalent weight/106g. Further, it is characterized in that a polycarbonate diol raw material comprises a plural kind of an alkylene chain formed from copolymerization of at least 2 kinds of diol raw materials, and has the number average molecular weight of 700-2,300.

Description

含羧基聚酯及含它之熱硬化性樹脂組成物Carboxyl group-containing polyester and thermosetting resin composition containing the same

本發明係關於一種能夠提供適用於汽車零件、電化製品等之印刷電路基板等的硬化被膜之熱硬化性樹脂組成物、及可用於它之含羧基聚酯。The present invention relates to a thermosetting resin composition capable of providing a cured film suitable for use in a printed circuit board or the like of an automobile part, an electrochemical product, or the like, and a carboxyl group-containing polyester which can be used therefor.

向來已知道的用以形成以FPC(Flexible Printed Circuits)、COF(Chip On Film)、TAB(Tape Automated Bonding)等為代表的撓性配線電路的表面保護膜之手段，其係有在將被稱為覆蓋層薄膜之聚醯亞胺薄膜沖打出與相合的圖案之模具時，使用接合劑貼附的手法、或者藉由網版印刷法來塗布賦與可撓性之紫外線硬化型、或熱硬化型的樹脂組成物塗料(paste)的手法。在此等之中，樹脂組成物之網版印刷法，因為作業性優良，所以一般可被使用於TAB、COF用途。A means for forming a surface protective film of a flexible wiring circuit represented by FPC (Flexible Printed Circuits), COF (Chip On Film), TAB (Tape Automated Bonding), etc., which is known as When a polyimine film of a cover film is punched with a mold of a matching pattern, a method of attaching with a bonding agent, or a screen printing method for coating a flexible ultraviolet curing type, or heat curing is used. Type resin composition paint method. Among these, the screen printing method of a resin composition is generally used for TAB and COF because it is excellent in workability.

此等多半是以經導入有丁二烯骨架、聚碳酸酯二醇骨架、矽氧烷骨架、長鏈脂肪族骨架等之柔軟成分的樹脂為主成分，藉以達到表面保護膜所要求的耐熱特性(長期信賴性可靠性、耐鍍敷性)、與互為抵消關係之柔軟特性(可撓性)間兩者兼顧之目標。Most of these are based on a resin in which a soft component such as a butadiene skeleton, a polycarbonate diol skeleton, a decane skeleton, or a long-chain aliphatic skeleton is introduced, thereby achieving the heat resistance characteristics required for the surface protective film. (long-term reliability reliability, plating resistance), and softness (flexibility) that cancel each other out.

然而，近年來，隨著電子機器之輕量小型化，撓性基板也往間距微細化邁進發展，對於覆蓋塗布(over coat)之樹脂組成物亦要求更高度的長期絕緣信賴性。關於長期絕緣信賴性之改良，雖然通常是藉由使樹脂組成物之極性成為低極性化來達成；在另一方面，目前的現況是藉由降低在樹脂組成物、與被覆材之銅箔間作動的分子間力，尚不能夠來達到與銅箔密接性間之兩者並立之功效。However, in recent years, with the miniaturization and miniaturization of electronic equipment, the flexible substrate has progressed toward a finer pitch, and a higher-temperature long-term insulation reliability has been required for an overcoat resin composition. The improvement of long-term insulation reliability is generally achieved by making the polarity of the resin composition low-polarized; on the other hand, the current state of the art is reduced by the resin composition and the copper foil of the coated material. The intermolecular force of action is not yet able to achieve the synergy between the two and the copper foil.

就長期絕緣信賴性優異的樹脂組成物而論，例如，已經有如專利文獻1這樣的報告指出一種聚胺基甲酸酯硬化物，其係由滿足 (i)數量平均分子量為500~50,000、(ii)在骨架中具有碳數為8以上18以下之伸烷基、(iii)在兩末端具有羥基之低極性聚碳酸酯二醇、與為使之具有羧基用的能夠與熱硬化劑形成高度的熱交聯構造之2,2-二羥甲基丁酸(DMBA)進行共聚合而成。然而，由於主成分之聚胺基甲酸酯的極性低，所以會有樹脂組成物與被覆材(銅箔)所形成的分子間力減低，銅箔密接性惡化不佳之問題；特別是在對於要求耐鍍敷性的用途上，更是會有鍍敷液從基材與前述聚胺基甲酸酯硬化物間界面滲入、聚胺基甲酸酯硬化物在鍍敷處理後剝離之問題。In the case of a resin composition excellent in long-term insulation reliability, for example, a report such as Patent Document 1 has indicated a cured polyurethane which satisfies (i) a number average molecular weight of 500 to 50,000, ( Ii) a low-polarity polycarbonate diol having a carbon number of 8 or more and 18 or less in the skeleton, (iii) a low-polarity polycarbonate diol having a hydroxyl group at both terminals, and a height capable of forming a carboxyl group for use with a thermosetting agent The thermal crosslinked structure of 2,2-dimethylolbutanoic acid (DMBA) is copolymerized. However, since the polar component of the main component has a low polarity, there is a problem that the intermolecular force formed by the resin composition and the covering material (copper foil) is lowered, and the adhesion of the copper foil is not deteriorated; in particular, In the application for plating resistance, there is a problem that the plating solution penetrates from the interface between the substrate and the cured polyurethane, and the cured polyurethane is peeled off after the plating treatment.

就在主鏈具有羧基之聚合物而論，其他如專利文獻2，亦對於由將含有四羧酸二酐末端的醯亞胺寡聚物、與聚碳酸酯二醇予以酯化而成的含羧基聚醯亞胺進行了研究檢討。In the case of a polymer having a carboxyl group in the main chain, the other is as disclosed in Patent Document 2, and is also obtained by esterifying a quinone imine oligomer containing a terminal of a tetracarboxylic dianhydride with a polycarbonate diol. Carboxypolyimine was reviewed for research.

同樣地，對於如專利文獻3所述之四羧酸二酐、與只由1,6-己二醇所聚碳酸酯化的聚碳酸酯二醇之羥基予以酯化而成的含羧基聚酯，已有報告指出：其一部分是樹脂酸價為1200當量/106 g以上的高酸價含羧基聚酯樹脂。然而，當樹脂的數量平均分子量為低到10000以下時，由於具備只有1種類的伸烷基之聚碳酸酯二醇，使得樹脂的結晶性更進一步地提高，以致會有阻焊劑硬化物的可撓性降低之問題。Similarly, a carboxyl group-containing polyester obtained by esterifying a tetracarboxylic dianhydride as described in Patent Document 3 and a hydroxyl group of a polycarbonate diol which is only polycarbonate-derived from 1,6-hexanediol It has been reported that a part thereof is a high acid value carboxyl group-containing polyester resin having a resin acid value of 1,200 equivalents/10 6 g or more. However, when the number average molecular weight of the resin is as low as 10,000 or less, since the polycarbonate diol having only one type of alkylene group is provided, the crystallinity of the resin is further improved, so that the solder resist can be cured. The problem of reduced flexibility.

此外，對於如專利文獻4所述之四羧酸二酐、與含磷二醇所聚碳酸酯化的聚碳酸酯二醇的羥基予以酯化而成的含羧基聚酯，則會有因含磷二醇之加氫分解而使得長期絕緣信賴性減低、由於樹脂的數量平均分子量為低到10000以下而導致可撓性不足之問題。 《先前技術文獻》 〈專利文獻〉Further, the tetracarboxylic dianhydride described in Patent Document 4 and the carboxyl group-containing polyester obtained by esterifying a hydroxyl group of a polycarbonate diol polycarbonateized with a phosphorus-containing diol may contain The hydrodecomposition of the phosphorus diol causes a decrease in long-term insulation reliability, and the problem that the flexibility is insufficient due to the number average molecular weight of the resin being as low as 10,000 or less. "Previous Technical Literature" <Patent Literature>

〈專利文獻1〉日本專利第4879663號公報 〈專利文獻2〉國際公開第2012/165457號手冊 〈專利文獻3〉日本特開2010-13527號公報 〈專利文獻4〉日本特開2010-13528號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No.

《發明所欲解決之課題》"The subject to be solved by the invention"

本發明係有鑑於如前述之習用技術的現狀而創新構思而完成者，其目的在於提供一種可顯示做為電子材料周邊的接合劑或塗布劑之優異的熱硬化性之熱硬化性樹脂組成物、以及一種可用於它之含羧基聚酯。此外，目的亦在於提供一種除了由此類的熱硬化性樹脂組成物所得到的可撓性外，銅箔密接性、長期絕緣信賴性、及耐鍍敷性亦均優異的硬化被膜。 《解決課題之方法》The present invention has been made in view of the current state of the art of the prior art, and an object of the present invention is to provide an excellent thermosetting thermosetting resin composition which can exhibit an adhesive or a coating agent as a periphery of an electronic material. And a carboxyl-containing polyester which can be used for it. In addition, it is an object of the present invention to provide a cured film which is excellent in copper foil adhesion, long-term insulation reliability, and plating resistance in addition to the flexibility obtained from such a thermosetting resin composition. "Methods for Solving the Problem"

本發明人等為了達成上述目的而潛心刻意反復研究的結果，發現藉由將四羧酸二酐與聚碳酸酯二醇予以酯化，能夠提供一種含有高濃度羧基之聚酯樹脂。再者，亦發現由該聚酯樹脂與熱硬化劑所組合而成的熱硬化性樹脂組成物顯示出做為電子材料周邊的接合劑或塗布劑之良好的熱硬化性；更進一步發現由該熱硬化性樹脂組成物所得到的硬化被膜，除了可撓性外，銅箔密接性、長期絕緣信賴性、及耐鍍敷性均是優異的。The inventors of the present invention have deliberately and repeatedly studied in order to achieve the above object, and found that a polyester resin containing a high concentration of a carboxyl group can be provided by esterifying a tetracarboxylic dianhydride with a polycarbonate diol. Further, it has been found that the thermosetting resin composition obtained by combining the polyester resin and the thermosetting agent exhibits excellent thermosetting properties as a bonding agent or a coating agent around the electronic material; In addition to flexibility, the cured film obtained by the thermosetting resin composition is excellent in adhesion to copper foil, long-term insulation reliability, and plating resistance.

即，本發明為具有以下(1)~(9)之構成。 (1) 具有以下 (a)~(d)的特徴之含羧基聚酯： (a) 具有一般式[I]之重複構造；R1 及R2 分別為以下之(i)~(ii)； (i) R1 係由從四羧酸二酐除去酸酐基而得之有機基，其也可以含有取代基、具有碳數1~30的芳香族基、脂環族基、脂肪族基、或雜環之基； (ii) R2 係由從聚碳酸酯二醇除去羥基而得之有機基，但該聚碳酸酯二醇具有複數種的伸烷基，該聚碳酸酯二醇的數量平均分子量為700~2300； (b) 數量平均分子量為超過10000且在50000以下； (c) 樹脂酸價為1200當量/106 g以上； (d) 在含羧基聚酯中之一般式[I]的重複構造之含有率為68質量%以上。 (2) 如(1)所記載之含羧基聚酯，特徵在於：其中前述聚碳酸酯二醇為以下(i)~(iii)之任一種； (i)      二醇成分為由3-甲基-1,5-戊二醇、與1,6-己二醇構成之共聚合聚碳酸酯二醇； (ii) 二醇成分為由1,5-戊二醇與1,6-己二醇、構成之共聚合聚碳酸酯二醇； (iii) 二醇成分為由2-甲基-1,8-辛二醇、與1,9-壬二醇構成之共聚合聚碳酸酯二醇。 (3) 一種熱硬化性樹脂組成物，特徵在於：其為含有如(1)或(2)所記載之含羧基聚酯、與具有環氧乙烷環之化合物。 (4) 如(3)所記載之熱硬化性樹脂組成物，特徵在於：其中具有環氧乙烷環之化合物為含有苯酚酚醛骨架或甲酚酚醛骨架之環氧化合物。 (5) 如(3)或(4)所記載之熱硬化性樹脂組成物，特徵在於：其中相對於100質量份之含羧基聚酯而言，所摻混的具有環氧乙烷環之化合物為40質量份以上90質量份以下。 (6) 如(3)至(5)中任一項所記載之熱硬化性樹脂組成物，特徵在於：其中熱硬化性樹脂組成物的總固態成分中所含之一般式[I]的重複構造之含有率為40質量%以上71質量%以下。 (7) 一種被膜形成材料，特徵在於：其係含有如(3)至(6)中任一項所記載之熱硬化性樹脂組成物。 (8) 一種阻焊劑，特徵在於：其係含有如(3)至(6)中任一項所記載之熱硬化性樹脂組成物。 (9) 一種硬化被膜，特徵在於：其係由將如(3)至(6)中任一項所記載之熱硬化性樹脂組成物、如(7)所記載之被膜形成材料、或如(8)所記載之阻焊劑予以熱硬化而得。 《發明效果》That is, the present invention has the following constitutions (1) to (9). (1) a carboxyl group-containing polyester having the following characteristics (a) to (d): (a) having a repeating structure of the general formula [I]; and R 1 and R 2 are each of the following (i) to (ii); (i) R 1 is an organic group obtained by removing an acid anhydride group from a tetracarboxylic dianhydride, and may also have a substituent, an aromatic group having 1 to 30 carbon atoms, an alicyclic group, an aliphatic group, or a heterocyclic group; (ii) R 2 is an organic group obtained by removing a hydroxyl group from a polycarbonate diol, but the polycarbonate diol has a plurality of alkylene groups, and the number of the polycarbonate diols is average The molecular weight is 700~2300; (b) the number average molecular weight is more than 10,000 and less than 50,000; (c) the resin acid value is 1200 equivalent/10 6 g or more; (d) the general formula [I] in the carboxyl group-containing polyester The content of the repeating structure is 68% by mass or more . (2) The carboxyl group-containing polyester according to (1), wherein the polycarbonate diol is any one of the following (i) to (iii); (i) the diol component is 3-methyl -1,5-pentanediol, a copolymerized polycarbonate diol composed of 1,6-hexanediol; (ii) a diol component consisting of 1,5-pentanediol and 1,6-hexanediol And constituting the copolymerized polycarbonate diol; (iii) the diol component is a copolymerized polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol. (3) A thermosetting resin composition comprising a carboxyl group-containing polyester as described in (1) or (2) and a compound having an oxirane ring. (4) The thermosetting resin composition according to (3), wherein the compound having an oxirane ring is an epoxy compound containing a phenol novolac skeleton or a cresol novolak skeleton. (5) The thermosetting resin composition according to (3) or (4), wherein the compound having an oxirane ring is blended with respect to 100 parts by mass of the carboxyl group-containing polyester It is 40 parts by mass or more and 90 parts by mass or less. (6) The thermosetting resin composition according to any one of (3) to (5), wherein the repeating of the general formula [I] contained in the total solid content of the thermosetting resin composition The content of the structure is 40% by mass or more and 71% by mass or less. (7) A film forming material comprising the thermosetting resin composition according to any one of (3) to (6). (8) A solder resist comprising the thermosetting resin composition according to any one of (3) to (6). (9) A thermosetting resin composition according to any one of (3) to (6), wherein the film forming material is as described in (7), or 8) The solder resist described is obtained by thermal hardening. Invention effect

本發明之含羧基聚酯，由於在主鏈中具有羧基，所以能夠藉由與熱硬化劑組合而形成高度的交聯構造，並顯示出優異的熱硬化性。更且，由此種熱硬化性樹脂組成物所得的硬化被膜，除了可撓性為優異以外，其銅箔密接性、長期絕緣信賴性、及耐鍍敷性亦皆優異。從而，能夠非常適合使用於光阻印墨或接合劑、使用該等之汽車零件、電化製品等之印刷電路基板等。Since the carboxyl group-containing polyester of the present invention has a carboxyl group in the main chain, it can form a highly crosslinked structure by combining with a thermosetting agent, and exhibits excellent thermosetting property. In addition, the cured film obtained from such a thermosetting resin composition is excellent in flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance. Therefore, it can be suitably used for a photoresist ink or an adhesive, a printed circuit board using such an automobile part, an electrochemical product, or the like.

《用以實施發明之形態》"Forms for Implementing Inventions"

以下，詳細地說明本發明之實施形態。Hereinafter, embodiments of the present invention will be described in detail.

本發明之含羧基聚酯係具有以下(a)~(d)之特徴。 (a) 具有一般式[I]之重複構造，R1 及R2 分別為以下之(i)~(ii)； (i)  R1 為由四羧酸二酐除去酸酐基而得的有機基，也可以含有取代基，具有碳數1~30之芳香族基、脂環族基、脂肪族基、或雜環之基； (ii)  R2 為由聚碳酸酯二醇除去羥基而得的有機基，但該聚碳酸酯二醇為具有複數種的伸烷基；該聚碳酸酯二醇之數量平均分子量為700~2300； (b) 數量平均分子量為超過10000且在50000以下； (c) 樹脂酸價為1200當量/106 g以上； (d) 在含羧基聚酯中之一般式[I]的重複構造之含有率為68質量%以上；。The carboxyl group-containing polyester of the present invention has the following characteristics (a) to (d). (a) having a repeating structure of the general formula [I], wherein R 1 and R 2 are each of the following (i) to (ii); (i) R 1 is an organic group obtained by removing an acid anhydride group from a tetracarboxylic dianhydride. Further, it may have a substituent, and has an aromatic group, an alicyclic group, an aliphatic group or a heterocyclic group having 1 to 30 carbon atoms; (ii) R 2 is obtained by removing a hydroxyl group from a polycarbonate diol. An organic group, but the polycarbonate diol is a plurality of alkylene groups; the polycarbonate diol has a number average molecular weight of 700 to 2300; (b) the number average molecular weight is more than 10,000 and less than 50,000; The resin acid value is 1200 equivalents/10 6 g or more; (d) the content of the repeating structure of the general formula [I] in the carboxyl group-containing polyester is 68% by mass or more; .

以下，詳細地說明本發明之含羧基聚酯。Hereinafter, the carboxyl group-containing polyester of the present invention will be described in detail.

＜含羧基聚酯(A)＞ 本發明之含羧基聚酯(A)係藉由將四羧酸二酐(C)之酸酐基、與聚碳酸酯二醇(D)之羥基予以酯化合成而得的。 再者，利用將(A)成分、與如含有環氧乙烷環的化合物(B)這種的熱硬化劑加以組合所形成的組成物，能夠在低溫形成高度的交聯構造，並顯示出優異的熱硬化性。此外，由(A)成分和(B)成分組合而成的熱硬化性樹脂組成物所得到之硬化被膜係能夠非常適用於要求具有可撓性、銅箔密接性、長期絕緣信賴性、及耐鍍敷性的電子材料周邊等。<Carboxyl group-containing polyester (A)> The carboxyl group-containing polyester (A) of the present invention is synthesized by esterifying an acid anhydride group of a tetracarboxylic dianhydride (C) with a hydroxyl group of a polycarbonate diol (D). And got it. Further, a composition obtained by combining a component (A) and a thermosetting agent such as a compound (B) containing an oxirane ring can form a highly crosslinked structure at a low temperature and exhibit Excellent thermosetting properties. In addition, the cured film obtained from the thermosetting resin composition in which the component (A) and the component (B) are combined can be suitably used for flexibility, copper foil adhesion, long-term insulation reliability, and resistance. Plating of electronic materials, etc.

＜四羧酸二酐(C)＞ 四羧酸二酐(C)並末特別加以限定，然而，舉例來說，例如，其可以是均苯四甲酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,3,2’,3’-二苯甲酮四羧酸二酐、2,3,3’,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯基四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、4,4’-氧二酞酸二酐、2,2-雙(3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-二羧基苯基)丙烷二酐、1,1-雙(2,3-二羧基苯基)乙烷二酐、1,1-雙(3,4-二羧基苯基)乙烷二酐、雙(2,3-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)甲烷二酐、雙(3,4-二羧基苯基)碸二酐、3,4,9,10-苝四羧酸二酐、雙(3,4-二羧基苯基)醚二酐、1,2,5,6-萘四羧酸二酐、2,3,6,7-萘四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、菲-1,8,9,10-四羧酸二酐、吡嗪-2,3,5,6-四羧酸二酐、噻吩-2,3,4,5-四羧酸二酐、雙(3,4-二羧基苯基)二甲基矽烷二酐、雙(3,4-二羧基苯基)二苯基矽烷二酐、1,4-雙(3,4-二羧基苯基二甲基矽烷基)苯二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二環己烷二酐、p-苯基雙(偏苯三酸單酯酸酐)、伸乙基四羧酸二酐、1,2,3,4-丁烷四羧酸二酐、十氫萘-1,4,5,8-四羧酸二酐、4,8-二甲基-1,2,3,5,6,7-六氫萘-1,2,5,6-四羧酸二酐、環戊烷-1,2,3,4-四羧酸二酐、吡啶-2,3,4,5-四羧酸二酐、1,2,3,4-環丁烷四羧酸二酐、雙(外型-二環[2,2,1]庚烷-2,3-二羧酸酐)碸、二環-(2,2,2)-辛(7)-烯-2,3,5,6-四羧酸二酐、2,2-雙(3,4-二羧基苯基)六氟丙酸二酐、2,2-雙[4-(3,4-二羧基苯氧基)苯基]六氟丙酸二酐、4,4’ -雙(3,4-二羧基苯氧基)二苯基硫酸二酐、1,4-雙(2-羥基六氟異丙基)苯雙(偏苯三酸酐)、1,3-雙(2-羥基六氟異丙基)苯雙(偏苯三酸酐)、5-(2,5-二氧四氫呋喃基)-3-甲基-3-環己烷-1,2-二羧酸酐、四氫呋喃-2,3,4,5-四羧酸二酐、1,3,3a,4,5,9b-六氫-5(四氫-2,5-二氧-3-呋喃基)萘并[1,2-c]呋喃-1,3-二酮、乙二醇雙(偏苯三酸酐)(「乙二醇雙脫氫偏苯三酸」或者也稱為「TMEG」)等。<Tetracarboxylic dianhydride (C)> The tetracarboxylic dianhydride (C) is particularly limited, but, for example, it may be pyromellitic dianhydride, 3, 3', 4, 4 '-benzophenone tetracarboxylic dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid Anhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 4,4'-oxydicarboxylic acid Anhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3- Dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, double (3,4 -dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) Ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene- 2,3,4,5-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethyl phthalane dianhydride, double (3, 4-dicarboxyphenyl)diphenylnonane dianhydride, 1,4-bis(3,4-dicarboxyphenyldimethyldimethylalkyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyl) Phenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylbis(trimellitic acid monoester anhydride), ethyltetracarboxylic dianhydride, 1,2, 3,4-butane tetracarboxylic dianhydride, decalin-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyridine-2,3,4,5-tetracarboxylic acid Anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride) hydrazine, bicyclo-( 2,2,2)-octyl (7)-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropionic acid dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropionic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfate Dihydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzene bis(trimellitic anhydride), 5-(2, 5-dihydrotetrahydrofuranyl-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5 (tetrahydro-2) ,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(trimellitic anhydride) ("ethylene glycol didehydrotrimellitic acid" or Also known as "TMEG").

較佳者為(C)成分是乙二醇雙(偏苯三酸酐)(TMEG)、3,3’,4,4’-二苯基四羧酸二酐(BPDA)、均苯四甲酸二酐(PMDA)、3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)、4,4’-氧二酞酸二酐(ODPA)。Preferably, the component (C) is ethylene glycol bis(trimellitic anhydride) (TMEG), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), pyromellitic dianhydride (PMDA) ), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic acid dianhydride (ODPA).

此等之(C)成分係可以單獨使用，或者也可以混合2種以上來使用。These (C) components may be used singly or in combination of two or more.

＜聚碳酸酯二醇(D)＞ 聚碳酸酯二醇(D)的數量平均分子量為700~2300。數量平均分子量較佳為800~2200，更佳為900~2100。由於在(D)成分之數量平均分子量為小於上述範圍的情況，則來自含羧基聚酯中之聚碳酸酯的伸烷基鏈之質量比例就減少，硬化被膜之可撓性就減低；當超過上述範圍時，則含羧基聚酯的酸價就減少，硬化被膜的交聯密度就降低，因而不理想。 聚碳酸酯二醇(D)的數量平均分子量之測定，其係可以四氫呋喃來溶解及/或稀釋(D)成分而使得樹脂濃度成為0.5質量%左右，以孔徑0.5μm的聚四氟乙烯製薄膜濾紙過濾得到之物做為測定用試料，以四氫呋喃為移動相，並藉由以示差折射計為偵測器之凝膠滲透層析儀(GPC)來進行。流速設定為1mL/分、管柱溫度設定為30℃。管柱為使用昭和電工製KF-802、804L、806L。分子量標準方面，其係可以使用單分散聚苯乙烯。<Polycarbonate diol (D)> The polycarbonate diol (D) has a number average molecular weight of 700 to 2,300. The number average molecular weight is preferably from 800 to 2,200, more preferably from 900 to 2,100. Since the number average molecular weight of the component (D) is less than the above range, the mass ratio of the alkyl chain derived from the polycarbonate in the carboxyl group-containing polyester is decreased, and the flexibility of the cured film is reduced; In the above range, the acid value of the carboxyl group-containing polyester is decreased, and the crosslinking density of the cured film is lowered, which is not preferable. The measurement of the number average molecular weight of the polycarbonate diol (D) by dissolving and/or diluting the component (D) with tetrahydrofuran so that the resin concentration is about 0.5% by mass, and the film of polytetrafluoroethylene having a pore diameter of 0.5 μm The filter paper was filtered as a sample for measurement, and tetrahydrofuran was used as a mobile phase, and was carried out by a gel permeation chromatography (GPC) using a differential refractometer as a detector. The flow rate was set to 1 mL/min, and the column temperature was set to 30 °C. The column is made of KF-802, 804L, and 806L manufactured by Showa Denko. In terms of molecular weight standards, monodisperse polystyrene can be used.

又，前述(D)成分理想上是以至少2種類的二醇(以下，亦稱為「原料二醇」。)做為原料二醇成分進行共聚合而得之具有複數種的伸烷基之聚碳酸酯二醇。舉例來說，例如，其二醇成分可以是由3-甲基-1,5-戊二醇和1,6-己二醇構成之共聚合聚碳酸酯二醇、或由1,5-戊二醇和1,6-己二醇構成之共聚合聚碳酸酯二醇、或由2-甲基-1,8-辛二醇和1,9-壬二醇構成之共聚合聚碳酸酯二醇等。只將1種類的原料二醇予以聚碳酸酯化而得到之僅具有1種類的伸烷基之聚碳酸酯二醇，其可提高(A)成分之結晶性、並減低硬化被膜之可撓性。 在由3-甲基-1,5-戊二醇和1,6-己二醇構成之共聚合聚碳酸酯二醇中之3-甲基-1,5-戊二醇和1,6-己二醇的莫耳比(d1/d2)可以是d1/d2=25/75~99/1之比例，較佳者為d1/d2=30/70 ~95/5之比例，更佳者為d1/d2=35/65~90/10之比例。 在由1,5-戊二醇和1,6-己二醇構成之共聚合聚碳酸酯二醇1,5-戊二醇中之1,6-己二醇的莫耳比(d3/d4可以是d3/d4= 25/75~99/1之比例，較佳者為d3/d4=30/70~95/5之比例，更佳者為d3/d4=35/65~90/10之比例。 在由2-甲基-1,8-辛二醇和1,9-壬二醇構成之共聚合聚碳酸酯二醇中之2-甲基-1,8-辛二醇和1,9-壬二醇之莫耳比(d5/d6)宜為d5/d6=25/75~ 99/1之比例，較佳者為d5/d6=30/70~95/5之比例，更佳者為d5/d6=35/65~90/10之比例。 另外，此處所述之「二醇成分」係指具有以下構造之化合物，其中該構造是藉由與碳酸酯或光氣間之反應來合成聚碳酸酯二醇用之原料，鏈式脂肪族烴或環式脂肪族烴的2個碳原子為1個個地被羥基所取代而成的構造。Further, the component (D) is preferably obtained by copolymerizing at least two types of diols (hereinafter also referred to as "raw material diols") as a raw material diol component, and having a plurality of alkylene groups. Polycarbonate diol. For example, the diol component may be a copolymerized polycarbonate diol composed of 3-methyl-1,5-pentanediol and 1,6-hexanediol, or 1,5-pentane A copolymerized polycarbonate diol composed of an alcohol and 1,6-hexanediol, or a copolymerized polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol. A polycarbonate diol having only one type of alkylene group obtained by polycarbonate-forming one type of raw material diol, which can improve the crystallinity of the component (A) and reduce the flexibility of the cured film. . 3-methyl-1,5-pentanediol and 1,6-hexane in a copolymerized polycarbonate diol composed of 3-methyl-1,5-pentanediol and 1,6-hexanediol The molar ratio (d1/d2) of the alcohol may be a ratio of d1/d2=25/75 to 99/1, preferably a ratio of d1/d2=30/70 to 95/5, and more preferably d1/ The ratio of d2=35/65~90/10. The molar ratio of 1,6-hexanediol in the copolymerized polycarbonate diol 1,5-pentanediol composed of 1,5-pentanediol and 1,6-hexanediol (d3/d4 may Is the ratio of d3/d4= 25/75~99/1, preferably the ratio of d3/d4=30/70~95/5, and the better is the ratio of d3/d4=35/65~90/10 2-methyl-1,8-octanediol and 1,9-anthracene in a copolymerized polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol The molar ratio of diol (d5/d6) is preferably a ratio of d5/d6=25/75~99/1, preferably d5/d6=30/70~95/5, and more preferably d5. The ratio of /d6=35/65 to 90/10. The term "diol component" as used herein refers to a compound having the following structure, wherein the structure is synthesized by reaction with a carbonate or phosgene. A raw material for a polycarbonate diol, a structure in which two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon are substituted by a hydroxyl group.

此種(D)成分較佳為在其骨架中具有碳數5~9的伸烷基(-CnH2 n-)。此種構造的聚碳酸酯二醇係能夠藉由使用碳數為5~9之二醇做為它的原料而形成。在原料二醇的碳數為小於5的情況，在(D)成分中之伸烷基的質量比例就會減少，而硬化被膜的可撓性就會降低。另一方面，當碳數為超過9時，則原料二醇的反應性就會減低，因而難以將原料二醇予以聚碳酸酯二醇化。The component (D) preferably has an alkylene group (-CnH 2 n-) having a carbon number of 5 to 9 in its skeleton. The polycarbonate diol having such a structure can be formed by using a diol having a carbon number of 5 to 9 as a raw material thereof. When the carbon number of the raw material diol is less than 5, the mass ratio of the alkylene group in the component (D) is decreased, and the flexibility of the cured film is lowered. On the other hand, when the carbon number is more than 9, the reactivity of the raw material diol is lowered, so that it is difficult to diolize the raw material diol.

就(D)成分之製造方法而論，舉例來說，例如，其可以是原料二醇與碳酸酯類之酯交換、原料二醇與光氣之脱氯化氫反應。As for the production method of the component (D), for example, it may be a transesterification of a raw material diol with a carbonate, and a dehydrochlorination reaction of a raw material diol with phosgene.

當考慮本發明之含羧基聚酯對於溶劑之溶解性時，前述(D)成分較佳為在其骨架中具有以1,5-戊烷骨架、1,6-己烷骨架、1,8-辛烷骨架、1,9-壬烷骨架所代表的伸烷基之共聚合聚碳酸酯二醇。When considering the solubility of the carboxyl group-containing polyester of the present invention with respect to a solvent, the above component (D) preferably has a 1,5-pentane skeleton, a 1,6-hexane skeleton, 1,8- in its skeleton. A copolymerized polycarbonate diol of an alkylene group represented by an octane skeleton or a 1,9-nonane skeleton.

在原料二醇之中，除了碳數為5~9之二醇以外，其他在不損害本發明目的之範圍，也可以含有碳數為4以下之二醇、碳數為10以上之二醇、聚醚二醇、兩末端羥基化聚丁二烯、聚酯二醇等。Among the raw material diols, a diol having a carbon number of 4 or less and a diol having a carbon number of 10 or more may be contained in addition to the diol having a carbon number of 5 to 9 insofar as the object of the present invention is not impaired. Polyether diol, hydroxylated polybutadiene at both ends, polyester diol, and the like.

在藉由酯交換來製造(D)成分的情況，原料之碳酸酯，舉例來說，例如，其可以是二甲基碳酸酯、二乙基碳酸酯等之二烷基碳酸酯；二苯基碳酸酯等之二芳基碳酸酯；及碳酸伸乙酯、碳酸伸丙酯等之碳酸伸烷酯。In the case of producing the component (D) by transesterification, the carbonate of the starting material may be, for example, a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate; diphenyl group; a diaryl carbonate such as a carbonate; and a alkyl carbonate such as an ethyl carbonate or a propyl carbonate.

藉由使此等之原料二醇與碳酸酯在100~230℃進行酯交換反應，可以製造出聚碳酸酯二醇。該酯交換反應係可以隨著反應的進行狀況等而在常壓或減壓之任意的壓力下進行。The polycarbonate diol can be produced by subjecting the raw material diol and the carbonate to a transesterification reaction at 100 to 230 °C. The transesterification reaction can be carried out under any pressure of normal pressure or reduced pressure depending on the progress of the reaction or the like.

又，在前述的酯交換反應中，雖然觸媒是不一定需要的，然而在想要加速反應的情況，理想上是使用觸媒。此種觸媒，可以採用在通常之聚碳酸酯的製造程序中所使用的酯交換觸媒，例如，其可以是四異丙氧鈦、四-n-丁氧鈦等之鈦化合物；月桂酸二-n-丁基錫、氧化二-n-丁基錫、二乙酸二丁基錫等之錫化合物；與乙酸錳、乙酸鈣等之乙酸金屬鹽、及氧化銻或上述鈦化合物之組合等。此等之觸媒之用量，較佳者是使相對於生成物而言成為如在1~300ppm之範圍內這種的量。Further, in the above-described transesterification reaction, although a catalyst is not necessarily required, in the case where it is desired to accelerate the reaction, it is desirable to use a catalyst. As such a catalyst, a transesterification catalyst used in a usual polycarbonate production process can be used. For example, it can be a titanium compound such as titanium tetraisopropoxide or tetra-n-butoxytitanium; lauric acid; a tin compound such as di-n-butyltin, di-n-butyltin oxide or dibutyltin diacetate; a metal acetate such as manganese acetate or calcium acetate; and a combination of cerium oxide or the above titanium compound. The amount of the catalyst to be used is preferably such an amount as to be in the range of from 1 to 300 ppm with respect to the product.

前述(D)成分較佳為在其骨架中具有複數種的伸烷基之聚碳酸酯二醇(共聚合聚碳酸酯二醇)；以市售品而言，舉例來說，例如，其可以是可樂麗多醇C-1015N(可樂麗(股)製碳酸酯二醇：2-甲基-1,8-辛二醇/1,9-壬二醇=85/15、數量平均分子量：約1,000)、可樂麗多醇C-1065N(可樂麗(股)製碳酸酯二醇：2-甲基-1,8-辛二醇/1,9-壬二醇=35/65、數量平均分子量：約1,000)、可樂麗多醇C-2015N(可樂麗(股)製碳酸酯二醇：2-甲基-1,8-辛二醇/1,9-壬二醇=85/15、數量平均分子量：約2,000)、可樂麗多醇C2065N(可樂麗(股)製碳酸酯二醇：2-甲基-1,8-辛二醇/1,9-壬二醇=35/65、數量平均分子量：約2,000)、可樂麗多醇C-1050(可樂麗(股)製碳酸酯二醇：3-甲基-1,5-戊二醇/1,6-己二醇=50/50、數量平均分子量：約1,000)、可樂麗多醇C-1090(可樂麗(股)製碳酸酯二醇：3-甲基-1,5-戊二醇/1,6-己二醇=90/10、數量平均分子量：約1,000)、可樂麗多醇C-2050(可樂麗(股)製碳酸酯二醇：3-甲基-1,5-戊二醇/1,6-己二醇=50/50、數量平均分子量：約2,000)、可樂麗多醇C-2090(可樂麗(股)製碳酸酯二醇：3-甲基-1,5-戊二醇/1,6-己二醇=90/10、數量平均分子量：約2,000)、DURANOL-T5651(旭化成化學品(股)製聚碳酸酯二醇：1,5-戊二醇/1,6-己二醇=50/50、數量平均分子量：約1,000)、DURANOL-T5652(旭化成化學品(股)製聚碳酸酯二醇：1,5-戊二醇/1,6-己二醇=50/50、數量平均分子量：約2,000)等。The above component (D) is preferably a polycarbonate diol (copolymerized polycarbonate diol) having a plurality of alkylene groups in its skeleton; in the case of a commercially available product, for example, it may be Is a colalyl C-1015N (carbonate diol produced by Kuraray): 2-methyl-1,8-octanediol/1,9-nonanediol=85/15, number average molecular weight: about 1,000), Colalyl C-1065N (carbonate diol produced by Kuraray): 2-methyl-1,8-octanediol/1,9-nonanediol = 35/65, number average molecular weight : about 1,000), colalyl C-2015N (carbonate diol produced by Kuraray): 2-methyl-1,8-octanediol / 1,9-nonanediol = 85/15, quantity Average molecular weight: about 2,000), colalyl C2065N (carbonate diol produced by Kuraray): 2-methyl-1,8-octanediol / 1,9-nonanediol = 35/65, quantity Average molecular weight: about 2,000), Claryl polyol C-1050 (carbonate diol produced by Kuraray): 3-methyl-1,5-pentanediol/1,6-hexanediol = 50/50 , number average molecular weight: about 1,000), colalyl C-1090 (carbonate diol produced by Kuraray): 3-methyl-1,5-pentanediol / 1,6-hexanediol = 90 /10, number average molecular weight: about 1, 000), Colalyl C-2050 (carbonate diol produced by Kuraray): 3-methyl-1,5-pentanediol/1,6-hexanediol = 50/50, number average molecular weight : about 2,000), colalyl C-2090 (carbonate diol produced by Kuraray): 3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10, quantity Average molecular weight: about 2,000), DURANOL-T5651 (polycarbonate diol manufactured by Asahi Kasei Chemicals Co., Ltd.: 1,5-pentanediol/1,6-hexanediol = 50/50, number average molecular weight: about 1,000 ), DURANOL-T5652 (polycarbonate diol manufactured by Asahi Kasei Chemicals Co., Ltd.: 1,5-pentanediol/1,6-hexanediol = 50/50, number average molecular weight: about 2,000).

又，為了改良本發明之含羧基聚酯的溶劑溶解性、本發明之硬化物的耐熱性之目的，除了前述(D)成分以外，也可以併用以碳數4以下之二醇為原料的聚碳酸酯二醇、聚丁二烯二醇、聚醚多醇、聚酯多醇、低分子量二醇；例如，相對於100質量份之前述聚碳酸酯二醇而言，可以併用5~80質量份的量。Further, in order to improve the solvent solubility of the carboxyl group-containing polyester of the present invention and the heat resistance of the cured product of the present invention, in addition to the above component (D), it is also possible to use a diol having a carbon number of 4 or less as a raw material. Carbonate diol, polybutadiene diol, polyether polyol, polyester polyol, low molecular weight diol; for example, 5 to 80 mass can be used in combination with 100 parts by mass of the aforementioned polycarbonate diol The amount of serving.

又，在上述酯交換反應中，有時也會附帶產生只在單末端上具有羥基的聚碳酸酯。在本發明中，像這種的副產物是極少量的，例如，也可以使用含有如5質量%以下的量之聚碳酸酯二醇。在超過5質量%的情況，則就會變得難以將含羧基聚酯予以高分子量化。Further, in the above transesterification reaction, a polycarbonate having a hydroxyl group only at a single terminal may be added. In the present invention, a by-product such as this is extremely small, and for example, a polycarbonate diol having an amount of, for example, 5% by mass or less can also be used. When it exceeds 5% by mass, it becomes difficult to polymerize the carboxyl group-containing polyester.

含羧基聚酯(A)成分的原料之投入莫耳比係可按照目的之(A)成分的分子量及酸價而調節的。The molar ratio of the raw material of the carboxyl group-containing polyester (A) component can be adjusted according to the molecular weight of the component (A) and the acid value.

＜含羧基聚酯(A)之製造方法＞ 以下，說明(A)成分的製造方法。 (A)成分係能夠藉由習用公知的方法而得到的。例如，較佳者為在安裝有攪拌器及溫度計之反應罐中，於溶劑之存在下，於70℃以上150℃以下使前述(C)成分與(D)成分起反應。更佳者為使之在90℃以上130℃以下起反應。只要是在70℃以上150℃以下，反應小時亦可縮短到4~6小時左右，則單體成分之分解就難以發生，而三次元化反應所引起的凝膠化也是難以發生的。反應溫度可以是以多階段來進行。反應小時是可以按照批次的規模、所採用的反應條件、特別是反應濃度而適當地選擇的。<Method for Producing Carboxyl Group-Containing Polyester (A)> Hereinafter, a method for producing the component (A) will be described. The component (A) can be obtained by a conventionally known method. For example, it is preferred that the component (C) and the component (D) are reacted in a reaction vessel equipped with a stirrer and a thermometer in the presence of a solvent at 70 ° C or more and 150 ° C or less. More preferably, it is allowed to react at a temperature of from 90 ° C to 130 ° C. As long as it is 70 ° C or more and 150 ° C or less, the reaction time can be shortened to about 4 to 6 hours, and decomposition of the monomer component hardly occurs, and gelation caused by the ternary reaction is hard to occur. The reaction temperature can be carried out in multiple stages. The reaction time can be appropriately selected in accordance with the scale of the batch, the reaction conditions employed, and particularly the reaction concentration.

＜有機溶劑＞ 在製造(A)成分時使用的有機溶劑，較佳為不含胺等之鹼基性化合物的溶劑。此種的溶劑，舉例來說，例如，其可以是甲苯、二甲苯、乙苯、硝基苯、環己烷、異佛爾酮、二乙二醇二甲基醚、三乙二醇二甲基醚、乙二醇二乙基醚、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、二丙二醇甲基醚乙酸酯、二乙二醇乙基醚乙酸酯、甲氧基丙酸甲酯、甲氧基丙酸乙酯、乙氧基丙酸甲酯、乙氧基丙酸乙酯、乙酸乙酯、乙酸n-丁酯、乙酸異戊酯、乳酸乙酯、丙酮、甲基乙基酮、環己酮、γ-丁內酯、二甲基亞碸、氯仿及二氯甲烷等。<Organic solvent> The organic solvent used in the production of the component (A) is preferably a solvent containing no base compound such as an amine. Such a solvent may, for example, be toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, triethylene glycol dimethyl Ethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, methoxy Methyl propionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, Methyl ethyl ketone, cyclohexanone, γ-butyrolactone, dimethyl hydrazine, chloroform, dichloromethane, and the like.

較佳的溶劑為溶解性優良的三乙二醇二甲基醚、γ-丁內酯。特佳者為γ-丁內酯。A preferred solvent is triethylene glycol dimethyl ether or γ-butyrolactone having excellent solubility. The most preferred one is γ-butyrolactone.

較佳者為使用在製造時顯現良好的溶解性之有機溶劑；具體而言，較佳者為相對於單一溶劑、或由2種以上混合而成的溶劑之任何者而言，能夠溶解所製造的樹脂之10質量%以上者。更佳者為可以溶解15質量%以上，更理想者為20質量%以上。此外，溶解與否之判定，在樹脂為固態狀的情況，在200ml之燒杯中添加規定重量的可通過80網目之樹脂粉末，於25℃靜靜地攪拌24小時後的溶液，於25℃靜置24小時，以目視觀察，當無凝膠化、不均一化、白濁、析出中之任何者時則判定為溶解。An organic solvent which exhibits good solubility at the time of production is preferably used. Specifically, it is preferably produced by dissolving in a single solvent or a solvent obtained by mixing two or more kinds. 10% by mass or more of the resin. More preferably, it is 15% by mass or more, and more preferably 20% by mass or more. In addition, in the case where the resin is solid, a predetermined weight of a resin powder which can pass 80 mesh is added to a 200 ml beaker, and the solution is stirred at 25 ° C for 24 hours, and is allowed to stand at 25 ° C. After 24 hours, it was visually observed that it was judged to be dissolved when there was no gelation, non-uniformity, white turbidity, or precipitation.

＜觸媒＞ 在製造(A)成分時所使用的反應觸媒，舉例來說，例如，其可以是胺、四級銨鹽、咪唑、醯胺、吡啶、膦、有機金屬鹽等。更佳者為胺、吡啶、膦。更具體而言，舉例來說，例如，其可以是三乙基胺、苄基二甲基胺等之胺；4-二甲基胺基吡啶等之吡啶；三苯基膦等之膦。特佳者為4-二甲基胺基吡啶。<Catalyst> The reaction catalyst used in the production of the component (A) may be, for example, an amine, a quaternary ammonium salt, an imidazole, a guanamine, a pyridine, a phosphine, an organic metal salt or the like. More preferred are amines, pyridines, and phosphines. More specifically, for example, it may be an amine such as triethylamine or benzyldimethylamine; a pyridine such as 4-dimethylaminopyridine; or a phosphine such as triphenylphosphine. Particularly preferred is 4-dimethylaminopyridine.

本發明之含羧基聚酯(A)係具有以下所示之特徴。 (1) 無凝膠化且能夠充分地形成高分子量化； (2) 在主鏈上具有多數個羧基。 在此高分子量的(A)成分中摻混含有環氧乙烷環的化合物(B)而成之熱硬化性樹脂組成物可顯示良好的熱硬化性。由此種熱硬化性樹脂組成物所得到的硬化被膜，因為具有強靭且高的凝集力，所以可對於薄膜或金屬箔等之基材顯示出良好的密接性。The carboxyl group-containing polyester (A) of the present invention has the following characteristics. (1) No gelation and sufficient formation of a high molecular weight; (2) A plurality of carboxyl groups in the main chain. The thermosetting resin composition obtained by blending the compound (B) containing an oxirane ring in the high molecular weight (A) component exhibits good thermosetting property. Since the hardened film obtained from such a thermosetting resin composition has a strong and high cohesive force, it can exhibit good adhesion to a substrate such as a film or a metal foil.

藉由使(C)成分的酸酐基、與(D)成分的羥基起反應，可進行酸酐基之開環反應。另一方面，可以形成酯鍵；又再一方面可以在(A)成分的主鏈中形成2個羧基(殘留羧基)。使存在有該羧基，以(B)成分為熱硬化劑，藉由適量摻混地使用就能夠呈現優異的熱硬化性(參照圖1)。 另外，在圖1中，R1 為從四羧酸二酐除去酸酐基而得之有機基，也可以含有取代基，具有碳數1~30之芳香族基、脂環族基、脂肪族基、或雜環之基。R2 為從聚碳酸酯二醇除去羥基而得之有機基，但該聚碳酸酯二醇為具有複數種之伸烷基；該聚碳酸酯二醇的數量平均分子量為700~2300。P只要是使得(A)成分之數量平均分子量成為超過10000且在50000以下的整數即可。The ring opening reaction of the acid anhydride group can be carried out by reacting the acid anhydride group of the component (C) with the hydroxyl group of the component (D). On the other hand, an ester bond can be formed; on the other hand, two carboxyl groups (residual carboxyl groups) can be formed in the main chain of the component (A). The carboxyl group is present, and the component (B) is a thermosetting agent, and it can exhibit excellent thermosetting property by being blended in an appropriate amount (see FIG. 1). Further, in Fig. 1, R 1 is an organic group obtained by removing an acid anhydride group from a tetracarboxylic dianhydride, and may have a substituent, and has an aromatic group having an carbon number of 1 to 30, an alicyclic group, and an aliphatic group. Or a heterocyclic group. R 2 is an organic group obtained by removing a hydroxyl group from a polycarbonate diol, but the polycarbonate diol has a plurality of alkylene groups; the polycarbonate diol has a number average molecular weight of 700 to 2,300. P may be an integer such that the number average molecular weight of the component (A) is more than 10,000 and not more than 50,000.

(C)成分與(D)成分之摻混量，在控制(A)成分的分子量上是重要的。The blending amount of the component (C) and the component (D) is important in controlling the molecular weight of the component (A).

(C)成分、與(D)成分之投入比例，當以莫耳比(C/D)表示時，可以是C/D=60/100~99/100、或140/100~101/100之比例，較佳為C/D=75/100~99/100、或125/100~101/100；更佳者為C/D=85/100~99/100、或115/100~101/100之比例。The ratio of the component (C) to the component (D), when expressed in molar ratio (C/D), may be C/D=60/100 to 99/100 or 140/100 to 101/100. The ratio is preferably C/D=75/100~99/100 or 125/100~101/100; more preferably C/D=85/100~99/100, or 115/100~101/100 The ratio.

莫耳比只要是C/D=60/100~99/100、或140/100~ 101/100，則就能夠得到耐熱性和溶劑溶解性之平衡特別良好的高分子量之(A)成分。從而，就能夠得到熱硬化性優異、處理容易之黏度的(A)成分。此外，亦能夠形成堅硬的硬化被膜。When the molar ratio is C/D=60/100 to 99/100 or 140/100 to 101/100, a high molecular weight (A) component having a particularly good balance between heat resistance and solvent solubility can be obtained. Therefore, the component (A) having excellent thermosetting properties and easy handling can be obtained. In addition, it is also possible to form a hard hardened film.

本發明之(A)成分的數量平均分子量為超10000且在50000以下。藉此，就能夠得到耐熱性與溶劑溶解性之平衡良好的羧基含有熱硬化性聚酯。數量平均分子量較佳為10200以上49000以下；更佳為10300以上47900以下。就(A)成分的數量平均分子量為在上述範圍以下而論，由於硬化被膜的可撓性就會減低；當超過上述範圍時，樹脂清漆的溶液黏度變高，對於阻焊劑之後加工就會變困難，因而是不理想的。The component (A) of the present invention has a number average molecular weight of more than 10,000 and not more than 50,000. Thereby, a carboxyl group containing a thermosetting polyester having a good balance between heat resistance and solvent solubility can be obtained. The number average molecular weight is preferably 10,200 or more and 49,000 or less; more preferably 10,300 or more and 47,900 or less. When the number average molecular weight of the component (A) is below the above range, the flexibility of the cured film is reduced; when it exceeds the above range, the viscosity of the solution of the resin varnish becomes high, and the processing after the solder resist is changed. Difficulties are therefore not ideal.

＜含羧基聚酯(A)之構造＞ 本發明之(A)成分，具體來說，較佳為具有以下之一般式[I]所示的重複構造者。〔在一般式[I]中，R1 為從四羧酸二酐除去酸酐基之有機基，也可以含有取代基，具有碳數1~30的芳香族基、脂環族基、脂肪族基、或雜環之基。R2 為從聚碳酸酯二醇除去羥基而得之有機基，但該聚碳酸酯二醇具有複數種之伸烷基，該聚碳酸酯二醇的數量平均分子量為700~2300。〕<Structure of the carboxyl group-containing polyester (A)> The component (A) of the present invention is preferably a repeating structure represented by the following general formula [I]. [In the general formula [I], R 1 is an organic group which removes an acid anhydride group from a tetracarboxylic dianhydride, and may have a substituent, and has an aromatic group having an carbon number of 1 to 30, an alicyclic group, or an aliphatic group. Or a heterocyclic group. R 2 is an organic group obtained by removing a hydroxyl group from a polycarbonate diol, but the polycarbonate diol has a plurality of alkylene groups having a number average molecular weight of 700 to 2,300. 〕

本發明之(A)成分的酸價為在1200當量/106 g以上。因此，可得到充分的交聯構造，並且熱硬化性、長期絕緣信賴性、銅箔密接性等成為特別良好。又，硬化收縮的發生亦變困難了。當樹脂酸價小於1200當量/106 g時，由於相對於100質量份之含羧基聚酯而言，熱硬化劑的摻混量就成為小於40質量份、而硬化被膜的銅箔密接性降低下，因而不理想。酸價的上限値，雖然是沒特別加以限制，然而較佳者為在2500當量/106 g左右。The acid value of the component (A) of the present invention is 1200 equivalents/10 6 g or more. Therefore, a sufficient crosslinked structure can be obtained, and thermosetting property, long-term insulation reliability, copper foil adhesion, and the like are particularly excellent. Moreover, the occurrence of hardening shrinkage becomes difficult. When the acid value of the resin is less than 1200 equivalents/10 6 g, the blending amount of the thermosetting agent is less than 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing polyester, and the adhesion of the copper foil of the cured film is lowered. Next, it is not ideal. The upper limit of the acid value is not particularly limited, but is preferably about 2,500 equivalents/10 6 g.

本發明之含羧基聚酯中的一般式[I]之重複構造的含有率(質量%)只要是68質量%以上即可，較佳者為可以是在70質量%以上。當成為68質量%以上時，藉由含有本發明之含羧基聚酯的熱硬化性樹脂組成物所得到的硬化被膜除了可撓性之外、銅箔密接性、長期絕緣信賴性、及耐鍍敷性亦皆特別優異。The content (% by mass) of the repetitive structure of the general formula [I] in the carboxyl group-containing polyester of the present invention may be 68% by mass or more, and preferably 70% by mass or more. When it is 68% by mass or more, the cured film obtained by the thermosetting resin composition containing the carboxyl group-containing polyester of the present invention has flexibility in addition to flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance. The compressibility is also excellent.

＜熱硬化性樹脂組成物＞ 本發明之熱硬化性樹脂組成物係指：至少為將「含羧基聚酯(A)」、及後述的「含有環氧乙烷環之化合物(B)」溶解於製造(A)成分之際使用來做為有機溶劑的例子所列舉的有機溶劑中而成之物。另外，本發明之熱硬化性樹脂組成物也可以含有後述的「(B)成分以外之熱硬化劑」、「硬化促進劑」、及/或「其他的添加劑」。熱硬化性樹脂組成物之固體成分濃度，較佳者為40質量%~60質量%，更佳者為45質量%~55質量%。當成為40質量%~60質量%時，則網版印刷性就特別的優異。 以下，舉例並說明「含有環氧乙烷環之化合物(B)」、「(B)成分以外的熱硬化劑」、「硬化促進劑」、及「其他的添加劑」的例子。<Thermosetting Resin Composition> The thermosetting resin composition of the present invention means at least the "carboxyl group-containing polyester (A)" and the "epoxide-containing compound (B)" which will be described later are dissolved. In the case of producing the component (A), it is used as an organic solvent exemplified as an example of an organic solvent. In addition, the thermosetting resin composition of the present invention may contain a "thermosetting agent other than the component (B)", a "hardening accelerator", and/or "other additives" which will be described later. The solid content concentration of the thermosetting resin composition is preferably 40% by mass to 60% by mass, more preferably 45% by mass to 55% by mass. When it is 40% by mass to 60% by mass, the screen printing property is particularly excellent. Hereinafter, examples of "the compound (B) containing an oxirane ring", "a thermosetting agent other than the component (B)", a "hardening accelerator", and "other additives" will be described by way of example.

＜含有環氧乙烷環之化合物(B)＞ 含有環氧乙烷環之化合物(B)為具有與(A)成分的羧基反應得到的官能基之化合物。(B)成分只要環氧乙烷環是在分子內所含有的即可，並未特別加以限定。舉例來說，例如，可以是含環氧基化合物、及含氧雜環丁烷基化合物等。<Ethylene oxide ring-containing compound (B)> The compound (B) containing an oxirane ring is a compound having a functional group obtained by reacting a carboxyl group of the component (A). The component (B) is not particularly limited as long as the oxirane ring is contained in the molecule. For example, it may be an epoxy group-containing compound, an oxetane group-containing compound, or the like.

含環氧基化合物，舉例來說，例如，其可以是雙酚A型環氧樹脂、加氫雙酚A型環氧樹脂、雙酚F型環氧樹脂、溴化雙酚A型環氧樹脂、苯酚酚醛清漆型環氧樹脂、o-甲酚酚醛清漆型環氧樹脂、可撓性環氧樹脂、胺型環氧樹脂、含雜環環氧樹脂、脂環式環氧樹脂、雙酚S型環氧樹脂、二環戊二烯型環氧樹脂、三縮水甘油基異三聚氰酸酯、聯二甲酚型環氧樹脂、具有縮水甘油基之化合物等。The epoxy group-containing compound may be, for example, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a brominated bisphenol A type epoxy resin. , phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, flexible epoxy resin, amine type epoxy resin, heterocyclic epoxy resin, alicyclic epoxy resin, bisphenol S Type epoxy resin, dicyclopentadiene type epoxy resin, triglycidyl isocyanurate, bisxylenol type epoxy resin, a compound having a glycidyl group, and the like.

含氧雜環丁烷基化合物，只要是在分子內具有氧雜環丁烷環、且能夠硬化之物即可，並未特別加以限定；舉例來說，例如，其可以是3-乙基-3-羥基甲基氧雜環丁烷、1,4-雙-{[(3-乙基-3-氧雜環丁烷基)甲氧基]甲基}苯、3-乙基3-(苯氧基甲基)氧雜環丁烷、二[1-乙基(3-氧雜環丁烷基)]甲基醚、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、3-乙基-3-{[3-(三乙氧基)丙氧]甲基}氧雜環丁烷、3,3-雙(羥基甲基)氧雜環丁烷、二[1-羥基甲基(3-氧雜環丁烷基)]甲基醚、3,3-雙(羥基甲基)氧雜環丁烷、及氧雜環丁烷基-倍半矽氧烷等。The oxetane group-containing compound is not particularly limited as long as it has an oxetane ring in the molecule and can be hardened; for example, it may be 3-ethyl- 3-hydroxymethyloxetane, 1,4-bis-{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl 3-( Phenoxymethyl)oxetane, bis[1-ethyl(3-oxetanyl)methyl ether, 3-ethyl-3-(2-ethylhexyloxymethyl) Oxetane, 3-ethyl-3-{[3-(triethoxy)propoxy]methyl}oxetane, 3,3-bis(hydroxymethyl)oxetane Alkane, bis[1-hydroxymethyl(3-oxetanyl)methyl ether, 3,3-bis(hydroxymethyl)oxetane, and oxetanyl-half Oxane and the like.

此等之(B)成分可以使用單一種類，或者也可以將2種類以上加以組合來使用。在此等之中，從銅箔密接性、耐鍍敷性的觀點來看，較佳者為使用苯酚酚醛清漆型環氧樹脂、或o-甲酚酚醛清漆型環氧樹脂。。These components (B) may be used in a single type or in combination of two or more types. Among these, from the viewpoint of copper foil adhesion and plating resistance, a phenol novolac type epoxy resin or an o-cresol novolak type epoxy resin is preferably used. .

於此等之(B)成分中也可以更進一步地含有在1分子中只具有1個環氧基的環氧化合物之稀釋劑。Further, the component (B) may further contain a diluent of an epoxy compound having only one epoxy group in one molecule.

添加此等之(B)成分的方法，可以是預先將要添加的(B)成分溶解於：與含有(A)成分的溶劑相同的溶劑中後再添加，或者也可以直接添加於(A)成分中。The method of adding the component (B) may be carried out by dissolving the component (B) to be added in advance in the same solvent as the solvent containing the component (A), or may be directly added to the component (A). in.

又，藉由調整與熱硬化有關的環氧乙烷環與羧基之比例，就能夠將熱硬化性設定於所期望的範圍。具體而言，環氧乙烷環與羧基之比例較佳為環氧乙烷環/羧基(莫耳比)=3/1~1/3，更佳者為2/1~1/2。當在環氧乙烷環/羧基(莫耳比)=2/1~1/2之範圍時，硬化性、交聯性就特別優異。Moreover, by adjusting the ratio of the oxirane ring to the carboxyl group related to thermosetting, the thermosetting property can be set to a desired range. Specifically, the ratio of the oxirane ring to the carboxyl group is preferably oxirane ring/carboxyl group (mole ratio) = 3/1 to 1/3, more preferably 2/1 to 1/2. When the range of the oxirane ring/carboxyl group (mole ratio) is 2/1 to 1/2, the hardenability and the crosslinkability are particularly excellent.

(B)成分的使用量可以是考慮本發明之(A)成分的用途等來決定，雖然並沒有特別加以限定，然而相對於100質量份之本發明的含羧基聚酯而言，較佳為40質量份~90質量份，更佳為40質量份~80質量份。由於藉由使用含有環氧乙烷環之化合物能夠將由本發明的(A)成分所得到之硬化被膜的交聯密度調整到適當的値，所以就能夠將硬化後之被膜的各種物性更向上提高一層。當(B)成分的使用量為少於上述範圍時交聯性就會惡化，又且在多於上述範圍的情況交聯性也會降低，因而有時就會有耐熱特性、及耐溶劑性等惡化的情況。The amount of the component (B) to be used may be determined in consideration of the use of the component (A) of the present invention, and the like. Although it is not particularly limited, it is preferably 100 parts by mass of the carboxyl group-containing polyester of the present invention. 40 parts by mass to 90 parts by mass, more preferably 40 parts by mass to 80 parts by mass. Since the crosslinking density of the cured film obtained from the component (A) of the present invention can be adjusted to an appropriate enthalpy by using a compound containing an oxirane ring, various physical properties of the film after hardening can be further improved. layer. When the amount of the component (B) is less than the above range, the crosslinkability is deteriorated, and when it is more than the above range, the crosslinkability is also lowered, so that heat resistance and solvent resistance sometimes occur. Waiting for the deterioration.

在本發明之熱硬化性樹脂組成物中，除了前述(B)成分以外，熱硬化劑也可以是使用具有與羥基、羧基等起反應而得之官能基的化合物。具體而言，舉例來說，例如，其可以是異氰酸酯化合物、嵌段異氰酸酯化合物、氰酸酯化合物、氮丙啶化合物、含酸酐基化合物、含羧基化合物、羧醯亞胺基含有化合物、苯并㗁嗪化合物、馬來醯亞胺化合物、檸康醯亞胺化合物、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、乙烯基苄基醚樹脂、硫醇化合物、三聚氰胺化合物、胍胺化合物、含胺樹脂、酚樹脂、醇酸樹脂、丙烯酸樹脂、不飽和聚酯樹脂、酞酸二烯丙酯樹脂、矽氧烷樹脂、二甲苯樹脂、呋喃樹脂、酮樹脂、三聚氰酸三烯丙酯樹脂、含有参(2-羥乙基)異三聚氰酸酯的樹脂、含有偏苯三酸三烯丙酯的樹脂、二環戊二烯樹脂、芳香族二氰亞胺之三聚合而得的熱硬化性樹脂等。此等之化合物可以單獨，或者也可以將2種類以上加以組合來使用。In the thermosetting resin composition of the present invention, in addition to the component (B), the thermosetting agent may be a compound having a functional group obtained by reacting with a hydroxyl group, a carboxyl group or the like. Specifically, for example, it may be an isocyanate compound, a blocked isocyanate compound, a cyanate compound, an aziridine compound, an acid anhydride group-containing compound, a carboxyl group-containing compound, a carboxium imine group-containing compound, a benzo compound. Pyridazine compound, maleic imine compound, citrate imine compound, nadic ylidene compound, allyl nadic ylide compound, vinyl ether compound, vinyl benzyl ether resin, thiol compound , melamine compound, guanamine compound, amine-containing resin, phenol resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl citrate resin, decane resin, xylene resin, furan resin, ketone resin , triallyl cyanurate resin, resin containing ginseng (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, dicyclopentadiene resin, aromatic A thermosetting resin obtained by the triple polymerization of dicyandiamide. These compounds may be used singly or in combination of two or more kinds.

＜硬化促進劑＞ 在本發明之熱硬化性樹脂組成物中，為了使熱硬化性、耐熱性、及耐溶劑性等之特性更為向上提高一層，則可以使用硬化促進劑。硬化促進劑，只要是能夠促進上述的(A)成分與(B)成分鐘之硬化反應即可，並未特別加以限制。<Curing accelerator> In the thermosetting resin composition of the present invention, a curing accelerator can be used in order to further improve the properties such as thermosetting property, heat resistance, and solvent resistance. The hardening accelerator is not particularly limited as long as it can promote the hardening reaction of the above component (A) and (B) in minutes.

諸如此類的硬化促進劑，舉例來說，例如，其可以是咪唑衍生物、乙醯胍胺、苯并胍胺等之胍胺類、二胺基二苯基甲烷、m-伸苯基二胺、m-二甲苯二胺、二胺基二苯基碸、二氰二醯胺、尿素、尿素衍生物、三聚氰胺、多鹼基醯肼等之多胺類、此等之有機酸鹽及/或環氧加合物、三氟化硼之胺錯合物、乙基二胺基-S-三嗪、2,4-二胺基-S-三嗪,2,4-二胺基-6-二甲苯基-S-三嗪等之三嗪衍生物類、三甲基胺、三乙醇胺、N,N-二甲基辛基胺、N-苄基二甲基胺、吡啶、N-甲基嗎啉、六(N-甲基)三聚氰胺、2,4,6-参(二甲基胺基苯酚)、四甲基胍、1,8-二氮雜二環[5,4,0]-7-十一烯(有時亦稱為「DBU」)、1,5-二氮雜二環[4,3,0]-5-壬烯(有時亦稱為「DBN」)等之三級胺類、此等之有機酸鹽及/或硼酸四苯基酯、聚乙烯基苯酚、聚乙烯基苯酚溴化物、三丁基膦、三苯基膦、参-2-氰基乙基膦等之有機膦類、溴化三-n-丁基(2,5-二羥基苯基)鏻、氯化十六基三丁基鏻、四苯基硼酸四苯基鏻等之四級鏻鹽類、氯化苄基三甲基銨、氯化苯基三丁基銨等之四級銨鹽類、前述聚碳酸酐、四氟硼酸二苯基錪鹽、六氟銻酸三苯基鋶鹽、六氟磷酸2,4,6-三苯基硫代吡喃鎓鹽、IRGACUREｰ261(汽巴特殊化學品(股)製)、OPTOMA-SP-170(ADEKA(股)製)等之光陽離子聚合觸媒、苯乙烯-馬來酸酐樹脂、苯基異氰酸酯與二甲基胺之等莫耳反應物、或甲苯二異氰酸酯、異佛爾酮二異氰酸酯等之有機聚異氰酸酯、與二甲基胺之等莫耳反應物等。可以將此等以單獨來使用、或者將2種類以上加以組合來使用。在此等之中，具有潛在硬化性之硬化促進劑，舉例來說，例如，較佳者為DBU、DBN之有機酸鹽及/或硼酸四苯基酯、及光陽離子聚合觸媒等。Such a hardening accelerator, for example, may be an imidazole derivative, an acetamide, a benzoguanamine or the like of a guanamine, a diaminodiphenylmethane or an m-phenylenediamine. a polyamine such as m-xylylenediamine, diaminodiphenylphosphonium, dicyanamide, urea, urea derivative, melamine, polybasic hydrazine, etc., organic acid salts and/or rings thereof Oxygen adduct, amine complex of boron trifluoride, ethyldiamine-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-di Triazine derivatives such as tolyl-S-triazine, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methyl? Porphyrin, hexa(N-methyl)melamine, 2,4,6-gin (dimethylaminophenol), tetramethylguanidine, 1,8-diazabicyclo[5,4,0]-7 Tertiary (also sometimes referred to as "DBU"), 1,5-diazabicyclo[4,3,0]-5-pinene (sometimes referred to as "DBN"), etc. Amines, organic acid salts and/or tetraphenyl borate, polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, cis-2-cyanoethylphosphine, etc. Organic a phosphine, a tri-n-sulfonium salt such as tris-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecylphosphonium chloride or tetraphenylphosphonium tetraphenylphosphonate, chlorine a quaternary ammonium salt such as benzyltrimethylammonium or phenyltributylammonium chloride, the above polycarbonic anhydride, diphenylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, hexafluorocarbon Photocationic polymerization of 2,4,6-triphenylthiopyranium phosphate, IRGACURE 261 (made by Ciba Specialty Chemicals Co., Ltd.), OPTOMA-SP-170 (made by ADEKA) a solvent, a styrene-maleic anhydride resin, a molar reaction such as phenyl isocyanate and dimethylamine, or an organic polyisocyanate such as toluene diisocyanate or isophorone diisocyanate, and dimethylamine. Ear reactants, etc. These may be used alone or in combination of two or more types. Among these, a hardening accelerator having a latent curing property is, for example, preferably an organic acid salt of DBU or DBN, and/or a tetraphenyl borate, a photocationic polymerization catalyst, or the like.

硬化促進劑之使用量，相對於100質量份的含有環氧乙烷環之化合物(B)而言，較佳者為30質量份以下。當超過30質量份時，由於含羧基聚酯的保存安定性、硬化被膜的耐熱性、及耐溶劑性就降低，因而不是理想的。The amount of the curing accelerator to be used is preferably 30 parts by mass or less based on 100 parts by mass of the oxirane ring-containing compound (B). When it exceeds 30 parts by mass, the storage stability of the carboxyl group-containing polyester, the heat resistance of the cured film, and the solvent resistance are lowered, which is not preferable.

本發明之熱硬化性樹脂組成物的總固態成分中所含之一般式[I]的重複構造之含有率(質量%)可以是在40質量%以上，較佳者為在41質量%以上。上限較佳為71質量%以下，更佳為在70質量%以下。當在40質量%以上71質量%以下時，由含有本發明的含羧基聚酯之熱硬化性樹脂組成物所得到的硬化被膜，除了可撓性以外，銅箔密接性、長期絕緣信賴性、及耐鍍敷性亦特別優異。The content (% by mass) of the repeating structure of the general formula [I] contained in the total solid content of the thermosetting resin composition of the present invention may be 40% by mass or more, preferably 41% by mass or more. The upper limit is preferably 71% by mass or less, and more preferably 70% by mass or less. When it is 40% by mass or more and 71% by mass or less, the cured film obtained from the thermosetting resin composition containing the carboxyl group-containing polyester of the present invention has flexibility in adhesion to copper foil, long-term insulation reliability, and flexibility. And plating resistance is also particularly excellent.

＜其他的添加劑＞ 本發明之熱硬化性樹脂組成物係非常適合於做為各種被膜形成材料使用。在本發明之熱硬化性樹脂組成物中，為了提高塗布時之作業性及被膜形成前後之膜特性，也可以添加消泡劑、整平劑、酚樹脂、染料或顏料等之著色劑類、熱安定劑、抗氧化劑、難燃劑、滑劑等來使用。其他，也可以使用、二氧化矽(SiO2 )、三氧化二鋁(Al2 O3 )、二氧化鈦(TiO2 )、氧化鉭(Ta2 O5 )、二氧化鋯(ZrO2 )、氮化矽(Si3 N4 )、鈦酸鋇(BaO･TiO2 )、碳酸鋇(BaCO3 )、鈦酸鉛(PbO･TiO2 )、鋯鈦酸鉛(PZT)、鋯鈦酸鉛鑭(PLZT)、氧化鎵(Ga2 O3 )、尖晶石(MgO･Al2 O3 )、莫來石(3Al2 O3 ･2SiO2 )、堇青石(2MgO･2Al2 O3 /5SiO2 )、滑石(3MgO･4SiO2 ･H2 O)、鈦酸鋁(TiO2 -Al2 O3 )、含氧化釔之二氧化鋯(Y2 O3 - ZrO2 )、矽酸鋇(BaO･8SiO2 )、氮化硼(BN)、碳酸鈣(CaCO3 )、硫酸鈣(CaSO4 )、氧化鋅(ZnO)、鈦酸鎂(MgO･TiO2 )、硫酸鋇(BaSO4 )、有機澎潤土、碳、水滑石等來做為無機微粒子；可以使用此等之1種或2種以上。<Other Additives> The thermosetting resin composition of the present invention is very suitable for use as various film forming materials. In the thermosetting resin composition of the present invention, in order to improve the workability at the time of coating and the film properties before and after the film formation, a coloring agent such as an antifoaming agent, a leveling agent, a phenol resin, a dye or a pigment may be added. Thermal stabilizers, antioxidants, flame retardants, slip agents, etc. are used. Others, cerium oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium dioxide (TiO 2 ), lanthanum oxide (Ta 2 O 5 ), zirconium dioxide (ZrO 2 ), nitriding may also be used.矽(Si 3 N 4 ), barium titanate (BaO·TiO 2 ), barium carbonate (BaCO 3 ), lead titanate (PbO·TiO 2 ), lead zirconate titanate (PZT), lead zirconate titanate (PLZT) ), gallium oxide (Ga 2 O 3 ), spinel (MgO·Al 2 O 3 ), mullite (3Al 2 O 3・2SiO 2 ), cordierite (2MgO·2Al 2 O 3 /5SiO 2 ), Talc (3MgO, 4SiO 2 · H 2 O), aluminum titanate (TiO 2 -Al 2 O 3 ), yttria-containing zirconium dioxide (Y 2 O 3 - ZrO 2 ), barium strontium silicate (BaO·8SiO 2 ) ), boron nitride (BN), calcium carbonate (CaCO 3 ), calcium sulfate (CaSO 4 ), zinc oxide (ZnO), magnesium titanate (MgO·TiO 2 ), barium sulfate (BaSO 4 ), organic barium The carbon, the hydrotalcite, and the like are used as the inorganic fine particles; one or two or more of these may be used.

＜被膜形成材料＞ 本發明之熱硬化性樹脂組成物係非常適合使用來做為被膜形成用樹脂組成物、或被膜形成材料。被膜形成材料，例如可以使用於電子構件用覆蓋塗布材、液狀密封材、漆包線用清漆、電性絕緣用含浸清漆、注模清漆、雲母、與玻璃纖維布等之基材組合而成之薄片用清漆、MCL積層板用清漆、摩擦材料用清漆、印刷基板領域等之中的層間絕緣膜、表面保護膜、阻焊劑層、接合層等。又，被膜形成用樹脂組成物或被膜形成材料也可以使用於半導體元件等之電子構件；特別是含有本發明之熱硬化性樹脂組成物的阻焊劑係可有效使用於形成COF用途等之撓性配線板的保護膜(硬化被膜)。 本發明之阻焊劑係可以使用本發明的熱硬化性樹脂組成物，也可以就照其本來樣子使用。<Film Forming Material> The thermosetting resin composition of the present invention is very suitably used as a resin composition for forming a film or a film forming material. The film forming material can be used, for example, in a cover material for an electronic component, a liquid sealing material, an enamel for an enameled wire, an impregnating varnish for electrical insulation, an injection molding varnish, a mica, and a substrate made of a glass fiber cloth or the like. A varnish, a varnish for a MCL laminate, a varnish for a friction material, an interlayer insulating film, a surface protective film, a solder resist layer, a bonding layer, and the like in the field of a printed circuit board. Further, the resin composition for forming a film or the film forming material can be used for an electronic component such as a semiconductor element; in particular, the solder resist containing the thermosetting resin composition of the present invention can be effectively used for forming flexibility of COF use or the like. Protective film of the wiring board (hardened film). The solder resist of the present invention may be a thermosetting resin composition of the present invention, or may be used as it is.

藉由將本發明之熱硬化性樹脂組成物、被膜形成材料、或阻焊劑予以熱硬化，能夠得到可撓性、銅箔密接性、長期絕緣信賴性、及耐鍍敷性皆優異的硬化被膜。 將基於本發明於熱硬化性樹脂組成物使用於配線圖案部經錫鍍敷處理過的COF用途之撓性配線板的保護膜(阻焊劑)之情況，從防止錫鍍敷層之擴散、且可得到適合做為保護膜之可撓性、銅箔密接性、長期絕緣信賴性、及耐鍍敷性的觀點來看，熱硬化的加熱溫度條件較佳為80~130℃；特佳者為90~120℃。又，從防止錫鍍敷層之擴散、且可得到適合做為保護膜之可撓性、銅箔密接性、長期絕緣信賴性、及耐鍍敷性的觀點來看，熱硬化之加熱小時較佳為30~150分，特佳者為45~120分。 《實施例》By thermosetting the thermosetting resin composition, the film forming material, or the solder resist of the present invention, it is possible to obtain a cured film which is excellent in flexibility, copper foil adhesion, long-term insulation reliability, and plating resistance. . In the case where the thermosetting resin composition is used in the protective film (solder resist) of the flexible wiring board for COF use in which the wiring pattern portion is tin-plated, the diffusion of the tin plating layer is prevented, and From the viewpoint of flexibility as a protective film, adhesion to copper foil, long-term insulation reliability, and plating resistance, the heating temperature condition of the heat curing is preferably 80 to 130 ° C; 90~120°C. Further, from the viewpoint of preventing the diffusion of the tin plating layer and obtaining flexibility suitable as a protective film, copper foil adhesion, long-term insulation reliability, and plating resistance, the heat hardening is less. Good for 30~150 points, especially for those with 45~120 points. "Embodiment"

以下，雖然藉由實施例來說明本發明，然而本發明並非僅限定於此等之實施例。另外，在各實施例中之特性値的評估係藉由以下的方法來進行的。Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. In addition, the evaluation of the characteristics 在 in each of the examples was carried out by the following method.

＜含羧基聚酯(A)中之組成＞ 將(A)成分溶解於氘代氯仿、或氘代二甲基亞碸中，使用VARIAN公司製 NMR裝置400-MR進行1 H-NMR分析，求得在含羧基聚酯(A)所含的各成分之莫耳比，換算成含有率(質量%)。<Composition in the carboxyl group-containing polyester (A)> The component (A) was dissolved in deuterated chloroform or deuterated dimethyl hydrazine, and subjected to 1 H-NMR analysis using a NMR apparatus 400-MR manufactured by VARIAN Co., Ltd. The molar ratio of each component contained in the carboxyl group-containing polyester (A) was converted into a content ratio (% by mass).

＜數量平均分子量＞ 以四氫呋喃溶解及/或稀釋(A)成分，使得樹脂濃度成為0.5質量%左右，以孔徑0.5μm之聚四氟乙烯製薄膜濾紙過濾所得到之濾過物做為測定用試料，以四氫呋喃做為移動相，藉由以示差折射計做偵測器之凝膠滲透層析儀(GPC)來測定分子量。流速設定為1mL/分、管柱溫度設定為30℃。管柱為使用昭和電工製KF-802、804L、806L。標準分子量係使用單分散聚苯乙烯。<Average average molecular weight> The filtrate obtained by filtering and concentrating the component (A) in tetrahydrofuran to a resin concentration of about 0.5% by mass and filtering the membrane paper of a polytetrafluoroethylene having a pore diameter of 0.5 μm is used as a sample for measurement. The molecular weight was determined by using a tetrahydrofuran as a mobile phase and a gel permeation chromatography (GPC) using a differential refractometer as a detector. The flow rate was set to 1 mL/min, and the column temperature was set to 30 °C. The column is made of KF-802, 804L, and 806L manufactured by Showa Denko. The standard molecular weight uses monodisperse polystyrene.

＜酸價＞ 將(A)成分0.2g溶解於20ml的N-甲基吡咯烷酮，以0.1N之氫氧化鉀乙醇溶液進行滴定，求出平均每106 g之(A)成分的當量(當量/106 g)。<Acid value> 0.2 g of the component (A) was dissolved in 20 ml of N-methylpyrrolidone, and titrated with a 0.1 N potassium hydroxide ethanol solution to obtain an equivalent of (A) component per equivalent of 10 6 g (equivalent/ 10 6 g).

＜熱硬化性＞ 按照使得乾燥後的厚度成為20μm的方式，將在實施例、比較例等所得到的熱硬化性樹脂組成物塗布在厚度為18μm的電解銅箔之光澤面、及聚醯亞胺薄膜((股)宇部興產製、UBREX-50S)。經熱風乾燥80℃×30分之後，在空氣環境下，於120℃加熱60分鐘而得到形成有硬化被膜之積層體(以下，稱為積層體)。以將由此積層體所切割成5.0cm×10cm大小之物體做為試驗片。 在測定丙酮浸漬前的試驗片之質量後，將試驗片浸漬於室溫之100ml的丙酮中歷60分鐘。對於浸漬後的試驗片，於100℃乾燥60分鐘完成時，測定質量，以質量之殘留率做為凝膠分率。 凝膠分率(質量%)=[(丙酮浸漬後之質量-電解銅箔之質量)/(丙酮浸漬前之質量-電解銅箔之質量)]×100<Thermosetting property> The thermosetting resin composition obtained in the examples and the comparative examples was applied to a glossy surface of an electrolytic copper foil having a thickness of 18 μm, and a polystyrene film, so that the thickness after drying was 20 μm. Amine film ((share) Ubetsu, UBREX-50S). After drying at 80 ° C for 30 minutes by hot air, the laminate was heated at 120 ° C for 60 minutes in an air atmosphere to obtain a laminate having a cured film (hereinafter referred to as a laminate). An object cut into a size of 5.0 cm × 10 cm by the laminated body was used as a test piece. After the mass of the test piece before acetone impregnation was measured, the test piece was immersed in 100 ml of acetone at room temperature for 60 minutes. When the test piece after immersion was dried at 100 ° C for 60 minutes, the mass was measured, and the residual ratio of the mass was used as the gel fraction. Gel fraction (% by mass) = [(mass after acetone impregnation - mass of electrolytic copper foil) / (mass before acetone impregnation - mass of electrolytic copper foil)] × 100

＜可撓性＞ 基於JIS K5600-5-1：1999之標準，使用芯軸為直徑2mm之物，於溫度為23℃±2℃、相對溼度條件為(50±5)%的條件下進行試驗。 將前述之芯軸安裝在試驗裝置上，更進一步地按照使得硬化被膜面成為在外側的方式，來彎折前述之積層體的試驗片(5.0cm×10cm)。試驗裝置之彎折為均等地進行1~2秒。在將試驗片彎折180°時，評估有無發生龜裂。 ○:未發生龜裂 ×:有發生龜裂<Flexibility> Based on the standard of JIS K5600-5-1:1999, a mandrel with a diameter of 2 mm is used, and the test is carried out under the conditions of a temperature of 23 ° C ± 2 ° C and a relative humidity condition of (50 ± 5) %. . The mandrel described above was attached to the test apparatus, and the test piece (5.0 cm × 10 cm) of the above-mentioned laminated body was bent so that the surface of the hardened film was made to be outside. The bending of the test device was performed uniformly for 1 to 2 seconds. When the test piece was bent by 180°, it was evaluated whether or not cracking occurred. ○: No crack occurred ×: Cracking occurred

＜銅箔密接性＞ 對於前述之積層體，基於JIS K5600-5-6：1999之標準，在溫度23℃±2℃、相對溼度(50±5)%之條件下進行試驗。在前述的積層體之硬化被膜層上，以1mm間隔形成10方格×10方格之合計100方格的交錯體，以目視觀察剝離透明膠帶後所殘留之硬化被膜的樣子。另外，剝離用膠帶係使用NICHIBAN(股)社製。 ○：棋盤格的數量為完全殘留的情況 △：棋盤格的數量為殘留50個以上且小於100個的情況 ×：棋盤格的數量為只殘留小於50個的情況<Copper Foil Adhesiveness> The above laminate was tested under the conditions of a temperature of 23 ° C ± 2 ° C and a relative humidity (50 ± 5)% based on the standard of JIS K5600-5-6:1999. On the hardened film layer of the above-mentioned laminated body, a total of 100 squares of interlaced bodies of 10 squares × 10 squares were formed at intervals of 1 mm, and the appearance of the cured film remaining after peeling off the transparent tape was visually observed. Moreover, the tape for peeling is manufactured by NICHIBAN Co., Ltd.. ○: The number of checkerboards is completely residual. △: The number of checkerboards is 50 or more and less than 100. ×: The number of checkerboards is less than 50.

＜長期絕緣信賴性＞ 在使用#200網目之不銹鋼製網版、由撓性敷銅積層板(商品名：UPISEL-N BE1310(等級名)、宇部興產(股)製)經蝕刻而成的櫛型基板(銅配線幅/銅配線間幅=20μm/20μm)(圖2)上，以#100網目聚酯版網版，藉由印刷塗布熱硬化性樹脂組成物，於80℃經乾燥30分鐘之後，再於120℃進行熱硬化1小時。該基板，於85℃、相對溼度85%之環境下，施加60V的偏向電壓，放置1000小時，按照以下之基準評估長期絕緣信賴性。 ○：無移位(migration)、且絕緣電阻值≧108 Ω ×：在1000小時以下移位、或絕緣電阻值＜108 Ω<Long-term insulation reliability> It is etched using a stainless steel mesh plate made of #200 mesh and a flexible copper-clad laminate (trade name: UPISEL-N BE1310 (grade name), Ube Industries Co., Ltd.) On the 栉-type substrate (copper wiring width / copper wiring width = 20 μm / 20 μm) (Fig. 2), the thermosetting resin composition was applied by printing with a #100 mesh polyester screen, and dried at 80 ° C. After a minute, heat hardening was further carried out at 120 ° C for 1 hour. The substrate was subjected to a bias voltage of 60 V at 85 ° C and a relative humidity of 85%, and left for 1000 hours, and the long-term insulation reliability was evaluated according to the following criteria. ○: no migration, and insulation resistance value ≧10 8 Ω ×: shifting under 1000 hours, or insulation resistance value <10 8 Ω

＜耐鍍敷性＞ 對於在厚度25μm之聚醯亞胺薄膜上積層有厚度12μm的銅箔之片面積層聚醯亞胺薄膜所構成之印刷基板〔UBREX(註冊商標)N、宇部興產(股)製〕，以酸性脱脂劑AC-401進行洗淨，在水洗後，於70℃乾燥3分鐘之物，以#100網目聚酯版，藉由網版印刷，塗布熱硬化性樹脂組成物。於80℃讓它乾燥30分鐘之後，於120℃熱硬化1小時，經水洗之後，再於23℃之ICP克林91中浸漬、水洗1分鐘，於23℃之10%硫酸水溶液中浸漬1分鐘之後，再進行水洗。將洗淨後的基板浸漬於70℃的錫鍍敷液(TINPOSIT LT-34、羅門哈斯社製)歷3分鐘，水洗之後，再於70℃的溫水中浸漬3分鐘。於120℃熱處理經鍍敷後的基板歷2小時之後，以目視觀察硬化被膜，按照以下的基準評估耐鍍敷性。 ○：硬化被膜未變色、並且無鍍敷潛沉 ×：硬化被膜有變色、或者有鍍敷潛沉<Plastic plating resistance> A printed circuit board composed of a polyimide film of a copper foil having a thickness of 12 μm laminated on a polyimide film having a thickness of 25 μm [UBREX (registered trademark) N, Ube Hiroshi (shares) The system was washed with an acidic degreaser AC-401, and after washing with water, it was dried at 70 ° C for 3 minutes, and a thermosetting resin composition was applied by screen printing using a #100 mesh polyester plate. After drying at 80 ° C for 30 minutes, it was thermally cured at 120 ° C for 1 hour, washed with water, then immersed in ICP Klin 91 at 23 ° C, washed with water for 1 minute, and immersed in a 10% sulfuric acid aqueous solution at 23 ° C for 1 minute. After that, it is washed again. The washed substrate was immersed in a tin plating solution (TINPOSIT LT-34, manufactured by Rohm and Haas) at 70 ° C for 3 minutes, washed with water, and further immersed in warm water of 70 ° C for 3 minutes. After the plated substrate was heat-treated at 120 ° C for 2 hours, the cured film was visually observed, and the plating resistance was evaluated according to the following criteria. ○: The hardened film is not discolored, and there is no plating. ×: The hardened film is discolored, or there is plating.

＜熱硬化性樹脂組成物的總固態成分中之一般式[I]的重複構造之含有率＞ 求得熱硬化性樹脂組成物的總固態成分中之含羧基聚酯(A)的含有率(質量%)，從含羧基聚酯(A)中所含的一般式[I]之重複構造的莫耳比，來計算出熱硬化性樹脂組成物之總固態成分中的一般式[I]之重複構造的含有率(質量%)。<Content ratio of the repeating structure of the general formula [I] in the total solid content of the thermosetting resin composition> The content ratio of the carboxyl group-containing polyester (A) in the total solid content of the thermosetting resin composition is determined ( (% by mass), from the molar ratio of the repeating structure of the general formula [I] contained in the carboxyl group-containing polyester (A), the general formula [I] in the total solid content of the thermosetting resin composition was calculated. The content rate (% by mass) of the repeating structure.

＜合成例1-1＞ 在裝設有攪拌器及溫度計的四口燒瓶中，加入114.84g(0.28莫耳)之做為四羧酸二酐之乙二醇雙(偏苯三酸酐)(新日本理化(股)製RIKACYD TMEG-100)、與294.60g(0.29莫耳)之做為聚碳酸酯二醇之C-1015N(可樂麗(股)製聚碳酸酯二醇、原料二醇莫耳比：1,9-壬二醇/2-甲基-1,8-辛二醇=15/85、分子量1000)、與409.44g之做為溶劑之γ-丁內酯(三菱化學(股)製)，在其中添加1.71g之做為觸媒之4-二甲基胺基吡啶(中合科技製)，氮氣流下使之起反應100℃×6小時。然後，冷卻到室溫而得到固體成分濃度為50質量%之含羧基聚酯。該聚合物的組成與物性係表示於表1。<Synthesis Example 1-1> In a four-necked flask equipped with a stirrer and a thermometer, 114.84 g (0.28 mol) of ethylene glycol bis(trimellitic anhydride) as tetracarboxylic dianhydride was added (New Japan Physical and Chemical ( RIKACYD TMEG-100), with 294.60g (0.29 mole) of C-1015N as a polycarbonate diol (carbonate diol made from Kuraray), raw material diol molar ratio: 1 , 9-nonanediol/2-methyl-1,8-octanediol=15/85, molecular weight 1000), and 409.44 g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent, 1.71 g of 4-dimethylaminopyridine (manufactured by Nikken Co., Ltd.) as a catalyst was added thereto, and the reaction was carried out at 100 ° C for 6 hours under a nitrogen stream. Then, it was cooled to room temperature to obtain a carboxyl group-containing polyester having a solid concentration of 50% by mass. The composition and physical properties of the polymer are shown in Table 1.

＜合成例1-2、1-3、1-4、1-5＞ 除了按照如表1所示變更聚碳酸酯二醇以外，與合成例1同樣地製作而得到各種的含羧基聚酯。此等之聚合物的組成與物性為表示於表1。<Synthesis Example 1-2, 1-3, 1-4, 1-5> Various carboxyl group-containing polyesters were obtained in the same manner as in Synthesis Example 1 except that the polycarbonate diol was changed as shown in Table 1. The composition and physical properties of these polymers are shown in Table 1.

＜合成例1-6、1-7、1-8、1-9＞ 除了按照如表1所示變更四羧酸二酐以外，與合成例1同樣地製作而得到各種的含羧基聚酯。此等之聚合物的組成與物性為表示於表1。<Synthesis Examples 1-6, 1-7, 1-8, and 1-9> Various carboxyl group-containing polyesters were obtained in the same manner as in Synthesis Example 1 except that the tetracarboxylic dianhydride was changed as shown in Table 1. The composition and physical properties of these polymers are shown in Table 1.

在表1中之簡略記號的意義為如以下之記載所示。 TMEG：乙二醇雙(偏苯三酸酐) BPDA：3,3’,4,4’-二苯基四羧酸二酐 PMDA：均苯四甲酸二酐 BTDA：3,3’,4,4’-二苯甲酮四羧酸二酐 ODPA：4,4’-氧二酞酸二酐 C1015N：可樂麗(股)製聚碳酸酯二醇(1,9-壬二醇/2-甲基-1,8-辛二醇=15/85)、數量平均分子量為約1000 C1065N：可樂麗(股)製聚碳酸酯二醇(1,9-壬二醇/2-甲基-1,8-辛二醇=65/35)、數量平均分子量為約1000 C1050：可樂麗(股)製聚碳酸酯二醇(3-甲基-1,5-戊二醇/1,6-己二醇=50/50)、數量平均分子量為約1000 C1090：可樂麗(股)製聚碳酸酯二醇(3-甲基-1,5-戊二醇/1,6-己二醇=90/10)、數量平均分子量為約1000 T5651：旭化成化學品(股)製聚碳酸酯二醇(1,5-戊二醇/1,6-己二醇=50/50)、數量平均分子量為約1000The meaning of the abbreviations in Table 1 is as shown in the following description. TMEG: ethylene glycol bis(trimellitic anhydride) BPDA: 3,3',4,4'-diphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride BTDA: 3,3',4,4'- Benzene ketone tetracarboxylic dianhydride ODPA: 4,4'-oxydiphthalic acid dianhydride C1015N: polycarbonate diol (1,9-nonanediol/2-methyl-1, manufactured by Kuraray Co., Ltd.) 8-octanediol = 15/85), the number average molecular weight is about 1000 C1065N: a polycarbonate diol made of Kuraray (1,9-nonanediol/2-methyl-1,8-octane) Alcohol = 65/35), the number average molecular weight is about 1000 C1050: a polycarbonate diol made of Kuraray (3-methyl-1,5-pentanediol/1,6-hexanediol = 50/ 50), the number average molecular weight is about 1000 C1090: polycarbonate diol (3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10) manufactured by Kuraray Co., Ltd. The average molecular weight is about 1000 T5651: Polycarbonate diol (1,5-pentanediol/1,6-hexanediol = 50/50) made from Asahi Kasei Chemicals Co., Ltd., and the number average molecular weight is about 1,000.

＜比較合成例2-1＞ 在裝設有攪拌器及溫度計的四口燒瓶中，加入170.89g(0.42莫耳)之做為四羧酸二酐之乙二醇雙(偏苯三酸酐)(新日本理化(股)製RIKACYDTMEG-100)、與35.01g(0.20莫耳)之做為二異氰酸酯化合物之2,4-甲苯二異氰酸酯(日本聚胺基甲酸酯(股)製冠羅納特T-100)、與349.51g之做為溶劑之γ-丁內酯(三菱化學(股)製)，在其中添加0.31g之做為觸媒之1,8-二氮雜二環[5.4.0]-7-十一烯(中合科技製)，使之起反應130℃×2小時。接著，經冷卻到室溫以後，添加248.50g(0.25莫耳)之做為聚碳酸酯二醇之C-1015N(可樂麗(股)製聚碳酸酯二醇、原料二醇莫耳比：1,9-壬二醇/2-甲基-1,8-辛二醇=15/85、分子量1000)、與87.19g之做為溶劑之γ-丁內酯(三菱化學(股)製)，在其中添加2.63g之做為觸媒之4-甲基胺基吡啶(中合科技製)，在氮氣流下使之起反應100℃×6小時。然後，藉由到冷卻室溫而得到固體成分濃度為50質量%之含羧基聚酯醯亞胺。此聚合物之組成與物性為表示於表2。<Comparative Synthesis Example 2-1> In a four-necked flask equipped with a stirrer and a thermometer, 170.89 g (0.42 mol) of ethylene glycol bis(trimellitic anhydride) as tetracarboxylic dianhydride was added (New Japan Physical and Chemical) (R) RIKACYDTM EG-100), with 35.01g (0.20 mole) of 2,4-toluene diisocyanate as a diisocyanate compound (Japan Polyurethane Co., Ltd.) And 349.51g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent, and 0.31 g of 1,8-diazabicyclo[5.4.0] as a catalyst is added thereto. 7-undecene (manufactured by Zhonghe Technology Co., Ltd.) was allowed to react at 130 ° C for 2 hours. Then, after cooling to room temperature, 248.50 g (0.25 mol) of C-1015N as a polycarbonate diol (carbonate diol made of Kuraray, raw material diol molar ratio: 1) was added. , 9-nonanediol/2-methyl-1,8-octanediol=15/85, molecular weight 1000), and 87.19 g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent, To this was added 2.63 g of 4-methylaminopyridine (manufactured by Nikken Co., Ltd.) as a catalyst, and the reaction was carried out at 100 ° C for 6 hours under a nitrogen stream. Then, by cooling to room temperature, a carboxyl group-containing polyester quinone having a solid concentration of 50% by mass was obtained. The composition and physical properties of this polymer are shown in Table 2.

＜比較合成例2-2＞ 在裝設有攪拌器及溫度計的四口燒瓶中，加入214.17g(0.52莫耳)之做為四羧酸二酐之乙二醇雙(偏苯三酸酐)(新日本理化(股)製RIKACYDTMEG-100)、與1353.00g(0.45莫耳)之做為聚碳酸酯二醇之C-3090(可樂麗(股)製聚碳酸酯二醇、原料二醇莫耳比：1,6-己二醇/3-甲基-1,5-戊二醇=10/90、分子量3000)、與1567.17g之做為溶劑之γ-丁內酯(三菱化學(股)製)，在其中添加3.19g之做為觸媒之4-二甲基胺基吡啶(中合科技製)，在氮氣流下使之起反應100℃×6小時。然後，藉由冷卻到室溫而得到固體成分濃度為50質量%之含羧基聚酯。所得到的聚合物之組成與物性為表示於表2。<Comparative Synthesis Example 2-2> In a four-necked flask equipped with a stirrer and a thermometer, 214.17 g (0.52 mol) of ethylene glycol bis(trimellitic anhydride) as tetracarboxylic dianhydride was added (New Japan Physical and Chemical) (R) RIKACYDTM EG-100), with 1353.00g (0.45m) of C-3090 as polycarbonate diol (Cola diol polycarbonate diol, raw material diol molar ratio: 1 , 6-hexanediol/3-methyl-1,5-pentanediol=10/90, molecular weight 3000), and 1567.17g of γ-butyrolactone (Mitsubishi Chemical Co., Ltd.) as a solvent, 3.19 g of 4-dimethylaminopyridine (manufactured by Nikken Co., Ltd.) as a catalyst was added thereto, and the reaction was allowed to proceed at 100 ° C for 6 hours under a nitrogen stream. Then, by cooling to room temperature, a carboxyl group-containing polyester having a solid concentration of 50% by mass was obtained. The composition and physical properties of the obtained polymer are shown in Table 2.

＜比較合成例2-3＞ 在高壓釜中添加86.73g(0.52莫耳)之做為二羧酸之異酞酸(EDI國際化學(股)製)、與475.00g(0.45莫耳)之做為聚碳酸酯二醇之C-1015N(可樂麗(股)製聚碳酸酯二醇、原料二醇莫耳比：1,9-壬二醇/2-甲基-1,8-辛二醇=15/85、分子量1000)，在其中添加0.05g之做為觸媒之四-n-丁基鈦酸酯(關東化學(股)製)，使之起反應220℃×3小時。然後，花20分鐘，將前述反應系減壓到5mmHg為止，於220℃實施縮聚反應歷45分鐘。繼續冷卻到室溫為止，加入519.92g之做為溶劑之γ-丁內酯(三菱化學(股)製)，而得到固體成分濃度為50質量%的聚酯。所得到的聚合物之組成與物性表示於表2。<Comparative Synthesis Example 2-3> 86.73 g (0.52 mol) of isophthalic acid as a dicarboxylic acid (manufactured by EDI International Chemical Co., Ltd.) and 475.00 g (0.45 m) were added to the autoclave. C-1015N for polycarbonate diol (polycarbonate diol made from Kuraray), raw material diol molar ratio: 1,9-nonanediol/2-methyl-1,8-octanediol = 15/85, a molecular weight of 1000), and 0.05 g of tetra-n-butyl titanate (manufactured by Kanto Chemical Co., Ltd.) as a catalyst was added thereto to carry out a reaction at 220 ° C for 3 hours. Then, the reaction was allowed to depressurize to 5 mmHg for 20 minutes, and the polycondensation reaction was carried out at 220 ° C for 45 minutes. While continuing to cool to room temperature, 519.92 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) was added as a solvent to obtain a polyester having a solid concentration of 50% by mass. The composition and physical properties of the obtained polymer are shown in Table 2.

＜比較合成例2-4、2-5、2-6＞ 除了將聚碳酸酯二醇變更為如表2所示以外，皆與合成例1同樣地製作而得到各種的含羧基聚酯。此等之聚合物的組成與物性表示於表2。<Comparative Synthesis Examples 2-4, 2-5, and 2-6> Various polycarbonate-containing polyesters were obtained in the same manner as in Synthesis Example 1 except that the polycarbonate diol was changed to those shown in Table 2. The composition and physical properties of these polymers are shown in Table 2.

＜P含有二醇之合成：比較合成例2-6＞ 比較合成例2-6所使用的(D)成分之P含有二醇為按照以下的順序而合成。 將21.27g(0.18莫耳)之1,6-己二醇(宇部興產(股)製)、33.84g(0.18莫耳)之n-丁基-雙(3-羥基丙基)氧化膦(PO-4500、含磷二醇、日本化學工業製)、57.84g(0.27莫耳)之二苯基碳酸酯(東京化成工業(股)製)、0.09g之觸媒之四-n-丁基鈦酸酯投入高壓釜中，升溫到220℃，確認酚已分餾出來之後，花20分鐘將前述反應系從常壓減壓到5mmHg。讓反應系於5mmHg之減壓下，一邊保持於200℃，一邊將酚分餾到反應系外，並實施80分鐘之縮聚反應。所得到的聚碳酸酯二醇之數量平均分子量為690。<P: Synthesis of diol: Comparative Synthesis Example 2-6> The P-containing diol of the component (D) used in Comparative Synthesis Example 2-6 was synthesized in the following order. 21.27 g (0.18 mol) of 1,6-hexanediol (manufactured by Ube Industries, Ltd.), 33.84 g (0.18 mol) of n-butyl-bis(3-hydroxypropyl)phosphine oxide ( PO-4500, phosphorus-containing diol, manufactured by Nippon Chemical Industry Co., Ltd., 57.84 g (0.27 mol) of diphenyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.09 g of catalyst tetra-n-butyl The titanate was placed in an autoclave, and the temperature was raised to 220 ° C. After confirming that the phenol had been fractionated, the reaction system was depressurized from normal pressure to 5 mmHg for 20 minutes. The reaction was carried out under reduced pressure of 5 mmHg, while maintaining the temperature at 200 ° C, the phenol was fractionated outside the reaction system, and a polycondensation reaction was carried out for 80 minutes. The obtained polycarbonate diol had a number average molecular weight of 690.

表2中的簡略記號之意為如以下之記載所示。 TMEG：乙二醇雙(偏苯三酸酐) IPA：異酞酸 TDI：2,4-甲苯二異氰酸酯 C1015N：可樂麗(股)製聚碳酸酯二醇(1,9-壬二醇/2-甲基-1,8-辛二醇=15/85)、數量平均分子量為約1000 T5650E：旭化成化學品(股)製聚碳酸酯二醇(1,5-戊二醇/1,6-己二醇)、數量平均分子量為約500 C3090：可樂麗(股)製聚碳酸酯二醇(3-甲基-1,5-戊二醇/1,6-己二醇=90/10)、數量平均分子量為約3000 UH-CARB100：宇部興產(股)製聚碳酸酯二醇(1,6-己二醇)、數量平均分子量為約1000The abbreviations in Table 2 are as shown in the following description. TMEG: ethylene glycol bis(trimellitic anhydride) IPA: isophthalic acid TDI: 2,4-toluene diisocyanate C1015N: polycarbonate diol (1,9-nonanediol/2-methyl-) 1,8-octanediol = 15/85), the number average molecular weight is about 1000 T5650E: Polycarbonate diol (1,5-pentanediol/1,6-hexanediol) made from Asahi Kasei Chemicals Co., Ltd. The number average molecular weight is about 500 C3090: a polycarbonate diol (3-methyl-1,5-pentanediol/1,6-hexanediol = 90/10) manufactured by Kuraray Co., Ltd., and a number average molecular weight It is about 3000 UH-CARB100: Polycarbonate diol (1,6-hexanediol) manufactured by Ube Industries Co., Ltd., and the number average molecular weight is about 1,000.

＜實施例1＞ 相對於100質量份之在合成例1-1所得到的含羧基聚酯之樹脂分，添加50質量份之HP-7200H(DIC(股)製含有二環戊二烯之酚酚醛清漆型環氧樹脂的商品名)，以γ-丁內酯進行稀釋。更進一步地，加入2.1質量份之做為硬化促進劑的UCAT-5002(三阿波羅(股)製)，一邊以γ-丁內酯進行調整，一邊以三輥研磨機((股)小平製作所製、型式:RIII-1RM-2)混練3次，而得到固體成分濃度為52質量%之熱硬化性樹脂組成物。按照使得乾燥後的厚度成為20μm的方式，將所得到的熱硬化性樹脂組成物塗布於厚度為18μm的電解銅箔之光澤面、聚醯亞胺薄膜((股)宇部興產製、UBREX-50S)上。熱風乾燥80℃×30分鐘之後，在空氣環境下，於120℃加熱60分鐘而得到形成有硬化被膜的積層體。所得到的熱硬化性樹脂組成物之組成與硬化被膜的物性表示於表3。<Example 1> 50 parts by mass of HP-7200H (DIC-containing dicyclopentadiene-containing phenol) was added to 100 parts by mass of the resin component of the carboxyl group-containing polyester obtained in Synthesis Example 1-1. The novolak type epoxy resin is traded as γ-butyrolactone. Furthermore, 2.1 parts by mass of UCAT-5002 (manufactured by Tri-Apollo) was added as a hardening accelerator, and while being adjusted with γ-butyrolactone, a three-roll mill was used. The system and the formula: RIII-1RM-2) were kneaded three times to obtain a thermosetting resin composition having a solid content concentration of 52% by mass. The obtained thermosetting resin composition was applied to a glossy surface of an electrolytic copper foil having a thickness of 18 μm, and a polyimide film (manufactured by Ube Industries, UBREX-) so that the thickness after drying was 20 μm. 50S). After hot air drying at 80 ° C for 30 minutes, the laminate was heated at 120 ° C for 60 minutes in an air atmosphere to obtain a layered body in which a cured film was formed. The composition of the obtained thermosetting resin composition and the physical properties of the cured film are shown in Table 3.

＜實施例2~9、比較例1~6＞ 除了變更為如表3記載之組成以外，皆和實施例1同樣地製作熱硬化性樹脂組成物，而得到形成有硬化被膜之積層體。所得到的熱硬化性樹脂組成物之組成與硬化被膜之物性表示於表3。<Examples 2 to 9 and Comparative Examples 1 to 6> A thermosetting resin composition was produced in the same manner as in Example 1 except that the composition shown in Table 3 was changed, and a laminate in which a cured film was formed was obtained. The composition of the obtained thermosetting resin composition and the physical properties of the cured film are shown in Table 3.

〈表3〉 <table 3>

在表3中之簡略記號的意義為如以下之記載所示。 HP-7200H：DIC(股)製、含有二環戊二烯之酚酚醛清漆型環氧樹脂 JER-152：三菱化學(股)製、酚酚醛清漆型環氧樹脂 YDCN-701：新日鐵化學(股)製、甲酚酚醛清漆型環氧樹脂 UCAT-5002：三阿波羅(股)製硬化促進劑、DBU系四苯基溴酸鹽The meaning of the abbreviations in Table 3 is as shown in the following description. HP-7200H: DIC (stock), phenol novolac type epoxy resin containing dicyclopentadiene JER-152: Mitsubishi Chemical Co., Ltd., phenol novolac type epoxy resin YDCN-701: Nippon Steel Chemical Co., Ltd. (stock) system, cresol novolac type epoxy resin UCAT-5002: tri-Apollo (strand) hardening accelerator, DBU tetraphenyl bromide

從表3明顯可知：在實施例1~9中皆顯示熱硬化性全部均為90質量%以上，而長期絕緣信賴性也全部都是良好的；又，可撓性、耐鍍敷性、銅箔密接性也是全部良好的。即，藉由含有滿足本發明之要件的含羧基聚酯之熱硬化性樹脂組成物所得到硬化被膜，顯示出熱硬化性、長期絕緣信賴性、可撓性、耐鍍敷性、及銅箔密接性之全部皆為良好的評估結果。As is apparent from Table 3, in all of Examples 1 to 9, all of the thermosetting properties were 90% by mass or more, and the long-term insulation reliability was also good; and flexibility, plating resistance, and copper. The foil adhesion is also all good. In other words, the cured film obtained by the thermosetting resin composition containing the carboxyl group-containing polyester which satisfies the requirements of the present invention exhibits thermosetting properties, long-term insulation reliability, flexibility, plating resistance, and copper foil. All of the adhesions are good evaluation results.

在比較例1中，由於聚合物酸價稍微低，因而賦與銅箔密接性之環氧樹脂的摻混量，就不能夠被提高到相對於100質量份之樹脂分而言為40質量份以上。從而，銅箔與硬化被膜間作動之分子間力就減低而致使銅箔密接性變為不佳。更且，可確認到鍍敷液從銅箔與硬化被膜界面滲入痕跡，以致耐鍍敷性不佳。In Comparative Example 1, since the acid value of the polymer is slightly lower, the blending amount of the epoxy resin imparting the adhesion to the copper foil cannot be increased to 40 parts by mass with respect to 100 parts by mass of the resin component. the above. Therefore, the intermolecular force acting between the copper foil and the hardened film is reduced, resulting in poor adhesion of the copper foil. Further, it was confirmed that the plating solution penetrated from the interface between the copper foil and the hardened film, so that the plating resistance was poor.

在比較例2也是因為和比較例1同樣的理由而導致銅箔密接性、耐鍍敷性不佳。更且，所使用的聚碳酸酯二醇(3-甲基-1,5-戊二醇/1,6-己二醇=90/10)的數量平均分子量為高到約3000，所以耐熱性減低、長期絕緣信賴性不佳。Also in Comparative Example 2, the copper foil adhesion and plating resistance were not good for the same reason as in Comparative Example 1. Furthermore, the polycarbonate diol (3-methyl-1,5-pentanediol/1,6-hexanediol = 90/10) used has a number average molecular weight of up to about 3,000, so heat resistance Reduced, long-term insulation reliability is not good.

在比較例3中，由於聚合物中的羧基為只在樹脂末端，所以酸價減低、熱硬化性成為73質量%，因而是不佳的。至於銅箔密接性、耐鍍敷性、長期絕緣信賴性，也和比較例2同樣是不佳的。In Comparative Example 3, since the carboxyl group in the polymer was only at the resin end, the acid value was lowered and the thermosetting property was 73% by mass, which was not preferable. Copper foil adhesion, plating resistance, and long-term insulation reliability were also inferior to Comparative Example 2.

在比較例4中，因為是由具有僅1種類的伸烷基之聚碳酸酯二醇所共聚合而成的含羧基聚酯，所以樹脂的結晶性變高、硬化被膜的可撓性不佳。In Comparative Example 4, since the carboxyl group-containing polyester is obtained by copolymerization of a polycarbonate diol having only one type of alkylene group, the crystallinity of the resin is high, and the flexibility of the cured film is poor. .

在比較例5中，由於聚碳酸酯二醇的數量平均分子量為低到500，所以能賦與柔軟特性之聚碳酸酯二醇的質量比例減少、硬化被膜的可撓性不佳。In Comparative Example 5, since the number average molecular weight of the polycarbonate diol was as low as 500, the mass ratio of the polycarbonate diol which imparts soft characteristics was reduced, and the flexibility of the cured film was not good.

在比較例6中，因為含P的二醇的耐加氫分解性不佳，所以長期絕緣信賴性亦不佳。In Comparative Example 6, since the hydrogen-decomposing property of the P-containing diol was not good, the long-term insulation reliability was also poor.

＜合成例3-1、3-2、3-3、3-4、3-5、3-6、3-7＞ 除了按照如表4所示變更四羧酸二酐、聚乙二醇以外，皆與合成例1同樣製作而得到各種的含羧基聚酯。此等之聚合物的組成與物性表示於表4。<Synthesis Example 3-1, 3-2, 3-3, 3-4, 3-5, 3-6, 3-7> In addition to changing tetracarboxylic dianhydride or polyethylene glycol as shown in Table 4 All of the carboxyl group-containing polyesters were obtained in the same manner as in Synthesis Example 1. The composition and physical properties of these polymers are shown in Table 4.

在表4中之簡略記號的意義為如以下之記載所示。 PTMG1000：(股)三菱化學製聚四亞甲基醚二醇、數量平均分子量為約1000 P-1010：可樂麗(股)製聚酯二醇(3-甲基-1,5-戊二醇//己二酸)、數量平均分子量為約1000 P-1050：可樂麗(股)製聚酯二醇(3-甲基-1,5-戊二醇//癸二酸)、數量平均分子量為約1000 其他的簡略記號之意義為和表1~3所記載之簡略記號之意味相同。The meanings of the abbreviations in Table 4 are as shown in the following description. PTMG1000: (shares) Mitsubishi Chemical polytetramethylene ether glycol, number average molecular weight of about 1000 P-1010: Keleli (stock) polyester diol (3-methyl-1,5-pentanediol / / adipic acid), the number average molecular weight is about 1000 P-1050: polyester diol (3-methyl-1,5-pentanediol / / azelaic acid) made from Kuraray, the number average molecular weight The meaning of about 1000 other abbreviations is the same as the abbreviations shown in Tables 1-3.

＜比較合成例4-1、4-2、4-3＞ 除了按照如表5所示來變更四羧酸二酐、聚乙二醇以外，皆與合成例1同樣製作而得到各種的含羧基聚酯。此等之聚合物的組成與物性表示於表5。<Comparative Synthesis Examples 4-1, 4-2, and 4-3> Various types of carboxyl groups were obtained in the same manner as in Synthesis Example 1 except that the tetracarboxylic dianhydride and polyethylene glycol were changed as shown in Table 5. Polyester. The composition and physical properties of these polymers are shown in Table 5.

在表5中之簡略記號的意義為如以下之記載所示。 PNOA1010：可樂麗(股)製聚酯二醇(1,9-壬二醇/2-甲基-1,8-辛二醇=65/35//己二酸)、數量平均分子量為約1000 PTXG1000：旭化成纖維(股)製四氫呋喃/新戊二醇共聚物聚醚二醇、數量平均分子量為約1000 其他的簡略記號之意義為和表1~4所記載之簡略記號之意義相同。The meaning of the abbreviations in Table 5 is as shown in the following description. PNOA1010: a polyester diol made of Kuraray (1,9-nonanediol/2-methyl-1,8-octanediol=65/35//adipic acid), and having a number average molecular weight of about 1,000 PTXG1000: Asahi Kasei Fiber Co., Ltd. produces tetrahydrofuran/neopentyl glycol copolymer polyether diol, and the number average molecular weight is about 1000. The meanings of other abbreviations are the same as those in Tables 1-4.

＜實施例10~17、比較例7~10＞ 除了變更為如表6記載之組成以外，皆和實施例1同樣地製作熱硬化性樹脂組成物，而得到形成有硬化被膜之積層體。所得到的熱硬化性樹脂組成物之組成與硬化被膜的物性表示於表6。另外，表6中的簡略記號之意義為和表1~5所記載之簡略記號的意味相同。(Examples 10 to 17 and Comparative Examples 7 to 10) A thermosetting resin composition was produced in the same manner as in Example 1 except that the composition shown in Table 6 was changed, and a laminate in which a cured film was formed was obtained. The composition of the obtained thermosetting resin composition and the physical properties of the cured film are shown in Table 6. In addition, the meaning of the abbreviations in Table 6 is the same as the meaning of the abbreviations shown in Tables 1 to 5.

〈表6〉 <Table 6>

由表6明顯可知：在實施例10~17顯示熱硬化性全部分是在90質量%以上，長期絕緣信賴性也全部都是良好的。又。可撓性、耐鍍敷性、銅箔密接性也全部是良好的。即，藉由含有滿足本發明之要件的含羧基聚酯之熱硬化性樹脂組成物所得到的硬化被膜，顯示出在熱硬化性、長期絕緣信賴性、可撓性、耐鍍敷性、及銅箔密接性上全部都是良好的評估結果。As is apparent from Table 6, in Examples 10 to 17, all of the thermosetting properties were 90% by mass or more, and the long-term insulation reliability was also good. also. Flexibility, plating resistance, and copper foil adhesion were all good. In other words, the cured film obtained by the thermosetting resin composition containing the carboxyl group-containing polyester which satisfies the requirements of the present invention exhibits thermosetting properties, long-term insulation reliability, flexibility, plating resistance, and The copper foil adhesion is all good evaluation results.

在比較例7、10中，由於含羧基聚酯(A)中之一般式[I]的重複構造之含有率減低、多半含有具有僅1種類的伸烷基的聚碳酸酯二醇，所以樹脂的結晶性變高、硬化被膜之可撓性不佳。In Comparative Examples 7 and 10, since the content ratio of the repeating structure of the general formula [I] in the carboxyl group-containing polyester (A) is lowered, and most of the polycarbonate diol having only one type of alkylene group is contained, the resin The crystallinity is high and the flexibility of the cured film is not good.

在比較例8、9中，同樣地由於在含羧基聚酯(A)中之一般式[I]的重複構造之含有率減低、多半含有長期絕緣信賴性不佳的聚酯多醇，所以硬化被膜的長期絕緣信賴性不佳。 《產業上利用之可能性》In Comparative Examples 8 and 9, the content of the repeating structure of the general formula [I] in the carboxyl group-containing polyester (A) was reduced, and most of the polyester polyols having poor long-term insulation reliability were hardened. The long-term insulation reliability of the film is not good. "The possibility of industrial use"

根據本發明，就能夠提供可得到同時且高度地符合熱硬化性、長期絕緣信賴性、耐鍍敷性、銅箔(基材)密接性、可撓性、作業性要求之硬化物的含羧基聚酯。此外，當將本發明的含羧基聚酯與熱硬化劑一起組合來使用時，就能夠形成高度的交聯構造、且能夠得到強靭的硬化被膜。從而，本發明之含羧基聚酯，由於高度地符合上述特性之要求，所以能夠非常適合使用於光阻印墨、接合劑、使用該等之汽車零件、電化製品等之印刷電路基板等；是以可期待能夠對於產業界提供大大的貢獻。According to the present invention, it is possible to provide a carboxyl group containing a cured product which simultaneously satisfies the requirements of thermosetting property, long-term insulation reliability, plating resistance, copper foil (substrate) adhesion, flexibility, and workability. Polyester. Further, when the carboxyl group-containing polyester of the present invention is used in combination with a heat curing agent, a highly crosslinked structure can be formed and a tough cured film can be obtained. Therefore, the carboxyl group-containing polyester of the present invention can be suitably used for a photoresist ink, a bonding agent, a printed circuit board using such an automobile part or an electrochemical product, etc., because it satisfies the above requirements. It is expected to provide a great contribution to the industry.

無。no.

圖1為顯示(C)成分之酸酐基、與(D)成分之羥基的反應樣式之說明圖。 圖2為顯示在實施例中由測定長期絕緣信賴性用的撓性銅張積層板經蝕刻而成的櫛型基板之說明圖。Fig. 1 is an explanatory view showing a reaction pattern of an acid anhydride group of the component (C) and a hydroxyl group of the component (D). 2 is an explanatory view showing a ruthenium-type substrate obtained by etching a flexible copper laminate layer for measuring long-term insulation reliability in the examples.

Claims (9)

一種含羧基聚酯，其係具有以下(a)~(d)之特徴： (a) 具有一般式[I]之重複構造，R1 及R2 係分別為以下之(i)~(ii)；(i) R1 為從四羧酸二酐除去酸酐基而得之有機基，其也可以含有取代基，具有碳數1~30之芳香族基、脂環族基、脂肪族基、或雜環之基；(ii) R2 為從聚碳酸酯二醇除去羥基而得之有機基，但該聚碳酸酯二醇係具有複數種的伸烷基，該聚碳酸酯二醇的數量平均分子量為700~2300；(b) 數量平均分子量為超過10000且在50000以下；(c) 樹脂酸價為1200當量/106 g以上；(d) 含羧基聚酯中之一般式[I]的重複構造之含有率為68質量%以上；。A carboxyl group-containing polyester having the following characteristics (a) to (d): (a) having a repeating structure of the general formula [I], and the R 1 and R 2 systems are respectively (i) to (ii) (i) R 1 is an organic group obtained by removing an acid anhydride group from a tetracarboxylic dianhydride, and may also have a substituent, having an aromatic group having 1 to 30 carbon atoms, an alicyclic group, an aliphatic group, or a heterocyclic group; (ii) R 2 is an organic group obtained by removing a hydroxyl group from a polycarbonate diol, but the polycarbonate diol has a plurality of alkylene groups, and the number of the polycarbonate diol is average The molecular weight is 700 to 2300; (b) the number average molecular weight is more than 10,000 and less than 50,000; (c) the resin acid value is 1200 equivalents/10 6 g or more; (d) the general formula [I] in the carboxyl group-containing polyester The content of the repeating structure is 68% by mass or more; . 如請求項1所記載之含羧基聚酯，其中前述聚碳酸酯二醇為以下(i)~(iii)中之任一種； (i)     二醇成分為由3-甲基-1,5-戊二醇、與1,6-己二醇構成之共聚合聚碳酸酯二醇、(ii)    二醇成分為由1,5-戊二醇、與1,6-己二醇構成之共聚合聚碳酸酯二醇、(iii)  二醇成分為由2-甲基-1,8-辛二醇、與1,9-壬二醇構成之共聚合聚碳酸酯二醇。The carboxyl group-containing polyester according to claim 1, wherein the polycarbonate diol is any one of the following (i) to (iii); (i) the diol component is 3-methyl-1,5- a copolymerized polycarbonate diol composed of pentanediol and 1,6-hexanediol, and (ii) a diol component which is a copolymer of 1,5-pentanediol and 1,6-hexanediol. The polycarbonate diol and the (iii) diol component are a copolymerized polycarbonate diol composed of 2-methyl-1,8-octanediol and 1,9-nonanediol. 一種熱硬化性樹脂組成物，特徵在於：其係含有如請求項1或2所記載之含羧基聚酯、與具有環氧乙烷環(Oxirane ring)之化合物。A thermosetting resin composition comprising the carboxyl group-containing polyester according to claim 1 or 2 and a compound having an oxirane ring. 如請求項3所記載之熱硬化性樹脂組成物，其中具有環氧乙烷環之化合物為含有苯酚酚醛骨架或甲酚酚醛骨架之環氧化合物。The thermosetting resin composition according to claim 3, wherein the compound having an oxirane ring is an epoxy compound containing a phenol novolac skeleton or a cresol novolak skeleton. 如請求項3或4所記載之熱硬化性樹脂組成物，其中所摻混的具有環氧乙烷環之化合物，相對於100質量份之含羧基聚酯而言為40質量份以上90質量份以下。The thermosetting resin composition according to claim 3, wherein the compound having an oxirane ring is 40 parts by mass or more and 90 parts by mass based on 100 parts by mass of the carboxyl group-containing polyester. the following. 如請求項3至5中之任一項所記載之熱硬化性樹脂組成物，其在熱硬化性樹脂組成物的總固態成分中所含之一般式[I]的重複構造之含有率為40質量%以上71質量%以下。The thermosetting resin composition according to any one of claims 3 to 5, wherein the content of the repeating structure of the general formula [I] contained in the total solid content of the thermosetting resin composition is 40. The mass% or more is 71% by mass or less. 一種被膜形成材料，特徵在於：其係含有如請求項3至6中之任一項所記載之熱硬化性樹脂組成物。A film forming material comprising the thermosetting resin composition according to any one of claims 3 to 6. 一種阻焊劑，特徵在於：其係含有如請求項3至6中之任一項所記載之熱硬化性樹脂組成物。A solder resist comprising the thermosetting resin composition according to any one of claims 3 to 6. 一種硬化被膜，特徵在於：其係藉由將如請求項3至6中之任一項所記載之熱硬化性樹脂組成物、如請求項7所記載之被膜形成材料、或如請求項8所記載之阻焊劑予以熱硬化而得。A hardening film according to any one of claims 3 to 6, wherein the film forming material according to claim 7 or the method of claim 8 The described solder resist is obtained by heat hardening.
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