TW201241081A - Thermal-curable resin composition comprising carboxyl-containing modified ester resin - Google Patents

Abstract

This invention provides a thermal-curable resin composition, which is a thermal-curable resin composition comprising (A) carboxyl-containing modified ester resin; (B) at least one compound selected from the group consisting of epoxy-containing compound isocyanate group-containing compound and blocked isocyanate group-containing compound; and (C) thermal-curable aids; wherein the (A) carboxyl-containing modified ester resin is obtained by reacting (a) polyol compound with at least one acid anhydride group-containing compound selected from alicyclic polybasic acid anhydride or aromatic polybasic acid anhydride to produce (c) carboxyl-containing ester resin; reacting (c) carboxyl-containing ester resin with (d) epoxy compound containing at least two epoxy groups per molecule to produce (e) modified ester resin containing hydroxy on its side chain; further, reacting (e) modified ester resin containing hydroxy on its side chain with (b) acid anhydride-containing compound.

Description

201241081 VI. Description of the Invention: [Technical Field] The present invention relates to a thermosetting resin for an adhesive and a coating agent, and to a product for use in the periphery of an electronic material such as a printed wiring board. A thermosetting resin composition of an adhesive and a coating agent. [Prior Art] In recent years, the development of the field of electronics has been excellent, especially in the miniaturization, lightening, and high-density of electronic equipment, and the requirements for such performance have become more and more serious. In order to meet such requirements, research on thinning, multilayering, and high precision of electronic materials including printed wiring boards is prevalent. Along with the adhesives and coatings used for the towels, there is a high degree of flexibility, flexibility, and adhesion that is not required in the case of a thick hard plate which is made of glass epoxy or the like. High electrical insulation, adhesion, and thermal stability with m narrowing. The further step requires flux resistance and the like which are necessary in the welding step of the material (SGldef_m) or post flux. The adhesive/coating agent used for the periphery of such an electronic material can be exemplified by (1) to (6) which will be described later. (1) Interlayer adhesive: The user directly connects to the copper wire circuit in order to bond the circuit boards. It is a layer of pure layers with a liquid or thin sheet. (2) Adhesive for the cover film: In order to bond the cover film (the polyimide film used for the purpose of protecting the outermost surface of the circuit) to the circuit board of the substrate, it is used in advance. The imine film and the subsequent layer are the ones. (3) Adhesive for copper clad film (CCL): used in order to bond a polyimide film to a copper box 323716 3 4 201241081. When the copper circuit is formed, etching or the like is performed. (4) Cover layer: For the purpose of protecting the outermost surface of the circuit, it is printed on the circuit using an ink, and after bonding the sheets, the film is cured to form a photosensitive property and a thermosetting property. ~to make. (7) Adhesive for reinforcing plate: To make up the mechanical strength of the wiring board. Use the reinforcing plate for fixing the part of the wiring board to metal, glass, oxygen, etc. (I) Electromagnetic wave shielding adhesive: It is attached to a flexible printed wiring board for the purpose of shielding the electronic circuit. Electric 礤哚 These forms are liquid (for printing (4) ink-based filming), etc., and appropriate separation is selected depending on the application. W (pre-reaction in response to the various types of electronic materials surrounding the material) (4) 胄, untransferred sub-divisions, although the second has a specific acid price of polyamine niobium citrate as the main component The good adhesion of the composition of the sulphate sulphate sulphate squid is shown to be derived from the distance between the scorpion and the sorrow of the scorpion, and it is difficult to fill the knives (4), so there is Lack of resistance to recording. In order to increase the amount of epoxy resin in order to make up the point, there is a problem that the wettability of the substrate is lowered and the strength is lowered. Further, the skeleton is used as the main chain, and there is a temperature in the south. The problem of insulation reliability at the time of humidification is remarkably inferior. t 1 has disclosed a binder containing a sulfhydryl sulphate containing a slow-acting group, and a binder of a hardener. Fantasy. Although, ', with = good adhesion from the carbamic acid to the key, but there is a lack of heat resistance. And 'amine vinegar resin has a low molecular weight, using a press (four) called etc. 5 323716 201241081 There is a problem of excessive processing of excessive excess in thermal hardening. Furthermore, blood Lishu 1 is the same, because the use of "framework as a line, there is a problem of insulation reliability at the time of high temperature humidification is significantly inferior. Also" has revealed the inclusion of polyimine oxime oxygen, two-end epoxy oxime And the hardening agent of the tree silk (special offer 3). Although the towel has the unique characteristics of Shi Xi oxygen resin _ miscellaneous and excellent (four) heat, _ oxygen fresh frame itself lacks the adhesion of the substrate, but by cross-linking The hardening of the ring having a low density has a problem that sufficient bonding strength cannot be obtained. χ, the distance between the crosslinking points of the epoxy groups is large. (4) The problem of excessive processing of the excess portion occurs when the machine is thermally hardened. The compatibility with other components is remarkably poor, and there is a lack of freedom in design of the composition, insufficient coating resistance with the composition, etc. Further, it has been revealed that epoxy resin is used to minimize ionicity. A thermosetting resin composition containing a NBR rubber of an impurity and a nitrogen-containing varnish resin (can be used as a main component) (Patent Document 4). This adhesive composition is thermally hardened by a press or the like. Excessively derived from the excess of NBR rubber, The disadvantage of poor workability. In addition, in order to complement this point, adding too much epoxy resin and phenols has the problem of lowering the strength. Furthermore, the NBR rubber which is as low as possible to reduce ionic impurities is expensive and industrially difficult to use. Further, a resin composition containing an epoxy resin, a phenol resin, a curing accelerator for an epoxy resin, and an elastomer has been disclosed (Patent Document 5). In this case as well, it is difficult to simultaneously improve the deterioration of the processability derived from the elastomer. The problem of lowering the strength of the epoxy-phenol hardening system. 201241081 Further, a resin composition of a polybutadiene which does not contain a soft skeleton has been disclosed. - For example, it has been disclosed to use a polyazide having a polybutadiene skeleton. An example of a resin composition of an amine* resin, a polybutadiene polyol, and a blocked isocyanate is an overcoat agent for a flexible circuit (Patent Document 6). Further, a resin composition in which a polyamidoximine imine resin having a polybutadiene skeleton and a polyoxyalkylene skeleton and an epoxy resin are blended is disclosed (Patent Document 7). It has been disclosed that a resin composition having a polybutadiene skeleton and a bad oxygen resin is disclosed (Patent Document 8). However, such a dibutyl resin needs to be oxidized at a high temperature and characteristic of a dibutyl skeleton. Intramolecular crosslinking is caused, and there is a problem that the resin is gelled in the reaction and the preservation stability of the composition is remarkably lowered. Prepare (four) Shi has revealed 7^ eyes on the hydrogenated poly 1' diterpene skeleton (specialized 9). As the ruthenium, a composite resin composed of a hydrogenated polybutylene resin having a slow base and an olefinic resin is used. Therefore, it is derived from the adhesion of hydrogenated polybutylene. However, the insulating properties and chemical resistance of the composite composite tree nose N are the basic characteristics of the insulating material of the circuit board. The modification of the two-component fiber-containing compound _ epoxy compound polymerization The second substrate has excellent adhesion strength and heat resistance. =, copper or poor ester skeleton as the main chain, there is a problem of high 汊 ', = hydrolysis resistance inhibition is poor. Also, because of the dibasic acid Main material, phase 323716 7 201241081 It is difficult to exhibit flexibility with an amine phthalate resin or an NBR rubber, and it is difficult to achieve heat resistance. [Prior Art Document] [Patent Literature] [Patent Document 1] 曰本特开平Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-91648. [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 9] JP-A-2000-302839 [ [Problems to be Solved by the Invention] The object of the present invention is to provide excellent adhesion, heat resistance, flexibility, buckling, adhesion, electrical insulation. In particular, it is excellent in adhesion and heat resistance, and is particularly excellent in adhesion and electrical insulating properties, and also excellent in flexibility and heat resistance. Further, it is suitable for use as a printed wiring board. For the purpose of the adhesive agent for the periphery of the electronic material and the thermosetting resin composition of the coating agent. (Means for solving the problem) 323716

S 201241081 £:==::=== That is, the first invention relates to a thermosetting resin composition, which is a modified ester resin containing a carboxyl group; (Β) is selected from the group consisting of epoxy-containing esters. a compound of the group, a compound containing an isocyanate group, and a compound containing a blocked isocyanate group; and, (C) a thermosetting assistant; (Α) a modified ester resin containing a carboxyl group The following steps are carried out to produce (c) a carboxyl group by reacting the (4) polyol compound with (b) at least one type of compound containing at least one selected from the group consisting of an alicyclic polydextrin, an aromatic compound, and phthalic anhydride. The ester resin; the above (4) contains the carboxyl group of the tree and (6) in! An epoxy compound having at least two epoxy groups in the molecule is reacted to form (4) a modified ester resin containing a side bond group; and further, (4) a modified vinegar resin containing a side chain vial and (8) is selected from an alicyclic ring At least one compound containing an acid anhydride group of the polybasic acid anhydride and the aromatic polybasic acid anhydride is reacted. According to a second aspect of the invention, in the thermosetting resin composition of the first aspect, the '(8) poly 70 alcohol compound is selected from the group consisting of (IV) a polyhydric alcohol, a polycarbonate polyhydric alcohol, a polyether polyol, a polybutadiene polyol, and At least one compound of the group formed by the polyoxyalkylene polyol. Further, the third invention relates to the thermosetting resin of the i- or the second invention, Z 9 323716 201241081. The composition of the (b) acid anhydride group-containing compound is selected from the group consisting of methyltetrahydroacetic anhydride and tetrahydrophthalic anhydride. , hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, nadic acid anhydride, quinonedic acid needle, hydrogenated quinone diacyl anhydride, styrenostyrene tetrahydrophthalic acid Anhydride), 3,6-endoarylenetetrahydrophthalic anhydride, methyl endonamidinotetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, phthalic anhydride, tetrabromoic anhydride, trimellitic anhydride and coke honey At least one compound of the group consisting of two needles of stearic acid. In the thermosetting resin composition according to any one of the first to third aspects, the acid ester of the (A) carboxyl group-containing modified ester resin is from 1 to 100 mgKOH/g. According to a fifth aspect of the invention, the thermosetting resin composition of any one of the first to fourth inventions, wherein (A) the carboxyl group-containing modified ester resin has a weight average molecular weight of 5,000 to 500,000. The thermosetting resin composition according to any one of the first to fifth invention, wherein the (C) thermosetting assistant is selected from an aziridine compound and contains a carbon dioxide. At least one of a group of a carb〇diimide-based compound, a benzoxazine compound, a phenol resin, an imidazole, and a di-monoamine. Furthermore, the seventh invention relates to a cured product obtained by curing the thermosetting resin composition according to any one of the first to sixth inventions by heating. According to a eighth aspect of the invention, there is provided a printed wiring board comprising the layer formed of the cured product of the seventh aspect. 323716

S 10 201241081 (Effect of the invention) The thermosetting resin composition of the present invention is excellent in adhesion, heat resistance, flexibility, flexibility, adhesion, electrical insulation, heat and humidity resistance, flux resistance (flux) In particular, it is excellent in terms of both adhesion and electrical insulation, and both buckling resistance and heat resistance. Therefore, it is possible to provide a thermosetting resin composition suitable for use as an adhesive and a coating agent for the periphery of an electronic material including a printed wiring board. [Embodiment] The (A) carboxyl group-containing modified ester resin of the present invention can be obtained by (a) a polyol compound and (b) an alicyclic polyacid needle and an aromatic plural. At least one acid anhydride group-containing compound (b) (hereinafter, only δ is contained in "(8) an acid anhydride group-containing compound") is reacted to form () a mercapto group-containing ester resin; and the above (c) contains a carboxyl group The ester resin is reacted with (d) an epoxy compound having at least two epoxy groups in one molecule to form a modified ester resin containing a side chain hydroxyl group; and further, (e) is modified by a side bond carboxy burst The ester resin is reacted with (b) at least one compound containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid liver. By using (A) a carboxyl group-containing modified ester resin, for example, storage stability before curing, flexibility after curing, insulation reliability, solder heat resistance, solder heat resistance after humidification, and the like can be remarkably improved. These physical properties are very important physical properties in the adhesives and coating agents used in the periphery of electronic materials such as printed wiring boards. A significant improvement in the above physical properties is due to the use of (a) a polyfluorene compound and (b) an anion group-containing compound selected from the group consisting of (a) a polyvalent anthracene compound and (b) an alicyclic polybasic anhydride and an aromatic polybasic acid anhydride selected from the group consisting of aliquots of 'P 323716 w 11 201241081. In other words, it is possible to impart the flexibility (processability, processability, etc.) of the polyfunctional polyol compound compared to the conventional resin using a polyester skeleton using a dibasic acid as a main chain. Further, (a) a polyol When the compound (b) contains an acid anhydride group-containing compound to form (c) a carboxyl group-containing ester resin, the ester bond group having poor insulating reliability is protected by a large amount of substituents of the (b) acid anhydride group-containing compound. Conventionally, a resin having a polyester skeleton as a main chain can remarkably improve insulation reliability, solder heat resistance, etc. For example, 'the acid anhydride group-containing compound which does not belong to (b) an acid anhydride group-containing compound is substituted (b) contains an acid anhydride group. In the case of a compound, in general, the substrate adhesion and heat resistance due to the polarity of the ester bond can provide a certain degree of adhesion strength and solder heat resistance. However, under strict conditions such as high temperature humidification, insulation The reliability is poor, and the solder heat resistance cannot satisfy the high solder heat resistance such as the high temperature solder test or the wet solder test. In order to solve these problems, high Tg (Tg: glass transition) is generally added. When the hardening agent is added to the resin of the skeleton or the high Tg skeleton, the entire layer of the subsequent layer is positively Tg, and the adhesion to the substrate is lowered, and the strength is remarkably lowered. On the other hand, (A) contains a carboxyl group. When the modified ester resin is formed from the polyol compound and (b) the acid-hepatic group-containing compound (b) to produce (4) a thiol-containing vinegar resin, the vinegar bond group is protected by a large number of substituents. Therefore, good insulation is satisfied at the same time. Reliability and solder heat resistance, and it is possible to exhibit high heat resistance without maintaining the Tg. ▲In addition, (A) a modified ester resin containing a carboxyl group, especially as a (a) polyol compound Polycarbonate polyol, alicyclic polyglycol polyol, etc.

12 323716 S 201241081 Ester polyols, polybutadiene polyols (including bismuth), polyether polyols and/or polyoxopolyols for higher electrical insulation and heat. Further, by appropriately selecting (d) an epoxy compound having at least two epoxy groups in one molecule, although a polycarbonate skeleton or a polyoxyalkylene skeleton which is generally difficult to adhere to a substrate is used, Can display high adhesion strength. For example, when a skeleton having excellent heat resistance such as polycarbonate or polysiloxane is used in order to ensure electrical insulation, the adhesion to the substrate is lowered, and the bonding strength cannot be ensured. On the other hand, the present invention solves the contradiction between high electrical insulation and adhesion strength for the above reasons. Further, since (A) the modified ester resin containing a carboxyl group does not need to use too much high Tg raw material, it exhibits excellent buckling property. In general, resins having high buckling tend to have a lack of heat resistance. However, (A) the modified ester resin containing a carboxyl group exhibits higher heat resistance than a general polyester resin because the S-bonding group in the molecule is protected by a large number of substituents. Further, (e) a modified ester resin containing a side chain group and (b) a compound containing an acid anhydride group are allowed to react, and a thermal crosslinking point is introduced into the main chain, whereby the heat resistance can be further improved by crosslinking. . Usually, in order to ensure the buckling property, a low Tg skeleton or an amine phthalate bond is introduced, which lacks heat resistance and cannot ensure high heat resistance. Further, in order to ensure heat resistance, a high Tg skeleton or a high heat-resistant bond is introduced, and since these generally lack buckling properties, heat resistance and buckling properties cannot be achieved. On the other hand, the present invention solves the contradiction between high buckling property and high heat resistance by the above reasons. As the (a) polyol compound, it is preferred to use a low Tg polycarbonate polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol, a polyether polyol, and/or a polyoxyalkylene polyol. Flexibility. At 13 323716 201241081 this, low Tg means below 0°c. Further, in the modified base resin (A) containing a thiol group of the present invention, a trifunctional polyol is appropriately introduced as a polyol compound, and these effects can be further enhanced. Specifically, the introduction of the branched structure increases the cohesive force of the resin layer. As a result, the storage stability, the process stability, the buckling property, and the electrical insulating properties are not adversely affected at all, and the adhesion strength and heat resistance can be improved. Hereinafter, the thermosetting resin composition containing the ester-containing modified ester resin (A) of the present invention will be described in detail. The carboxyl group-containing modified ester resin (A) of the present invention is obtained by the following description: First, (a) a polyol compound and (b) are selected from the group consisting of an alicyclic polyacid needle and a fragrant polyacid needle. At least one compound containing an acid anhydride group is reacted to form (c) a carboxyl group-containing ester resin ', and then (c) a carboxyl group-containing vinegar resin and (d) a ring having at least two epoxy groups in one molecule The oxygen compound is reacted to form (e) a modified ester resin containing a side chain hydroxyl group 'return' to (e) a modified ester resin containing a side chain hydroxyl group and (b) an alicyclic polybasic acid anhydride and an aromatic plural At least one acid anhydride group-containing compound of the acid anhydride is reacted. The polyol compound (a) used in the present invention preferably has two or more warp groups and has a repeating unit having a degree of polymerization of 2 or more in the structure. Further, from the viewpoint that the adjustable molecular weight is an intended value, the polyol compound (a) is preferably a compound containing two hydroxyl groups. From the point of view that a good balance between heat, buckling, and adhesion can be exhibited by the hardened coating film, the reset average converted to polystyrene by gel permeation chromatography (hereinafter also referred to as rGPC) is used. The molecular weight is preferably from 500 to 50,000. The polyol compound (a) is not limited to 323716 14 201241081, and is limited to the following examples, and examples thereof include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polyoxyalkylene oxides. Polyols • etc. Further, in the present application, unless otherwise specified, the weight average molecular weight means the weight average molecular weight converted to polystyrene by GPC. The polyester polyol used in the present invention, for example, a polyester polyol in which a polyfunctional alcohol component and a dibasic acid component are subjected to a condensation reaction. Among the polyfunctional alcohol components, the glycol may, for example, be ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol or 3-mercapto-1. 5-pentanediol, 3,3'-dihydroxydecylheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol , octyl glycol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, bisphenol A, etc., and a polyfunctional alcohol component having three or more hydroxyl groups can be exemplified Trimethylolethane, polytrimethylolethane, trihydroxydecylpropane, polytrihydroxydecylpropane, neopentylol, polyneopentaerythritol, sorbitol, mannitol, arabitol, Xylitol, galactitol, glycerin, etc. The dibasic acid component may, for example, be an aliphatic or aromatic dibasic acid such as citric acid, adipic acid, sebacic acid, sebacic acid, phthalic anhydride, isophthalic acid or benzoic acid, and the like. Also:|Can use lu-butyrolactone, /3-propiolactone, 7-butyrolactone, 7-pental vinegar, <5-pental vinegar, ε-hexene S, 7-hexane vinegar A polyglycol polyol obtained by ring-opening polymerization of a cyclic ester compound such as a lactone or a lactone such as α-mercapto-/3-propiolactone. A polyester polyol having a phosphorus atom can be used, and specifically, 2-(9,10-dihydro-9-oxa-10-phosphaphenanthryl-10-yl)methylsuccinic acid or its acid 15 can be exemplified. 323716 201241081 Polycondensate of anhydride and ethylene glycol, or 2-(9,10-dihydro-9-oxa-10-oxy-iodo-10-phosphaphenan-10-yl)methylsuccinic acid- A bis-(2-hydroxyethyl)-ester or a polyester polyol obtained by polycondensation thereof. The Kuraray polyol P series of Kuraray Co., Ltd. can be specifically used for the polyester polyol. Among them, P-1041, P-2041, P-2010, P-2020, P-1030, and P-2030 have better insulation reliability and heat resistance. The polycarbonate polyol used in the present invention has a structure represented by the following formula (1) in its molecule. -[-R8-0-C0-]m- Formula (1) (wherein R8 represents a divalent organic residue, and m represents an integer of 1 or more). The polycarbonate polyol can be obtained, for example, by reacting (1) a diol or a bisphenol with a carbonate, (2) a reaction of a diol or a bisphenol with a phosgene in the presence of a base, and the like. The carbonate used in the production method (1) may specifically be dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethyl carbonate, or propyl carbonate.

The diol or bisphenol used in the processes (1) and (2) may specifically be ethylene glycol, propylenglycol, dipropylene glycol, diethylene glycol, triethylene glycol, butanediol, 3-mercapto -1,5-pentanediol, 2-mercapto-1,8-octanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propylene glycol (propanediol), 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, xin Glycol, butyl ethyl pentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol or bisphenol A or bisphenol F 16 S 323716 201241081 and other bisphenols 'the aforementioned bisphenols and Ethylene oxide such as ethylene oxide or propylene oxide, and bisphenols. These compounds may be used alone or in combination of two or more.

As the polycarbonate polyol, Kuraray polyol c series of Kuraray Co., Ltd. can be specifically used. Among them, PMHC-1050, PMHC-2050, C-1090, C-2090, C-1065N, C-2065N, C-1015N, and C-2015N are soft and preferable. Further, ETERNACOLLUC-100, UM-90 (l/3), UM-90 (1/1), and UM_9 (3/1) of Ube Industries Co., Ltd. are excellent in heat resistance. For the polyether polyols used in the ruthenium, for example, polymers, copolymers and graft copolymers of ethylene oxide, such as tetrahydrofuran, Weiyi, glycerin, and butyl butyl bromide; a poly-bonded polyol obtained by combining an alcohol, a heptanediol, a octanediol or a mixture thereof; (10) an A or a double-order F, etc., and an epoxy burning addition of epoxy epoxide, epoxy propylene or the like. Aromatic diols such as bismuth; a use of di(tetra)-ethyl bromide, polytrimetic methyl bromide, tri-propyl propyl cyanide, t-propylpropanol, neopentyl alcohol, polyneopentaerythritol Polyethylene epoxide, polyepoxypropylene, epoxy, sorbitol, mannitol, I1 "Lappol, alcohol, xylitol, galactitol, glycerol, etc. Block copolymers or random copolymers of ethane "hydropropane, polybutanediol, block copolymers of butanol and neopentyl glycol, or random copolymers such as poly-alcohols It is more than two. The polybutene polyol used in the present invention may, for example, be a hydrogenated intramolecular unsaturated bond, including a polyethylene polyol, a polypropylene polyol, or a polybutadiene polyol, which contains 17 323716 201241081. Hydrogenated polybutadiene polyol, polyisoprene polyol, hydrogenated polyisoprene polyol, and the like. The commercial product of the polybutadiene polyol may, for example, be NISSSOPB (G series) of Japan Soda Co., Ltd., Poly-Pd of Idemitsu Petrochemical Co., Ltd., and liquid polybutadiene having hydroxyl groups at both ends; NISSSOPB (GI series) of Co., Ltd., PolytailH, Polytail HA of Mitsubishi Chemical Co., Ltd., hydrogenated polybutadiene having hydroxyl groups at both ends, and Poly-iP manufactured by Idemitsu Petrochemical Co., Ltd. C5-based polymer; Epole, manufactured by Idemitsu Petrochemical Co., Ltd., hydrogenated polyisoprene having hydroxyl groups at both ends, such as ΤΗ-1, TH-2, and TH-3, manufactured by Kuraray Co., Ltd., but not Limited to this. The polyoxane polyols used in the present invention may, for example, be compounds represented by the formulae (2) and (3). CH3 X—R1-Si-0 ch3

Ch3 ch3 -Si-O-Si-R2-X General formula (2) ch3 ch3 gate (X represents a hydroxyl group, R1 and R2 each represent an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 5 or more).

18 323716 S 201241081 ch3 R3—Si-O I ch3 ch3 r5-y ch3 ( -Si-O^Si-R4- ch3 -R7 CH3 r6-y General formula (3) n (Y represents a hydroxyl group, and R3 represents a carbon number of 1 to 6 The alkyl group, R4, R5 and R6 respectively represent a C 1 to 6 alkyl group, R 7 represents a hydrogen atom or a C 1 to 6 pit group, and η represents an integer of 5 or more. The polyol compounds (a) Among them, a polyester diol composed of 1,4-cyclohexanedicarboxylic acid and 3-mercapto-1,5-pentanediol, using only 1,6-hexanediol as a diol Polycarbonate polyol, polycarbonate diol using 1,6-hexanediol and 3-methyl-1,5-pentanediol as diol, using 1,9-nonanediol Copolymerized polyether polyol with polycarbonate diol, polybutane diol, polypropylene glycol or butane diol and neopentyl glycol formed by using 2-mercapto-1,8-octanediol as a diol a polybutadiene polyol, a hydrogenated polybutadiene polyol, a polyoxyalkylene polyol, etc. The polyol compound (a) is excellent in flexibility, heat resistance, and hydrolysis resistance of the skeleton. Electrical insulating properties, buckling, heat resistance, and resistance to carboxyl modified ester resin (A) In the present invention, the polyol compounds (a) may be used singly or in combination. The most characteristic feature of the present invention is the polyol compound (a) and an alicyclic polybasic acid anhydride and aroma. The at least one acid anhydride group-containing compound (b) is reacted to obtain a thiol-containing resin group (c), which is protected by a large number of substituents. The alicyclic ring is used in the present invention. Polybasic acid anhydride and aromatic polybasic acid

19 323716 201241081 At least one acid anhydride group-containing compound (b), which may be exemplified by mercaptotetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl Nadickic anhydride, hydrogenated quinone diacyl anhydride, stupid vinyl styrene tetrahydrophthalic anhydride, 3,6-endylene fluorene tetrahydrophthalic anhydride, methyl endonamidinotetrahydro uric anhydride, three-yard four An alicyclic dibasic acid anhydride such as hydrogen oxyhydrogen anhydride; an alicyclic polyanthracene acid having a tribasic acid or the like such as hydrogenated trimellitic anhydride or hydrogenated pyrogallic anhydride; phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, etc. An aromatic dibasic acid anhydride; an aromatic polybasic acid anhydride having a tribasic acid or the like such as biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, pyrogallic anhydride, or diphenyl ketone tetracarboxylic acid dianhydride. Among the acid anhydride group-containing compounds (b), preferred are a mercaptotetrahydrofuran acid needle, a tetrahydrofuran acid needle, a hexahydrophthalic anhydride 'methyl hexahydrophthalic anhydride', a nadic acid needle, and a quinone didike anhydride. , hydrogenated quinone diacyl anhydride, and the like. When the polyol compound (a) is reacted with the polyol compound (a) to form a carboxyl group-containing ester resin (c), the ester bond group having poor insulation reliability is protected by a large number of substituents, and the ester bond group protected by a large number of substituents constitutes a main chain, compared with the conventional one. A resin using a polyester skeleton as a main chain can maintain high adhesion and remarkably improve insulation reliability, solder heat resistance, and the like. Further, the acid anhydride group-containing compound (b) is preferably trimellitic anhydride or pyrogallic anhydride. The amount of terminal carboxyl groups of the ester-containing resin (c) which is reacted with the polyol compound (a) may be increased, and then, in the reaction with the epoxy compound (d) having at least two epoxy groups in one molecule , can be polymerized. Then, the amount of the polymer is increased, and the cohesive force of the resin is increased, so that flexibility can be maintained and a coating film which is more excellent and tough can be formed after the formation of the coating film. 20 323716

S 201241081 In the present invention, a compound (a l) containing a hydroxyl group can be optionally used. The compound containing the & base (a_i) is a compound containing one or more kinds of a trans group, and a compound other than the compound of the above-mentioned "polyol compound (a)" is exemplified, and a representative example thereof may be exemplified in the molecule. A monohydric alcohol monool compound (a-1-i), a diol compound having two hydroxyl groups in the molecule, 2), and a compound (a-1-3) having three or more hydroxyl groups in the molecule. These may also have a functional group other than a hydroxyl group or a hydroxyl group in the molecule. Also, it can be used alone or in combination. The monool compound (a_M) having i hydroxyl groups in the molecule may, for example, be methanol, ethanol, n-propanol, isopropanol, n-butylene glycol, isobutylene glycol, tertiary butanediol, lauryl alcohol, or hard. An aliphatic monoalcohol such as a fatty alcohol; an alicyclic monoalcohol such as cyclohexanol; an aromatic monool such as benzyl alcohol or decyl alcohol; a phenol such as phenol or methoxyphenol; and a monool compound having a functional group other than a hydroxyl group; For example, a compound containing a sulfonate such as a ketone, a oxetane alcohol, or the like containing a thiol or a ketone, such as a hydroxybutyric acid, or a butyl ketone, may be used. . Other examples include oligomer-type monoalcohols such as mono-terminal methoxypolyethylene glycol, early-end methoxypolypropylene glycol, and an internal vinegar addition polymer using a monool as a starting agent. In the present invention, the use of the monoalcoholization having i radicals in the molecule: the (a 1 1)b can be encapsulated to obtain the thiol-containing ester resin (4). Therefore, it is thought to be low in synthesis. When the molecular weight contains the modified vinegar resin (A), it is necessary to adjust the molecular weight. In addition, when a compound containing a radical group having a functional group other than a radical is used, a functional group other than a carboxyl group may be introduced at the terminal of the ester-containing ester resin (C), and a carboxyl group-containing ester resin is required. When the end of the product is modified, it can be suitably used. In view of the reactivity of the hydroxyl group and the polymerization control, the monool compound is preferably lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidyl alcohol, 2-hydroxyethyl (meth) acrylate. , (meth)acrylic acid 4-hydroxybutyl ester, and the like. Further, the diol compound (a small 2) having two groups in the molecule may, for example, be ethylene glycol, propylene glycol, 2-methyl-1,3-propylene glycol, or 2-mercapto-2-ethyl hydrazine. Propylene glycol, 2,2-diethyl-i, 3-propanediol, 2-methyl-2-propylpropanediol, 2-butyl-2-mercapto-l,3-propanediol, 2-butyl-2- Ethyl-i,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-2,4·pentanediol 1,3,5-trimethyl-i,3-pentanediol, 2-mercapto-1,8-octanediol, 3'3 _-methyl ketone, propylene glycol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, iota, 9-decanediol, neopentyl glycol, octanediol, 3-butyl 3-ethyl-1,5-pentanediol, 2-ethyl-l,6-hexanediol, cyclohexanediol, cyclohexanedonol, tricyclodecanol, cyclopentadiene An aliphatic or alicyclic diol such as dihydric alcohol, dimer diol, hydrogenated bisphenol A or spirodiol (Spir〇giyC〇i); 1,3-bis(2-hydroxyethoxy) Benzene, 12-bis(2-hydroxyethoxy)benzene, M-bis(2-hydroxyethoxy)benzene, 4,4'-methylenediol, 4,4, sub-drop ά base) 4,4 -(2-norbornylidene) diphenol), 4,4,· Dihydroxybiphenol 'o-, m- and p-dihydroxy stupid, 4,4,-isopropylidene phenol 1,2-decanediol, i,3-naphthalenediol, itnaphthalenediol, 17^diol, 9,9,_bis(4-hydroxyphenyl)anthracene, 9,9'-double (3 - mercapto-4-hydroxyphenyl) first aromatic 323716 22 201241081 diols and the like. Others include a diol containing a hole, a diol containing a sulfur atom, a diol containing a bromine atom, and the like. Further, a compound having a functional group other than a hydroxyl group can be exemplified. The N,N-bis(2-hydroxypropyl)aniline, N:,N-bis(2-hydroxyethyl)aniline, N,N-bis (N,N-bis(2-hydroxyethyl)aniline), such as a compound containing a tertiary amino group, may be exemplified. 2-hydroxyethyl)methylamine, N,N.·bis(2-hydroxyethyl)propylamine, n,N-bis(2-hydroxyethyl)butylamine, N,N•. 2-hydroxyethyl)hexylamine, N,N-bis(2-hydroxyethyl)octylamine, N'N-bis(2-ylethylethyl)benzylamine, postal_double (2_jing a diol compound containing a tertiary amino group such as a hydroxy group, and a thiol compound containing a thiol group, such as dihydroxymercaptobutyric acid, dimethylolpropionic acid, and 3-hydroxyl Acid, 4, kutaric acid, 5-hydrazalic acid, 2-mercapto-M-cyclohexanedimethanol, etc. wherein 'di(tetra)ylbutyric acid, di-methylpropionic acid and acid-containing liver group ^ The reaction of the substance (1)) can increase the number of terminal two groups of the lysine (4) containing a radical, and then the reaction with a ring (d) having at least two epoxy groups in one molecule, From the point of view of the molecular weight, the face of the present invention is good, and the final use of the N-N-bis(2-propylpropyl) aniline contains a 3-grade soil-alcohol compound. The coating power is increased, and it is a compound having three or more subtractions (α·1·3) in the molecule from the viewpoint of being able to maintain flexibility and more excellent properties. Bovine such as - hydroxydecyl ethane, trihydroxy decyl propane, neopentyl alcohol, sorbitol, ▲ sugar, aronia, sugar alcohol, ketamine, galactitol, glycerol compound. It is equal to the number of radicals in the molecule. 23 323716 201241081 'The final product can be increased in height due to the increase in the weight of the base (4), and the final product can be polymerized, which can improve the hardened coating film. H is rich in the way to improve the resistance of hardening and coating. It can be used as needed. From the aspect of reaction regulation, it is equal to the better system of compounds with more than 3 meridines in the molecule (a_M). The use of dimethicone or neopentyl alcohol is used herein. In the present invention, the polyol compound (4) and the compound containing the compound (a-oxime) can be used in an arbitrary ratio depending on the purpose, with respect to the polyol compound. The base group L0 in (4), the base group containing the base compound (4) is preferably fine (10) mol to (4) Mohr, more preferably used in a ratio of 5 mils to 0.50 moles, relative to the radicals in the compound (a-oxime) having a warp group of 1.0 molar 3 in the polyol compound (4). When the ratio of 1 mol or more is used, excellent heat resistance can be obtained. When the amount is less than 1 mol, the cohesive force of the finally obtained coating film is in an appropriate range, and then the strength is excellent. In the case of the resin (4), the ratio of the reaction of the starting material to the compound (8) and the compound containing the radical (a-oxime) added as the case may be, when the total of the radicals contained in the resin is i mole, The acid anhydride group contained in the acid anhydride group-containing compound (b) is preferably reacted in a ratio of 0.70 moles per L30 mole, more preferably in a ratio of from 9 moles to 1.10 moles. When the total of the acid anhydride groups is 〇7〇 mol or more, the obtained ester group-containing ester resin (e) has a large amount of base, and the subsequent reaction with the epoxy compound (4) having at least two epoxy groups in the i molecule A sufficient reaction occurs in the step, and the weight average molecular weight _ of the finally obtained ester-containing ester resin (A) is sufficiently large. Also, the total acidity is 13g for 323716

When S 24 201241081 is used, the next reaction with the ring gas having at least two epoxy groups in one molecule - the compound (d) reacts very little, and does not gel in the middle of the reaction. Further, in the range of 0.90 mol to 1.10 mol, when reacted in a ratio close to 丨(10) mol (ie, 0.95 mol to 1.05 mol), the next step has at least 2 epoxy groups in one molecule. A sufficient reaction occurs further on the way of the reaction step of the epoxy compound. Thereby, the weight average molecular weight of the finally obtained carboxyl group-containing modified ester resin (A) is made sufficiently larger, and the heat resistance, buckling property, and adhesion of the cured coating film can be further enhanced. In the present invention, the synthesis conditions of the vinegar-containing vinegar resin (c) are not particularly limited, and can be carried out under known conditions. For example, a polyol compound (a) and a solvent [a compound containing a hydroxyl group (al) as required] are placed in a flask, and heated and scrambled at 20 to 12 ° C under a nitrogen gas stream to be uniformly dissolved, and then charged. The acid anhydride group-containing compound (b) can be obtained by heating with 50 to 15 Torr σ while stirring to obtain a carboxyl group-containing ester resin (c). In the reaction, a compound containing a tertiary amino group or the like may be used as needed. Further, before the addition of the acid anhydride group-containing compound (1)), the polyol compound (a) and the solvent previously placed in the flask may be heated/stirred at 1 Torr or more to desolvate a part of the solvent. . This operation is usually carried out in order to remove moisture (dehydration treatment) in the system, and by this operation, at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride can be inhibited. A ring opening reaction of an acid anhydride group due to water. Next, an epoxy compound (d) having at least two epoxy groups in one molecule of the present invention (hereinafter also referred to simply as "epoxy compound (4)") will be described. In the present invention, the epoxide epoxide W is preferably a compound containing two epoxy groups in the molecule, and is not particularly limited. Specifically, for example, ethylene glycol dimethicone (IV), polyethylene glycol diepoxypropyl ether, hexanediol diepoxypropyl ether, bisphenol A_table alcohol (A W (tetra) hydrin) type epoxy can be exemplified. Resin, double F_ watch gas alcohol tour epoxy tree month, hope - gas alcohol type epoxy resin, glycerol _ gas alcohol adduct polycyclic ring: propyl sulphate, m-phenylene diene oxide Propyl Jun, polybutadiene diepoxypropyl, hydrogen diepoxypropyl bond, di-pentanediol diepoxypropyl bond, new I, diol diepoxypropyl ether, hexahydro ugly Acid diepoxypropyl §|, hydrogenated double A diglycidyl ether, dihydroxy oxime epoxy resin, polypropylene glycol diepoxypropyl sulphide, diphenyl sulfonium diepoxide propyl shout, two counties Diphenyl ketone diglycidyl ether, lion diepoxypropyl, diphenyl carbodimethacrylate, bisphenol second epoxy propyl ether, double bismuth diacetate, double Phenoxy, diglycidyl ether, U, N, N-diepoxypropylaminomethyl) hexyl hexane, N,N-diepoxypropyl aniline, N,N-diepoxy Anthracene aniline, 曰本特开2004-156024, Japanese Patent Laid-Open No. 4-315595, transcript Open No. 2004-323777 disclosed the epoxy compound of heterologous excellent flexibility 'and epoxy compounds, etc. by the following structural formula (1) to (3). 323716 26 201241081

Formula (1)

The formula (3> wherein 1,6-hexanedi-alcohol diglycidyl ether is preferably softened to give the finally obtained carboxyl group-containing modified ester resin (A). Bisphenol A_milk The alcohol type epoxy resin is preferably used in the case where the heat resistance is given to the finally obtained carboxyl group-containing resin (A). Thus, in the present invention, the oxygen compound (d) can be selected depending on the purpose. Alternatively, it may be used singly or in combination. ^ This is a ratio of the carboxyl group of the carboxyl group-containing ester resin (c) to 10 mol, and the ratio of the resin containing the filament (4) to the epoxy compound (d). The epoxy group in the preferred epoxy compound (d) is reacted in an amount of from 0.50 moles to 15 moles, more preferably from 〇7〇mol to i3〇mol. When the epoxy oxime in the epoxy compound (d) having at least two epoxy groups in 1 minute + in the 1.0 mil of the vinegar resin (4) containing a slow base is 0.5 G mole or more, the final result is obtained. The molecular weight of the modified® oxime resin (A) is sufficiently high and excellent film resistance and film formation are obtained, and the carboxyl group of the carboxyl group-containing ester resin (c) is used. When the ratio of the epoxy group in the substance (d) is 15 Torr or less, the amount of the end ring 323716 27 201241081 is suitable, and in the final synthesis stage, the compound containing the acid liver group (b) In the present invention, the synthesis conditions of the modified vinegar resin (e) containing a side chain vial are not particularly limited, and can be carried out according to known conditions. The resin (4), the epoxy compound (4), and the solvent having a few bases are placed in the flask, and the edge is imparted; and the heat is heated to i5〇c to obtain a modified resin (e) containing a side chain hydroxyl group. When necessary, a catalyst such as triphenylphosphine or a compound containing a tertiary amino group may be used as needed. Next, the modification of the money-containing group f_m(A) of the present invention will be described. The modified group containing the (four) group of the present invention A) can be obtained by reacting a modified vinegar resin (e) having a side chain group with a compound (b) containing an acid anhydride group. Here, when a modified ester resin (A) containing a mercapto group is synthesized, it will contain When the hydroxyl group in the side chain hydroxyl group-modified ester resin (e) is 1.0 mol, the acid anhydride group-containing compound (b) is reacted. The ratio is preferably such that the acid anhydride group in the acid anhydride group-containing compound (b) is reacted in a ratio of 〇〇5 mol to 丨〇mol, and the reaction is carried out at a ratio of 0.10 mol to 0 90 mol. The ratio of the acid anhydride group in the acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride is 1.0 mol of the hydroxyl group in the modified ester resin (e) having a side chain hydroxyl group. When the amount is more than 5 moles, the ratio of the reforming is sufficient and the effect of introducing the crosslinkable functional group in the main chain is high. Further, when the work is below the molar amount, the remaining acid anhydride group-containing compound is not easily retained, and the final coating film It is excellent in flexibility, solder heat resistance, and insulation reliability. In the present invention, the synthesis conditions of the modified ester resin (A) containing a carboxyl group are not particularly limited.

S 28 201241081 is not limited and can be carried out according to known conditions. For example, a modified ester resin (e) containing a side chain radical, a compound (b) containing an acid anhydride group, and a solvent 'heating' at 50 to 1 〇〇 °c are placed in a flask. An esterified ester resin (A) containing an enemy group. This reaction is carried out without a catalyst, but a catalyst such as a compound having a tertiary amino group may also be used as needed. The acid value of the carboxyl group-containing modified ester resin (A) of the present invention is preferably from 1 to 100 mgKOH/g, more preferably from 5 to 90 mgKOH/g. When the acid value is 1 mgKOH/g or more, the function of the carboxyl group as a curable group is sufficient, and the coating film resistance after curing is extremely excellent. Further, when the acid value is 10 〇 mg K 〇 H / g or less, the hardness of the coating film is in an appropriate range, and the strength is extremely excellent. Further, the acid value is in the range of 1 to 100 mgKOH/g, and is set to §10 (preferably, 1 mgKOH/g to 1 OmgKOH/g) in a range close to imgK〇H/g, and the resulting film is buckling property. And the adhesion is improved. On the other hand, when designed in the range of approximately 100 mg KOH/g (specifically, 80 mg K 〇 H / g to 100 mg KOH / g), the crosslinking point is increased and the heat resistance of the finally obtained coating film is improved. Thus, in the present invention, the acid value of the carboxyl group-containing modified ester resin (A) may be in the range of 1 to 100 mgKOH/g, which is adjusted depending on the purpose. The weight average molecular weight of the carboxyl group-containing modified ester resin (A) of the present invention is preferably from 5,000 to 500,000, more preferably from loooo to 300,000. When the weight average molecular weight is 5,000 or more, it is possible to obtain extremely excellent solder heat resistance and flexibility. Further, when the weight average molecular weight is 500,000 or less, the viscosity at the time of coating is in an appropriate range, and handling is easy. Further, the weight average molecular weight is in the range of 5,000 to 500,000, and when designed at a value close to 5,000 (specifically, 5,000 to 10,000), the end of the obtained resin (ie, carboxyl group) 29 323716 201241081 is more than cross-linked. The resin can improve the heat resistance of the finally obtained coating film. On the other hand, when designed at a value close to 500,000 (specifically, 300,000 to 500,000), the coating film finally obtained is excellent in adhesion and buckling property. Thus, in the present invention, the weight average molecular weight of the modified vinegar resin (A) containing a carboxyl group may be in the range of 5,000 to 500,000, which is adjusted depending on the purpose. The thermosetting resin composition of the present invention comprises (A) a modified ester resin containing a mercapto group, and (B) a compound selected from the group consisting of an epoxy group-containing compound, an isocyanurate group-containing compound, and a block-containing compound. At least one compound of the group formed by the isocyanate group, and (C) a thermal hardening aid. Here, at least one compound CB) selected from the group consisting of a compound containing an epoxy group, a compound containing an isocyanate group, and a compound containing a blocked isocyanate group (hereinafter also referred to simply as "compound (B)"] . The thermosetting resin composition of the present invention is characterized in that the compound (B) is used as a curing agent for the carboxyl group-containing modified resin (A). The epoxy group-containing compound of the present invention is not particularly limited as long as it contains a compound having an epoxy group in the molecule. For example, a compound having one epoxy group in the molecule may, for example, be a compound such as a group of epoxypropyl Weimine, lenone or (meth)acrylic acid propylene. These compounds can be suitably used by using the compound having two or more epoxy groups in the molecule, which is exemplified below, as needed, and the crosslinking density of the cured product. Further, a compound having two or more epoxy groups in the molecule may, for example, be ethylene glycol diepoxypropyl ether, polyethylene glycol diglycidyl ether, ruthenium hexylene glycol dipropylene fine, or double Α_epichlorohydrin type epoxy resin, double test f• epichlorohydrin

S 30 201241081 'Epoxy Resin, Bisphenol S-epichlorohydrin Epoxy Resin, Bisphenol AD-Epichlorohydrin Type - Epoxy Resin, Bisphenol-epichlorohydrin Epoxy Resin, Bisphenol A Epoxy An epichlorohydrin type epoxy resin of an ethane. adduct or a propylene oxide addition product, a polyepoxypropyl ether of a glycerol-epichlorohydrin adduct, a naphthalene glycol diepoxypropyl ether, and an Hydroquinone diglycidyl ether, polybutadiene diepoxypropyl ether, hydroquinone diepoxypropyl ether, dibromo neopentyl glycol diepoxypropyl ether, neopentyl glycol diepoxy Propyl ether, diglycidyl hexafluoroantimonate, hydrogenated bisphenol A diepoxypropyl ether, polypropylene glycol diepoxypropyl ether, diphenyl sulfone diepoxypropyl ether, dihydroxydiphenyl Ketone diglycidyl ether, biphenol diglycidyl ether, diphenyl decane diglycidyl ether, bisphenol quinone diepoxypropyl ether, bisphenol quinone diepoxy propyl ether , bisphenoxyethanol, second epoxypropyl ether, 1,3-bis(N,N-diepoxypropylaminoindenyl)cyclohexane, N,N-diepoxypropylaniline, N , N-diepoxypropyl toluidine, JP-A-2004-156024, and JP-A-2004-3155 An epoxy compound having excellent flexibility as disclosed in JP-A-2004-323777, an epoxy compound having a structure represented by the following formulas (4) to (6), and the like.

201241081 Further, 'three (polyethylidene) tripolyisocyanate can be used to make a triepoxypropyl bond, diisocyanate triepoxy (IV), manufactured by Mitsubishi Chemical Corporation, 1031S, . rEpiK〇TE 1〇32H6〇j ^ ΓΕρικ〇ΤΕ 604", "ΕΡΙΚΟΤΕ63〇", and phenol novolac type epoxy resin, 曱 秘 清 清 四 四 四 四 四 氧 氧 揭示 _ 环 环 环 环 环 环 环 环 环 环Ethylene-diluent epoxy resin, naphthalene epoxy resin, ethylene glycol _ gas alcohol plus money, Weiweijing, new fine alcohol polyepoxypropyl scale, three classics: base shouting Ν, Ν, Ν, Ν, · tetraepoxypropyl dimethyl diphenylene diamine. Further, other thermosetting groups of compounds having an epoxy group can be used. For example, the Shihwa modified epoxy resin disclosed in Japanese Laid-Open Patent Publication No. 2, 159, No. 11 and No. 2003-48953. In particular, bis(hydroxyethyl)trimeric isocyanate triepoxypropyl ether, trimeric isocyanate triepoxide material containing a trimeric isocyano-ring epoxy compound is used in the present invention The tendency of the amine and copper to increase in strength is preferred. In addition, "Ερικ〇ΤΕ 1031S", "ΕΡΙΚΟΤΕ 1032Η60", "ΕΡΙΚΟΤΕ 604", and "ΕΡΙΚΟΤΕ 630" manufactured by Mitsubishi Chemical Corporation are excellent in the present invention because of their high polyfunctionality and excellent heat resistance, and are also aliphatic. The epoxy compound described in JP-A-2004-156777, and the epoxy compound described in JP-A-2004-323777 is preferably excellent in flexibility of the cured coating film. Further, a dicyclopentadiene type epoxy compound, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, and a phenol-epichlorohydrin type described in JP-A-2002-254 Epoxy resin or the like in the present invention, thermosetting and hygroscopicity and heat resistance as the first hardening 323716

S 32 201241081 The durability level of the coating film is excellent and preferable. • The compound containing an isocyanate group is not particularly limited as long as it is a compound having an isocyanic acid group in the molecule. Specifically, the diisocyanate compound may, for example, be an aromatic diisocyanate having 4 to 50 carbon atoms, an aliphatic diisocyanate, an aromatic aliphatic diisocyanate or an alicyclic diisocyanate. The aromatic diisocyanate may, for example, be 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate or diiso isocyanate. 4,4'-diphenylmethane cyanate, 2,4-diphenylene diisocyanate, 2,6-phenylene diisocyanate, diisocyanate 4,4' - Toluidine, 2,4,6-triisocyanate, benzene, 1,3,5-triisocyanate benzene, diisocyanate, dianisidine triisocyanate, diisocyanate 4,4'-di Phenyl decyl ester, 4,4',4"-triphenyldecyl triisocyanatoate, etc. The aliphatic diisocyanate may, for example, be tridecyl diisocyanate or tetradecylene diisocyanate. Ester, hexamethylene diisocyanate, pentadecyl diisocyanate, 1,2-propyl propyl diisocyanate, 2,3·butyl butyl diisocyanate, diiso) 1,3-butyl butyl cyanate, dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Aromatic aliphatic diisocyanate can be exemplified Such as ω,ω'-diisocyanate-1,3-dimercaptobenzene, anthracene, 6; '-diisocyanate-1,4-dimercaptobenzene, 61;,〇'-diiso An ester-1,4-diethylbenzene, a 1,4-tetramethyl decyl diisocyanate, a 1,3-tetradecyl decyl diisocyanate, etc. an alicyclic diisocyanate For example, 3-isocyanate decyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], diisocyanide 33 323716 201241081 acid 1,3-cyclopentane ester, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, decyl-2,4-cyclohexane diisocyanate, decyl diisocyanate-2 , 6-cyclohexane ester, 4,4'-fluorenylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanate decyl)cyclohexane, 1,4-bis(isocyanate decyl)cyclohexane The isocyanate group-containing compound having one or three or more isocyanate groups in the molecule, specifically, a monofunctional isocyanate having one isocyanate group in one molecule, and isocyanate Oxyethylethyl ester, 1,1-bis[(indenyl)propenyloxyindenyl]ethyl isocyanate, vinyl isocyanate, allyl isocyanate, isocyanate Propylene decyl ester, isopropenyl isocyanate-α,α-dimercaptobenzoquinone Et., 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenyldecane diisocyanate, polymer diisocyanate Pyridyl ester, diisocyanate diisopropylate, phenylene 2,4-diisocyanate, phenylbenzene diisocyanate, toluene 2,4-diisocyanate, diisocyanate Hexamethylene decyl ester, 4-mercapto-m-phenylene diisocyanate, naphthyl diisocyanate, p-phenylene diisocyanate, tetramethyl decyl diisocyanate , cyclohexyl decyl diisocyanate, hydrogenated dithiocyanate, cyclohexyl diisocyanate, hydrazine diisocyanate, 2,2,4-trimethane diisocyanate Hexamethylene methacrylate, 2,4,4-tridecylhexamethylene diisocyanate, m-tetradecyl decyl diisocyanate, dimethyl decyl diisocyanate A diisocyanate compound such as a dimer acid diisocyanate or a compound which reacts with a vinyl monomer having a hydroxyl group, a carboxyl group or a mercaptoamine group in an equivalent molar amount can also be used as the isocyanate compound. Further, the polyfunctional isocyanate having three or more isocyanate groups in one molecule may, for example, be an aromatic polyisocyanate or an isocyanuric acid triisocyanate.

34 323716 S 201241081 Aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, etc., may be exemplified by the above-mentioned diisocyanate of diisocyanate Addition. A biuret that reacts with water, a terpolymer with a trimeric isocyanate ring. The compound having a blocked isocyanate group is not particularly limited as long as it contains a compound having an isocyanate group which is protected by ε-caprolactam, MEK® (MEK®) or the like. Specifically, the isocyanate group of the above-mentioned compound containing an isocyanate group may be blocked by ε-caprolactam, hydrazine, cyclohexanone oxime, pyrazole, phenol or the like. In the present invention, the compound (Β) may be used singly or in combination. The amount of the compound (anthracene) to be used may be determined in consideration of the use of the curable resin composition of the present invention, etc., and is not particularly limited, and the weight fraction of the eucalyptus (Α) 含有 with respect to the carboxyl group is contained. The amount of use is preferably 5% by weight to 4 weights, more preferably 1 part by weight to part by weight. By using the compound (B), the crosslinking density of the hardenable resin composition of the present invention can be adjusted to a suitable value, and various physical properties of the cured coating film can be further improved. When the amount of the compound (β) used is 5% by weight or more, the crosslinking density of the coating film after heat curing is an appropriate range, and the strength and heat resistance are both excellent. In addition, when the amount is less than 1 part by weight, the crosslinking density after heat curing is in an appropriate range, and as a result, the buckling property, flexibility, and adhesion strength of the coating film are extremely excellent. Next, the hot hardening aid of the present invention (the heat hardening aid (C) of the present invention directly assists the hardening reaction when the compound (B) and the modified ester resin (A) having a carboxyl group are subjected to a hardening reaction. The compound or the compound assisted by the catalyst 323716 35 201241081. The heat hardening aid (c) represents a compound which directly assists the hardening reaction, and has a function capable of reacting with a hydroxyl group, an amine group, an epoxy group, a carboxyl group or the like. The compound of the present invention or the compound which assists the hardening reaction by a catalyst may be suitably used in the thermosetting resin composition of the present invention, except for the compound (B). Specifically, cyanide may be exemplified. Acid ester compound, aziridine compound, acid anhydride group-containing compound, carboxyl group-containing compound, carbodiimide group-containing compound, oxetane group-containing compound, benzofluorene compound, maleic acid a quinone imine compound, a mercapto cis-butanediamine compound, a nadic ylidene compound, an allyl nadic amide compound, a vinyl ether compound, Alkenylbenzyl ether resin, thiol compound, melamine compound, gUanamine compound, amine resin, phenol resin, alkyd resin, acrylic resin, unsaturated polyester resin, decanoic acid diene a propyl ester resin, a decyloxy resin, a diphenyl benzene resin, a cough resin, a ketone resin, a triallyl cyanurate resin, a resin containing tris(2-hydroxyethyl) isocyanate, A thermosetting resin obtained by tri-polymerizing a resin containing triallyl trimellitate, a dicyclopentadiene resin, or an aromatic dicyanamide. The cyanate compound may be exemplified by a double (4- Cyanate phenyl)ethane, 2,2-bis(4-cyanylphenyl)propane, 2,2-bis(3,5-dimercapto-4-c-cyanophenyl)nonane, 2,2-bis(4-cyanate), hexafluoropropane, "," bis(4-c-cyanophenyl)-m-diisopropylbenzene, phenol addition A cyanate compound of a dicyclopentadiene polymer or the like, a prepolymer or the like thereof may be used singly or in combination, wherein 2,2-bis(4-cyanylphenyl)propane and 2,2 - double (3,5- 36 323716

S 201241081 - mercapto 4-3⁄4 acid phenyl) is particularly preferred because of the particularly good dielectric properties of the cured product. When a cyanate vinegar compound is used, a metal-based reaction can be used as needed. The medium can be used as a metal catalyst such as violent, iron, agglomerate, brocade, copper or zinc. Specifically, it can be used as an organic metal salt compound such as 2-ethylhexane salt or a naphthenate or an organic metal complex such as an acetamidineacetate complex. The compounding amount of the metal-based reaction catalyst is preferably from 1 to 1 ppm, more preferably from 1 to 1 ppm, even more preferably from 2 to 3 (8) of the melon with respect to the cyanate compound. When the amount of the metal-based reaction catalyst is 1 ppm or more, it can be sufficiently obtained.

When the effect is 3,000 ppm or less, the reaction is easily regulated, and the hardening speed is in a preferable range. The X aziridine compound may, for example, be N,N,diphenylmethane_4,4,-bis(1-azacyclopropanecarbonyl), N,N, 曱 benzene, 2, 4 bis (1_azacyclopropane carbonyl), bis- ugly thiol 1 (2·methylaziridine), tris(l-aziridinyi)ph〇sphine oxide , N'N-hexamethylene-ij-bis-azepine carbonyl), trimethylolpropane propionate-tri-n-azetidinyl vinegar, acid tetramethylmethanone-three _ --azetidyl vinegar, tris-2,4,6·(1-azetidinyl)], 3,5-trimorphine, ^methylpropane tris[3-(1-nitrogen Heteropropyl)propionic acid vinegar], triacetinylpropane aziridine)butyric acid vinegar], trimethyl ketone tris[3_(1_(2_ fluorenyl)azetidinyl) Sour vinegar], tri-propyl sulfonium triacetate [3_(1-azacyclohemany)-2-methylpropionic acid vinegar], 2,2' bis-bis-mercaptobutanol three [3_(1- Nitrogen heterocycle 2 yl) propionic acid vinegar], pentaerythritol tetrakis [3_(1_azacyclopropyl)propionic acid vinegar], bis-methyl ketone-4,4_bis-N,N' _ Ethyl urea, hexamethylene di-n, n, ethyl urea, 2,4,6-(tri-ethylethylenimine)_Syn_i哄, [[Mu] B 323 716 37 201 241 081 yl) propyl gas heterocyclyl] Ben -1,3_ Zealand Amides like. The compound containing an acid group is not particularly limited as long as it is a compound containing an acid anhydride group (b) and an acid anhydride group in the molecule. The acid anhydride group-containing compound other than the acid anhydride group-containing compound (b) may, for example, be a polycarboxylic acid anhydride such as a dicarboxylic anhydride, a hexacarboxylic acid trihydride, a hexacarboxylic dianhydride or a maleic acid liver copolymer resin. Classes, etc. Further, the compound containing an acid needle group is exemplified, and in addition to phthalic anhydride, tetrahydrophthalic anhydride, and the like, the maleic S*» anhydride copolymer resin may be exemplified by Sartomer Company SMA resin series, 岐阜Shellac Benzene ethylene-maleic anhydride copolymerized resin such as GSM series, p-phenyl ethene-maleic anhydride copolymerized resin, α-olefin/parabutylene such as polyethylene-maleic anhydride Diacid anhydride copolymer resin, "VEMA" (a copolymer of mercapto vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industry Co., Ltd., and cis-butyl dihydride anhydride acrylic modified polyolefin ("AUROREN series": Nippon Paper Chemicals Co., Ltd.), maleic anhydride copolymerized acrylic resin, and the like. The compound having a carboxyl group may, for example, be an ortho-decanoic acid, isophthalic acid, p-citric acid, 1,4-dimercaptopurine, 1,3-dimercaptodecanoic acid or 5-sulfonate-1. 3-dimethylisodecanoic acid, 4,4-biphenyldicarboxylic acid, 1,4-naphthoic acid, 2,6-naphthalene dibasic acid, norbornene dicarboxylic acid, diphenylmethane- An aromatic dicarboxylic acid such as a 4,4'-dicarboxylic acid or a phenyldicarboxylic acid; an alicyclic dicarboxylic acid such as a hexahydro-p-hydrogen acid, a hexahydroisophthalic acid, a hexahydro-glycolic acid or a tetrahydro-o-acid Acids; oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, 323716 38 201241081 Suberic acid, maleic acid, gas; oleic acid, anti-butene Diacid, dodecanedioic acid, pimelic acid, methyl maleic acid, glutaric acid, Ikonic acid, etc.: aliphatic dicarboxylic acid and the like.化合物 The compound containing a carbodiimide group can be exemplified by the CARBODILITE series of Nissin Textile Co., Ltd. Among them, CARB〇DILITEV〇1, 05, 07, and 09 are preferable because they are excellent in compatibility with an organic solvent. The oxetane group-containing compound may, for example, be anthracene bismuth [(3, oxetane-3-yl)methoxy]methyl fluorene benzene [manufactured by Toagosei Co., Ltd., trade name; Aronoxetane OXT-121, etc.], 3_ethyl winter {[(3-ethyloxa-2-butan-3-yl)methoxy]indolyl}oxetane [manufactured by Toagosei Co., Ltd., trade name; Aronoxetane OXT- 221, etc.], hydrazine, 3-bis[(3-ethyloxetan-3-yl)nonyloxy]benzene, 4,4'-bis[(3_ethyl_3_oxetane) (Ethyloxymethyl)biphenyl, (2-ethyl-2-oxetanyl)ethanol and an esterified product of p-nonanoic acid, (2-L»-yl-2-oxabendyl) An ester of ethanol and a vinegar varnish resin, an esterified product of (2-ethyl-2-oxetanyl)ethanol and a polycarboxylic acid compound, and the like. The compound of the present invention can be exemplified by "Pa", "P-alp", "p-ala", "B-ala", Macromolecules, 34, 7257 (hereinafter referred to as Macromolecules, 36, 6010 (2003). 2001) "p-appe", "Bappe:" 'RB-a type benzopyrene produced by Shikoku Chemicals Co., Ltd.", "Fa type benzopyrene:", "B_m type benzopyrene "Wait. The vinyl benzoyl ether resin may, for example, be ν_1000χ (manufactured by Showa Polymer Co., Ltd.), US Pat. No. 4,116,936, US Pat. No. 4,170,711, US Patent No. 4,278,708, and Japanese Patent Laid-Open No. 39 323716 201241081 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-283076 Vinyl benzoquinone based resin, etc. described in the booklet No. 2/〇8361. The maleimide compound has at least one maleimide group in the molecule, and may, for example, be a phenyl thidium diimide or an i.methyl-2,4_bis cis. Dimethylene iminobenzene, N,N,·········································· _ phenyl bis-butyric diimide, N, N, Miao (3,3-dimethyl-linked phenyl) dicis-butane quinone imine, N, N, -4, 4_ ( 3,3_Dimethyldiphenylmethane)bis-n-butylenediamine, hydrazine, Ν' ·4,4_(3,3·:ethyldiphenyl f) Imine, hydrazine, hydrazine · 4, 4 _ 2 基 基 院 双 双 顺 顺 二 二 酿 酿 酿 酿 酿 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -4 -44_ : Stupid base scales are two (four) amines, Ν, Ν ' · 4, 4 _ 2 secret shun _; 2 bis-imine, 2, 2. double [4_(4_; liT^ said iminobenzene Oxy)phenyl]propan-2-bis(tetra): butyl as... smear: quinone imine phenoxy fluorenyl] hydrazine, 1,1-bis[4-(4-cis-butyl bis-imide phenoxy) Base) decane, 4,4'-cyclohexylene-bis[called cis-butyl quinone diamine imine phenoxy)phenoxycyclohexyl , 2,2-bis [4- (4, butadiene dilute two (PEI) phenoxy) propan-octafluoro like burning 'may be used alone may also be used more than two kinds together dead. a methyl cis-butanthine imine compound having at least one compound in the molecule: a cis-butenylene-imide group-based compound or a polymer thereof, such as phenylmethylbis-succinimide, i-曱基_2, 'bismethyl succinimide, _,-m-phenylene bis-indenyl succinimide, sputum, 乂 323 716 40 201241081 phenyl bismethyl Maleimide, N,N,_4,4_linked phenyl bismethyl succinimide, N,N, _4,4-(3,3-dimethyl benzene Dimercaptosynyl succinimide, hydrazine, Ν'·4,4·(3,3-dimethyldiphenyl decane) bismethyl succinimide, hydrazine, hydrazine , _4,4_(3,3_diethyldiphenyl fluorene) bismethyl cis enediminoimine, hydrazine, hydrazine, _4,4_diphenyl dimethyl bis-butylene Imine, hydrazine, hydrazine, _4,4_diphenylpropane bismethyl succinimide, hydrazine, Ν'-4,4-diphenyl ether bismethyl succinimide, Ν,Ν, -4,4-monophenyl bis-methyl cis-butane diimide, 2,2-bis[4_(4-methyl- succinimide phenoxy)phenyl] Propane, 2,2-bis[3-t-butyl-3,4-(4-methyl cis Butylenediamine phenoxy)phenyl]propane, u-bis[4-(4-methylsuccinimide phenoxy)phenyl]decane, 4,4, cyclohexylene - bis[1-(4-methylsuccinimide phenoxy)phenoxy]_2_cyclohexylbenzene, 2,2-bis[4-(4-methylcis-butenylene) 'Amine phenoxy)phenyl]hexafluoropropane or the like can be used singly or in combination of two or more kinds. Nadickylimine compound 'a compound having at least one nadic amide group in the molecule or the polymer, such as phenyl nadic ylide, 1-methyl-2,4-double Nadickia Amine benzene, n, N'-meta-phenylene dipyridinium imine, N,N'-p-phenylene dipyridinium imine, n,N,-4,4-coupling Double nadic ylidene imine, N,N' -4,4-(3,3-dimethyl-linked phenyl) double nadic quinone imine, N, Ν' -4,4-(3,3- Dimethyldiphenylmethane) bis nadic ylidene imine, N,N' -4,4-diphenyl fluorene double nadic quinone imine, N,N' -4,4-diphenylpropane Double nadic ylidene imine, n,N'-4,4-diphenyl ether double nadic quinone imine, N,N'-4,4-diphenylfluorene double nadic ylide, 2,2 - bis[4-(4-nadickimine phenoxy)phenyl]propane, 2,2-bis[3-

41 323716 201241081 Second butyl-3,4-(4-nadickimine phenoxy) phenyl]propane, bis[4-(4-nadickimine phenoxy)phenyl]indole Alkane, 4,4, _cyclohexylene^[1-(4-nadickimine phenoxy)phenoxy]_2_cyclohexyl stupid, 2,2-bis[4-(4-nadick醯iminophenoxy)phenyl]hexafluoropropane or the like may be used alone or in combination of two or more. In the case of the allyl nadic quinone imine compound, there is a biguanide 4_(allylbicyclo[2.2.1]hept-5-ene-2,3-diimideimine)phenyl decane, The alkane-bis-allyl n-didecimide, the exo-indole group, the bis-allyl-naphthylamine, and the like may be used alone or in combination of two or more. In the case of the vinyl ether compound, there are 2-hydroxyethyl vinyl ether, deducted butyl vinyl scale, diethylene glycol monoethyl sulfonate, cyclohexane dimethanol diethyl _, cyclohexane dimethanol Monovinyl fluorenylcyclohexyl vinyl ether, cyclohexanyl methoxide oxime, ethylcyclohexanol, methoxyethyl vinyl fluorene, ethoxyethyl ethyl ketone, propyl Ethyl hydrazide, pentyl vinyl scale, diethylaminoethyl vinyl light, tricyclic oxime epoxy vinyl ether, ethylene glycol divinyl ether, diethylene glycol diethylene Ether, diethylene glycol divinyl ether, tetraethylene glycol divinyl ether, neopentyl alcohol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropanol divinyl ether , neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1, hydrazine dihydroxycyclohexane divinyl ether, 1,4-monohydroxymethylcyclohexane divinyl ether, hydroquinone diethylene ether, ethylene oxide modified hydroquinone divinyl ether Ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified 42323716

S 201241081 Bisphenol s divinyl ether, glycerol trivinyl ether, sorbitol tetravinyl ether, dimethicone diethylene bond, neopentyl alcohol triethyl sulfhydryl bond, neodymidine tetraol Vinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, bis(trimethylol)propane tetravinyl ether, bis(trihydroxyl)propane polyvinyl ether, etc. It can be used alone or in combination of two or more types. In the case of thiol compounds, there are 2,4,6-trimercapto-s-triazole, 2-dibutyl-indolyl-4,6--sulfo-s-dioxin, 2-anilinoyl -4,6-di-sulphate triterpenoid, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris- 3_mercaptopropionic acid crocodile, tris-(ethyl-3-mercaptopropionate The trimeric isocyanate, the neopentyl alcohol tetra-trimethyl propyl acrylate, and the dipentaerythritol hexa-trimethyl propyl propionate may be used singly or in combination of two or more kinds. The amine-based resin may, for example, be an addition compound with formaldehyde or a partial condensate thereof such as urea, melamine, benzoguanamine or acetamide. Further, the resin of the age may, for example, be an addition compound or a partial condensate of a compound such as a genus, a genus or a dioxin. Specifically, an anthracene resin, a nonylphenol resin, a third butyl phenol resin, a dicyclopentadiene formazan resin, a dicyclopentadiene phenol resin, a hydrazine-modified phenol resin, a tetraphenol resin, and a bisphenol can be exemplified. A resin 'polyethylene-based resin soluble enzyme brewing type (res〇1) resin or varnish type resin. Other examples include a naphthol compound, a triphenol compound, and a phenol aralkyl resin. Among them, the novolac type resin of the phenol resin is excellent in heat resistance and hardenability, and can be suitably used in the present invention. The heat hardening aid (C) 'catalyst means a compound which assists the hardening reaction, and may be exemplified by a tertiary amine and a salt thereof, a dicyandiamide, a carboxy hydrazine, an imidazole, an azabicyclic compound, a phosphine, The scale salts are preferably used because the thermosetting reaction 43 323716 201241081 is carried out more efficiently and the coating film resistance is excellent. Specifically, it can be exemplified by triethylamine, tributylamine, aglyldidecylamine, 2,4,6-tris(didecylaminodecyl)phenol, N_mercaptopiped, etc. Amines, and their salts; 2-mercapto-salt, 2-succinyl azole, 2,11- oxazole, 2 ethyl-4-methylimidazole, 1-cyanoethyl-2-methyl Imidazoles such as imidazole, 2 4 dicyanyl-6 (2methylimidazolyl-1)-ethyl-S-triazine, 2-ethyl-4-yl-imidazolium tetraphenyl borate, and salts thereof 1,5-diazabicyclo[5,4,〇]-7-undecane, anthracene, 5-diazabicyclo-[4,3,0]-5-anthracene, 1,4-two Azabicyclobutanes such as azabicyclo[2,2,2,]octane, bismuth borate, 8-diazabicyclo[5.4.0]undecene-7-tetraphenyl ester; dibutylphosphine a phosphine such as diphenylphosphine, tris(dimethoxyphenyl)phosphine, tris(hydroxypropyl)phosphine or tris(cyanoethyl)phosphine; tetraphenylphosphinium tetraphenylborate, methyl three a scaly salt such as butyl quaternary tetraphenyl boron salt or decyl tricyanoethyl quaternary tetraphenyl boron salt; other compounds which are in the form of a catalyst and which directly assist the hardening reaction, may be dicyandiamide. , carboxy oxime, etc. The carboxy hydrazine may, for example, be a diterpenoid or a diterpene. These thermosetting assistants (C) may be used alone or in combination of two or more. The amount of use of the thermosetting auxiliary (C) may be determined in consideration of the cured physical properties of the curable resin composition, and is not particularly limited, and is used in an amount of 100 parts by weight based on 100 parts by weight of the carboxyl group-containing modified ester resin (A) of the present invention. The amount is preferably in the range of 5 323 716 44 201241081 parts by weight to 20 parts by weight, more preferably in the range of 1 part by weight to 忉 by weight. Thereby, the cross-linking speed, cross-linking density, and cohesive force of the thermosetting resin group of the present invention can be adjusted to further enhance various physical properties. When the amount of the heat-curing auxiliary (C) is 5 parts by weight or more, the effect of the addition can be sufficiently obtained, and when the amount is 20 parts by weight or less, the electrical insulating property, the bonding strength, and the solder heat resistance are excellent. . Others, the thermosetting resin composition of the present invention may further contain any of the following components, solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, antifoaming agents, within a range not impairing the purpose thereof. , leveling agent, ion trapping agent, moisturizing agent, viscosity adjusting agent, preservative, antibacterial agent, antistatic agent, anti-blocking agent, ultraviolet absorber, infrared absorber, electromagnetic wave shielding agent, filler. In particular, when it is used for electronic materials, it is used for insulating parts (such as circuit protection films, coating layers, interlayer insulating materials, etc.) that directly contact the circuit, and when there is a possibility of high heat (such as a printed wiring board adhesive, a supporting substrate, etc.) around the circuit. It is preferred to use a flame retardant in combination. The flame retardant may, for example, be a melamine-filled acid, a poly-capric acid melamine, a strontium sulphate, a cesium polyphosphate, an ammonium phosphate, an ammonium polyphosphate, a guanamine amide, a polyamid ammonium amide, an ammonium phosphate phthalate, Phosphate-based compounds such as polystearate and polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphoric acid compounds, diethylphosphonic acid ( Ph〇Sphinicacid), phosphoric acid compounds such as thiol ethylphosphonate, aluminum diphenylphosphinate, aluminum ethyl butylphosphinate, aluminum decyl butylphosphinate, aluminum polyphosphinate, phosphine oxide compounds, Phosphorus-based flame retardants such as phosphine compounds and phosphoniumamine compounds; melamine, melain, 45 323716 201241081 melamine, meloxime, trimeric amine trimerization Triterpenoids such as sulphuric acid vinegar, nitrogen-based flame retardants such as cyanuric acid compound, iso-cyanuric acid compound, di-salt compound, time compound, diazo compound, urea, etc.; Compounds such as Shixi flame retardant; toothing double A, toothing Low molecular inclusions such as oxygen compounds and toothed phenoxy compounds: (4) oligomers or polymers, etc. (4) flame retardants; hydroxides, antimony, magnesium, oxyhydroxide, barium hydroxide, Oxidation of metal hydroxide by oxidation: reduction of tin, alumina, magnesia, zirconia, zinc oxide, molybdenum oxide, ruthenium, zinc carbonate, carbonic acid, carbonic acid, carbonation, zinc citrate, hydrated glass, etc. Inorganic flame retardant and the like. In the present invention, it is preferable to use an antimony-based flame retardant and a nitrogen-based non-dental flame retardant in the influence of the environmental impact to the public in recent years, among which the thermosetting resin group of the present invention is used. 'It is preferred to use a flame retardant scaly nitrogen compound. The material is melamine, ammonium polyphosphate, melamine, and the like. In the present invention, these flame retardants may be used singly or in combination. The second leveling agent can be used as an example, a smoke system, or an acrylic resin. The ion trapping agent can be applied to an inorganic or organic ion exchanger. In detail, the ion exchange tree D ion trapping of the inorganic ion exchanger ixe of the East Asia Synthetic Co., Ltd. and the three-injury company may be used, and is not limited thereto. There is a (4) person to apply! The thermosetting resin composition of the invention may be prepared by mixing the above-mentioned modified ester resin, (8) compound, (C) thermal hardening aid, and the like as required Available from any component. 323716 46 201241081 The cured product of the invention of the present application is coated by a conventionally known method such as comma coating, knife coating, die coating, and nozzle coating. (lip coating), roll coating, curtain coating, bar coating, gravure printing, flexography, dip coating, spraying By a method such as spray coating or spin coating, the thermosetting resin composition is applied to at least one surface of the release substrate, and then dried at 40 to 150 ° C. Further, the dry film thickness of the adhesive layer is preferably from 5 μm to 500 μm, and more preferably from μμηη to ΙΟΟμηι, in order to exhibit sufficient adhesion and solder heat resistance. Further, a method of manufacturing a printed wiring board using a thermosetting resin composition will be described next. The conductive pattern of the flexible printed wiring board formed by the printing technique of the conductive pattern on the flexible or insulating plastic film such as polyester or polyimide, and the thermosetting resin of the present invention When the composition is superimposed and heated and pressurized, the thermosetting resin composition is cured, and a flexible printed wiring board provided with a protective layer can be obtained. a method of δ and a conductive circuit, for example, forming a photosensitive etch photoresist layer on a copper foil of a flexible copper-clad plate formed by providing a copper foil on a base film without or via an adhesive layer, and having a circuit The pattern is exposed to the mask film, and only the exposed portion is cured, and then the copper foil of the unexposed portion is removed by etching, and the remaining photoresist layer or the like is peeled off, and a conductive circuit can be formed from the copper foil. Alternatively, only a desired circuit may be provided on the base film by means of sputtering, plating or the like. Further, a hardenable adhesive layer obtained by peeling off the peelable substrate from the thermosetting 323716 47 201241081 resin composition of the present invention is sandwiched between the plurality of flexible printed wirings, and heat is applied by heating/pressurization. The curable resin composition is cured to obtain a multi-reed printed wiring board. The thermosetting resin composition of the present invention can be used to laminate a copper foil and a heat-resistant insulating flexible substrate. Further, by using the thermosetting resin composition of the present invention, a flexible printed wiring board with a reinforcing material can be obtained. A flexible printed wiring board with a reinforcing material is a flexible printed wiring board, and a reinforcing material such as glass epoxy, metal, or polyimide is peeled off from the thermosetting resin composition of the present invention. The curable adhesive layer formed of the material is cured by heat/pressure to cure the thermosetting dendritic composition, and the reinforcing printed wiring board is attached to the flexible printed wiring board. According to the present invention, it is excellent in adhesive strength, electrical insulating properties, heat resistance, buckling property, workability, and solder resist resistance, and in particular, it satisfies both storage stability and processing stability, and further maintains high adhesion strength while exhibiting high heat resistance. Further, it is possible to achieve both the strength and electrical insulation properties, heat resistance and buckling properties, and the resin containing the (four) base and the thermosetting resin grade. These can be applied to an adhesive for an electronic material, a bonding sheet, a coating agent, a solder resist for a circuit coating, a cover film, an adhesive for electromagnetic wave shielding, a plating resist, and a printed wiring, which are mainly used for the periphery of a flexible printed wiring board. Interlayer electrical insulation materials, optical waveguides, etc. The thermosetting resin composition of the present invention is particularly suitable for use as an adhesive composition. (Embodiment) Hereinafter, the present invention will be further described by way of examples, and the scope of the present invention is not limited to the following examples. In addition, the "parts" and "%" of the examples represent "parts by weight" and "% by weight", respectively, and Mw means weight average molecules 48 323716

S 201241081 Quantity. * <Measurement of Weight Average Molecular Weight (Mw)> The measurement of Mw was performed by GPC (gel permeation chromatography) "HPC-8020" manufactured by TOSOH CORPORATION. GPC is a liquid chromatography method in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified depending on the difference in molecular size. In the measurement system of the present invention, the column "LF-604" (made by Showa Denko Co., Ltd., GPC column for rapid analysis: 6 mm ID x 150 mm) was connected in series and connected to 2 tubes, and the flow rate was 0.6 ml/min, and the column temperature was 40°. The conditions of C were carried out, and the weight average molecular weight (Mw) was determined by conversion into polystyrene. [Production Example 1] A polycarbonate diol (Kuraray Polyol C-2090: manufactured by Kuraray Co., Ltd.) was placed in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer. - mercapto-1,5-pentanediol/1,6-hexanediol =: 9/1 (mole ratio) copolymerized polycarbonate diol: hydroxyl value = 56 mg KOH / g, Mw = 2000) 292.1 parts 44.9 parts of tetrahydrophthalic anhydride (RIKACID TH: manufactured by Nippon Chemical Co., Ltd.) and 350 parts of benzene in a solvent were heated to 60 ° C under a nitrogen gas stream to be uniformly dissolved. The flask was then warmed to 110 ° C and allowed to react for 3 hours. Thereafter, after cooling to 40° C., '6 lb bis bisphenol A type epoxy resin (YD-8125: ET: 175 g/eq, manufactured by Tosho Kasei Co., Ltd.) was added, and triphenylphosphine 4 was used as a catalyst. The temperature was raised to ll 〇 ° C, and the reaction was carried out for 8 hours. After cooling to room temperature, 11.8 parts of tetrahydrophthalic anhydride was added and reacted at 110 ° C for 3 hours. After cooling to room temperature, the solid content was adjusted to 35% with toluene. A modified ester resin (A) solution containing a plurality of groups of the present invention is obtained. The thiol-containing modified 323716 49 201241081 obtained from the present production example has a weight average molecular weight of 12,600, based on the measured solid content of the resin. The acid value was 15.3 mgKOH/g. [Production Examples 2 to 36, Comparative Production Examples 1 to 9] The same procedures as in Production Example 1 were carried out except that the materials shown in Tables 1 to 3 were replaced, and the carboxyl group-containing product of the present invention was obtained. The ester resin (A) solution was modified.

50 323716 S 201241081

Oi 本| S CJ «1 in in (Ο CD X CM <〇I YD-8125 cn with XS a 1 inch 09 this § Csl 〇S OJ glare ας s csi X CM CC S ω >· O) a ί : 1 o OJ cn 卜孩i; 〇«η S CO right< X to ai 00 na ω ό >〇> X 5 o 卜r- ίο (D this ί3 〇00 gc〇 right in in CJ 〒 Q s σ> o § s ir> CO IT3 联 S 0 ιο m CM S 1 ZI <〇ci 1Λ ΙΩ eg Ξ 1 Q 00 a X ai o wear in in ri § S 〇gn X in K ai >r> ί <〇(D g § in r- s Γ5 本 m § S 〇<〇s X io ? O CO 棼X CO CO os rt s Cl 本〇SS tA s CO X 卜<b S o > 00 Φ f CO ms in l〇ri Ϊ: Φ S 8 〇r*i 〇> C\JX a> 5 ST o O) <〇X \- oo o § CM <〇IO τ 3 吞<〇§ f^s Τ Ι s2 Φ £ 0V Lane 03 Race 5 Right Think Umbrella Φ ί Γ X 〇1 m Ϊ Child 1 UHC50-200 i 〇> ιο X 1- 1 EX-214L 1 (C CO X r- σι ο ο 岂ΙΟ CO 寸 i nt u 泛 c〇ιο K 03 g C7 X σ> to esi 5 I ΙΑ ci 8 CNJ ΙΟ CO c〇S 〇S CM Q. Σ h X s Q >- σ> X 5 ο (Ο η (Ο气 CM i § 3 Ο 00 CM < a. I QQ esj ί e<g 妄to CM ¥ Q 〇> I ai ο S fen eo W ϊ 1 S g CNJ < ω Έ Q a X CSJ (Ο a >· σ> ai v X 甘σι ο S ΙΟ (Ο in to 〇i § S 〇o 00 CNJ Ί Ί v> I 1- OJ s 〒 >a> CT X 1-inch σΐ ο r- <0 ιο <〇co 联3赛S r· i &务<〇想<〇错审<0 屮4t ίΓ牛> P1 XO Think A, - 51 323716 201241081 Undergraduate 〇O eg »1 <〇eg CO m YD-8125 1 r* S' f ο ο § (η in' 本〇5 σ> OJ ί 03 5 ω > r - s ο § ο; 々5 eg eg this § ώ (O eo CVJ ΰ • 1 ϊί S CO f σ> Λί tn e^ Q f- inch f ο g in ΙΟ CO η this m axis 8 early σ 〇n X 00 > O) te I Ν 00 Ο £ 9 S § S 1 〇σ><d another X 3 in M CO a >- 卜 9 X Oi 8 S φ c4 〇> Ϊ Q 8 a £ in 〇 > O) CM X 〇> \n CM 00 a in oi in X 5 ο 云ΙΟ C5 00 5 W § ώ £ s evj » «ι 货 tn (Ο σί X CM CO s tt <〇s X η &> ο S LO S Ϊ eg ia C5 s CO f <〇s 5 > (0 sf η ai SS ΙΟ esi c〇<〇Ϊ « 〇 5 3 <〇m eg ί σι Bu 2 tn in <0 X CO « ο S 5 联 3 <〇♦ τ· 1 JO 々>Christine·<〇$ right 3 ·<〇影右坩φ ΦΙ 屮«* 申1 Example 5 X o S 〇〇> CO 1 s r> [132.3/139.8 I CM <d GO ◦ 〇a Γ- f tn ir> PD g 运 r- s 〇> 5 Axis 芑ο Ο g 2 3 00 B §_ XO) 8 CO ? X Oi To β) I l〇<nss; CO tn 兖S 坩« s Ο δ > eo 1 SD CO CO CO M ή X c〇in CO s 〒 Q CO i Oi in CO os in CO CO s S5 5 mmg ΐ 5 nf 〇> 2 csi ί to σί o § CO ms iO CN mga CM to sfa» 2 Oi \ei (O ί CO tn og CO a S 5 聃si cn ai C3 X Γ5 m (SJ ? 〇5 To X CO ib os ro - engage in 3 matches 4〇jj i r-\ »- v5 swallow <8 £ Christine right η *<〇5. η <〇右Φί 屮ίΓ .Ιι- VI S 苞3, String 52 323716 201241081 I Comparative Manufacturing Example 3 I UCH00 I 274.5 s§ [ 54.9 I I_ EX-212L I I_me IX 16.9 1 29400 1 19.4 | CM This «ί 1 Ρ-20 41 丨I 327.1 I_____ 31.9_____” 1 EX-212L I f ; 9.83 1 50400 1 13.6 I 丨Comparative Manufacturing Example 1 II 02090 ! 1 315.8 I < CO I_3L6_I I YD8125 I ! 52.6 II 9.73 1 51000 I 13.5 | I C590 1 208.9 1 I 83.6 II EX-212L II 107.5 | fE 1 128.7 1 ! 19400 II 105.4 j 5 g gi c 1 330.75 1 X I- I_33J_I I YD8125 II 36.2 IXH i 3.34 1 4100 1 8.25 I Eng! C20SO ! 1 318.5 1 1 snail fermentation 1 00 cd f I_m_i 1 YD-8125 II 64.4 IX 1 34.4 1 S 53400 | 32.3 IS t— ) ί :s :3 1 265.1 i X _88J_I 1 YD-8125 II 96.9 j 36.2 1 42300 1 37.4 I 丨 Manufacturing Example 32 I o 3i 2 DI 264.8 IX _88J_ I YD-8125 I Γ-* σ> X 1 36.3 1 1 45500 | I 33.9 I 丨 Manufacturing Example 31 1 os 5 Discussion 3 I 131.9/139.4 1 XI 85.9 II ZX-1059 II 92.8 IX h* 35.4 1 44200 1 33.3 I Ά U Polyester compound (a) Polyol compound (a-1) Compound containing an acid anhydride group (b) Epoxide compound (d) Compound containing an acid anhydride group (b) tf UN «tw i 1 1 Comparative Manufacturing Example 9 1 I 1.6-HD | 1_8L3_1 S5 | 137.8 | | YD8125 | ! 231.0 | X 5 | 1660D I | 8 | 1 Comparative Manufacturing Example 8 1 I 1.6-HD | 1_Z5J_1 X | 180.7 | | YDBI25 | | 199.2 | X 1_3M_I | 14300 | 1 31.9 I | Comparative Manufacturing Example 7 1 | C2090 | | 282.9 | 1_§A_I I_28J_I | YD8125 I_4M_I | 8.85 1 | 59900 | od | Comparative Manufacturing Example 6 1 | PTG-2000SN 1 丨302*5 ] | 45.9 I ! YD8125 | I „ 50.4 I 1__10.5 I | 56700 | 1 24.1 I |Comparative Manufacturing Example 5 1 | C2090 | 1^271,5__I ί L 42,3__I | YD9125 | | 46.4 | I 8.48 | [60100 | I 17.6 | | Comparative Manufacturing Example 4 | | P-2010 | | 325.6 | S5 3Z6 | YD8125 | 41.9 | I_10.2 _I | 49400 | ! 13.9 I | Production example / Comparative manufacturing example | Polyol compound (a) Polyester compound (a-1) Compound containing an acid anhydride group (b) Epoxy compound (d> Compound (b) | Weight average molecular t| | Acid value [mgKOH/dl 53 323716 201241081 C-2090: Kuraray Co., Ltd., 3-mercapto-1,5-pentanediol/1,6-hexanediol = 9/1 (Morby) copolymerized polycarbonate diol T-5652: Asahi Kasei Chemicals Co., Ltd., C5C6 copolymerized polycarbonate diol UHC50-200: Ube Hsing Co., Ltd. Company, 1,6-hexanediol / caprolactone = 5/5 copolymerized polycarbonate diol UC-100: manufactured by Ube Hiroshi Co., Ltd., based on 1,4-cyclohexanedhenol Polycarbonate diol UM90 (l/3): manufactured by Ube Industries, Ltd., 1,4-cyclohexanedodecanol/1,6-hexanediol = 1/3 copolymerized polycarbonate diol UM90(1/1): 1,4-cyclohexanedimethanol/1,6-hexanediol = 1/1 copolymerized polycarbonate diol UM90 (3/1): Ube Hiroshi Co., Ltd., 1,4-cyclohexanedodecanol/1,6-hexanediol = 3/1 copolymerized polycarbonate diol PTG-2000SN: made by Baotu Valley Chemical Co., Ltd. Tetra-decyl diol PTG-L2000: manufactured by Baotu Valley Chemical Co., Ltd., polytetradecyl diol (weight average molecular weight fishing 2000) GI-2000: manufactured by Japan Soda Co., Ltd., hydrogenated polybutadiene II Alcohol (weight average molecular weight about 2100) G-2000: ,本曹达股份有限公司, α,ω-polybutadiene diol (weight average molecular weight about 1800)

Poly-ip: manufactured by Idemitsu Kosan Co., Ltd., hydroxyl terminated liquid isoprene (weight average molecular weight about 2500) KF-6002: manufactured by Shin-Etsu Chemical Co., Ltd., two ends 曱54 323716 201241081 ~ Alcohol-modified type Polyoxygenated oil (weight average molecular weight about 3000) • P-1041: 3-methyl-1,5-pentanediol, manufactured by Kuraray Co., Ltd. / 1,4-cyclohexanedicarboxylic acid copolymerized polyester Polyol (weight average molecular weight about 1000) P-2041 : 3-mercapto-1,5-pentanediol/1,4-cyclohexanedicarboxylic acid copolymerized polyester polyol manufactured by Kuraray Co., Ltd. (weight Average molecular weight: about 2000) P-2010 : Made by Kuraray Co., Ltd., aliphatic polyester polyol (weight average molecular weight about 2000) C-590 : Kuraray Co., Ltd., 3-mercapto-1,5-pentanediol /1,6-hexanediol = 9/1 (mole ratio) copolymerized polycarbonate diol (weight average molecular weight about 600) C-1090: manufactured by Kuraray Co., Ltd., 3-mercapto-1,5- Pentylene glycol/1,6-hexanediol = 9/1 (mole ratio) copolymerized polycarbonate diol (weight average molecular weight about 1000) TH : New Japan Physical and Chemical Co., Ltd. , tetrahydrophthalic anhydride HNA-100: manufactured by New Japan Physical and Chemical Co., Ltd., methyl bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride TMA anhydride: trimellitic anhydride SA: New Japan Physical and Chemical Co., Ltd. Company, succinic anhydride YD-8125: manufactured by Dongdu Chemical Co., Ltd., bisphenol A epoxy resin EX-216L: Nagase ChemteX Co., Ltd., cyclohexanol diethylene oxide diglycidyl ether

55 323716 201241081 EX-214L : 1,4-butanediol diepoxypropyl ether EX-212L manufactured by Nagase ChemteX Co., Ltd.: Nagase ChemteX Co., Ltd., 1,6-hexanediol diepoxypropyl Ether YX-8800: manufactured by Mitsubishi Chemical Corporation, dihydroxy fluorene type epoxy resin YDF-8170C: manufactured by Dongdu Chemical Co., Ltd., bisphenol F type epoxy resin ZX-1059: manufactured by Dongdu Chemical Co., Ltd., bisphenol Epoxy resin BHPA : N,N-bis(2-hydroxypropyl)aniline DMBA: dihydroxymercaptobutyric acid TMP: trihydroxymethyl propane 1,6-HD : 1,6-hexanediol (Example 1) 100 parts of a solid content of a solution of a modified ester resin (A) containing a carboxyl group obtained in the production example, and a polyfunctional epoxy propyl ether type epoxy resin of the compound (B) (EPIKOTE 1031S, manufactured by Mitsubishi Chemical Corporation) 20 parts and CHEMITITE PZ (manufactured by Nippon Shokubai Co., Ltd., polyfunctional nitrogen heterocyclic propyl compound) in 20 parts and thermosetting agent (C) to obtain a thermosetting resin composition. The resin composition is applied to the peeled after the film thickness after drying is 30"m$ The film is dried on the film, and then the layer is attached. Then, another peeling-treated polyester film is laminated on the side of the adhesive layer to obtain a double-sided protective film. 323716

S 56 201241081 (Examples 2 to 27) * The modification of the carboxyl group-containing modified product (A) of Production Example 1 used in Example 1 was replaced with the change of the carboxyl group obtained in Production Examples 2 to 27, respectively. Except for the solution of the ester resin (A), the same operation as in Example i was carried out to form a back sheet with a double-sided protective film. (Example 28) A polyfunctional epoxy propyl ether type epoxy resin compounded with respect to the solid content of the carboxyl group-containing modified ester resin (A) solution obtained in Production Example 28, and the compound (B) 18 parts of "EPIK〇TE1〇31S" manufactured by Mitsubishi Chemical Corporation, and 1 part of dicyandiamide of the thermosetting assistant (C), and a thermosetting resin composition was obtained. The thermosetting resin composition was uniformly coated on the release-treated polyester film so that the film thickness after drying became 3 Å #m, and dried, and an adhesive layer was provided. Then, another polyester film which was subjected to the release treatment was laminated on the side of the adhesive layer to obtain a back sheet having a double-sided protective film. (Examples 29 to 36) The carboxyl group-containing modified ester resin (A) solution of Production Example 28 used in Example 28 was replaced with the carboxyl group-containing modified ester resin obtained in Production Examples 29 to 36, respectively. Except for the solution, the same operation as in Example 1 was carried out to prepare a back sheet with a double-sided protective film. (Examples 37 to 64) A gusset having a double-sided protective film was formed in the same manner as in Example 1 except that the thermosetting resin composition was obtained in the composition shown in Table 4. 57 323716 201241081 1 Real mask 5〇| I 100 I m CNJ 1 embodiment 49 〇in CSJ - ir> 丨 Example 48 8 in CM - in 1 Example 47 1 100 in eg • - l〇1 implementation inverted 46 〇m CNJ produced u> | Example 45 I 100 m eg LA | Example 44 I 1〇〇U) esi in 5 i 〇CM io | Example 42 〇tn CM δ s 1_ Real mask 40 〇CO - Ο) P1 本〇-〇8 η 本〇 in eg CO T· CNJ 本 oblique I Manufacturing Example 17 ί I Manufacturing Example 23 I 丨Manufacturing Example 28 I CO CM CO I EOCN-102S I 1 EPPN-201L 1 1 VH434L 1 1 ONCOAT 1040 II BL3175 1 1 B80T I 1 DICY 1 I CHEMITITE PZ I 1 RIKACID TMTA-C 1 Aronoxetane OXT-121) Ba II CARBODILITE V-07 I ZISNET DB I TD-2131 I BMI-2300 I ws B) Thermal hardening aid (C) 1 Example 64| 〇- <〇〇T- T«« 〇ST—I Example 61| 〇〇〇T—I Example 6〇| 100 I cn in 本L i〇〇_J - I Example 58| § g - 掩 掩 57 57| I 100 -1 § SL祖" l〇CM一in 丨Example 55| LmJ l〇CM - LA I Example 54| 〇mm 丨Example 53| I 100 1 in OJ - in S τ 埃 1 100 1 m CM τ — m U) This 1 1〇〇I in CM s T·· 丨 Manufacturing Example 2 I I I Manufacturing Example 23 I Manufacture 锎 28 CO 坩 Vt 1 828 1 EOCN-102S EPPN-2Q1L YH434L ONCOAT 1040 BL3175 B80T 1 DICY 1 NE- s 3 RIKACID TMTA-C 1 Aronoxetane OXT-121 Ba r- ? > g 〇ύ «< ZISNET DB I TD-2131 I BM1-2300 1 Compound (B) Thermal Hardening Aid (c) 828 : Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy compound EOCN-102S: manufactured by Nippon Kayaku Co., Ltd., nonylphenol novolak type epoxy resin 58 3237 16 201241081 ^ EPPN-201L: Made by Nippon Kayaku Co., Ltd., phenol novolak type ring * Oxygen resin. YH434L:: Dongdu Chemical Co., Ltd., tetrafunctional polyepoxypropylamine ONCOAT 1040 : Nagase ChemteX Co., Ltd. , the first type of multifunctional epoxy resin BL3175: manufactured by Bayer Urethane Co., Ltd., a trimeric isocyanate type block isocyanate B80T: manufactured by Asahi Kasei Chemicals Co., Ltd., block isocyanuric acid DICY: dicyandiamide CHEMITITE PZ , manufactured by Sakamoto Catalyst Co., Ltd., polyfunctional nitrogen heterocyclic propylidene compound RIKACID TMTA-C : New 曰 理 理 ,, polyfunctional acid needle

Ar_xetaneOXT-121: manufactured by Toagosei Co., Ltd., 14 pairs of {[(3-ethyloxetan-3-yl)methoxy]indolyl oxirane Ba: Siguohuacheng Co., Ltd. , benzopyrene D well compound CARBODILITEV-07: manufactured by Nisshinbo Co., Ltd., polycarbodiimide compound ZISNET DB ··Sanxie Chemical Co., Ltd., 2_dibutylamino group _4 6_ dimercapto- S-三D井' TD-;2131 : DIC phenolic varnish resin BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd., polyphenylmethane maleimide compound ^ ^ (Comparative example 1 to 9) 323716 59 201241081 The same operation as in Example 1 was carried out except that the carboxyl group-containing modified ester resin (A) solution of Example 1 was replaced with the resin solutions obtained in Comparative Production Examples 1 to 9, respectively. The adhesive sheet of the double-sided protective film. The storage stability, processing stability, adhesion strength, solder bath resistance, solder adhesion strength, humidification, bathing bath compatibility, insulation reliability, and solder resist resistance of the back sheets obtained in the examples and the comparative examples were evaluated by the following methods. . (1) Processing stability The 65 mm x 65 mm backsheet with the protective film removed was lost to a 75 mm thick polyimide film [Kapton 300H manufactured by DUPONT-TORAY Co., Ltd.] and a copper laminate of 45 mm thick. The sheets were laminated at 80 ° C, and then subjected to crimping treatment at 160 ° C and 1.0 MPa for 1 hour. Again, the test piece was taken at 160. (2) Thermal hardening for 2 hours, and a test piece for evaluation was prepared. The difference in area between the edge of the test piece before and after the heat curing was measured, and the work stability was evaluated as the excess area. When the edge layer is softened by heat, the degree of contact between the circuit board and the contact between the wirings is evaluated, and the result of the reference determination will be described later. ◎...... "Excess area S 100mm2" 〇... ..."100mm2 &lt;exceeded area^25〇mm2" △..."250mm2<exceeding area $50〇mm2" X..."500mm2<out of area" (2) Then the intensity will The test piece prepared for the evaluation of processing stability was cut into a width l〇mm, a length of 65 mm, and an elongation rate of 60 323716 in an environment of 23% relative humidity of 50%.

S 201241081 £&gt; A tear peel test was carried out at 300 mm/min, which was determined to be followed by a strong yield - (N/cm). This test evaluates the strength of the adhesive layer at normal temperature use =

Then, the reference judgment result will be described later ^ X ◎ ...... "18 (N / cm) &lt; subsequent strength" 〇 ... "12 (N / cm) &lt; then the strength S 18 (N / Cm) J △..."8(N/cm) &lt;then strength S 12(N/Cm)" x..."Continuous strength S 8(N/cm)" (3) Preservation stability will be implemented The adhesive sheet with the double-sided protective film prepared in the examples and the comparative examples was subjected to heating and storage at 40 ° C for 3 months, and then laminated, crimped, and thermally cured under the above condition (1) to be the same as (2) above. The method evaluates the subsequent strength comparisons obtained by pressing the sheets which have not been heated and stored. This test evaluates the stability of the adhesive layer in the uncured state by the difference in adhesion strength caused by the presence or absence of heat, heat, and presence. The better the stability of the unhardened state is, the more stable the unhardened state is. At the same time, the strength is less reduced, and the worse the stability over time, the less stable the unhardened state, the heating promotes the hardening reaction, and the strength is greatly lowered as compared with the case where the heating is not applied. : The criteria described below determine the results of these evaluations. ◎ ...... "The heating promotes the final strength to be completely unchanged" 〇... "The heating promotes almost no change in the bonding strength" △... "The heating promotes the subsequent strength to be slightly lowered" X..." Heat promotion promotes a significant decrease in the strength of the bond. (4) Solder bath resistance The test piece having a width of 1 mm and a length of 65 mm 323716 201241081 is cut in the same manner as in the above (2), and the polymer is fused at 260 ° C. The imine film surface floated in contact with it for 1 minute. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of abnormality such as foaming, floating, peeling, and the like of the subsequent layer was evaluated. In this test, the thermal stability of the adhesive layer in the case of contact soldering was evaluated by appearance, and the appearance was not changed before and after the soldering treatment with respect to the heat resistance, and the heat resistance was poor, and foaming and peeling occurred after the soldering treatment. The evaluation results are judged based on the criteria described later. ◎...... "There is no change in appearance" 〇... "A slight foaming is observed" △... "Foaming is observed" X... "Strong foaming and peeling are observed" (5) Strength after soldering The test piece after the evaluation of the solder bath resistance of the above (4) was measured for the adhesive strength in the same manner as in the above (2), and the adhesive strength before the soldering treatment and the bonding strength after the soldering treatment were compared. In this test, the thermal stability of the adhesive layer at the time of solder contact was evaluated by the change in the adhesive strength before and after the soldering treatment, and the strength was not changed before and after the soldering treatment with respect to the heat resistance, and the heat resistance was poor after the soldering treatment. Significantly lower. The evaluation results are judged based on the criteria described later. ◎...... "There is no change in strength at all" 〇... "There is almost no change in strength" △... "The strength is slightly lowered" X... "The strength is then significantly lowered" (6) Humidity solder bath resistance 62 323716

S 201241081 A test piece of a width i〇mm and a length of 65 mm was cut in the same manner as in the above (2), and placed in an environment of 40 ° C and a relative humidity of 90% for 96 hours* to be humidified, at 26 〇. . In the molten solder of (:, the polyimide film surface was floated in contact with the surface for 1 minute. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of abnormality such as foaming, floating, peeling, and the like of the adhesive layer was evaluated. The thermal stability of the adhesive layer in the case of contact with fresh tin in a humidified state is evaluated by the appearance, and the appearance is not changed with respect to the heat and humidity resistance, and the heat and humidity resistance is poor, and foaming and peeling occur after the soldering treatment. Judging the results of these evaluations. ◎ ...... "There is no change in appearance" 〇... "There is almost no change in appearance" △...... "Observation of foaming" x.... .. "Strong foaming and peeling was observed" (7) 65 mm x 65 mm-size adhesive sheet of the insulation-relieving protective film was sandwiched between polyimine films having a thickness of 25 m [DU PONT-TORAY (Kapton) 100H"] and a printed pattern of a comb pattern (conductor pattern width/space width = 50 with 111/50//111) forming a copper circuit on polyimine, laminated at 8 ° C, then 16 (rc and 1 MPa conditions for 1 hour crimping. Again, this test piece was at 160t: thermosetting 2 In the hour, a test piece for evaluation was prepared, and a DC voltage of 50 V was continuously applied for 100 hours in a conductor circuit of the test piece in an environment of a temperature of 13 ° C and a relative humidity of 85%, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are the same as below. ◎ ......Insulation resistance value 108Ω or more 63 323716 201241081 〇......Insulation resistance value 107 or less is less than 108Ω △ ......Insulation resistance value 106 or more is less than 107Ω X...Insulation resistance value is less than 106 Ω (8) Solder resistance The thermosetting resin composition is uniformly coated on a thickness of 75/m in such a manner that the film thickness after drying is 30 β m. The yttrium imide film [Kapton 300H manufactured by DU PONT-TORAY Co., Ltd.] was dried, and the test piece was thermally cured at 160 ° C for 1 hour to prepare a test piece for evaluation. A few drops of weakly active rosin were dropped. (rosin) flux (manufactured by Alpha Metals Co., Ltd., Japan, trade name: RM-615) was heat-treated in an oven at 260 ° C for 3 minutes on this test piece. The test piece was taken out from the oven, and the flux was wiped with isopropyl alcohol. After the 'thickness of the cured film on the polyimide, it is judged as follows. If there is no problem, it is 〇. 〇...The film thickness changes less than 5/zm △ ...... The film thickness changes from 5 to l〇# m X... The film thickness changes more than 10ym (9) Flexibility The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75/m in such a manner that the film thickness after drying was 30/m [DU PONT-TORAY rKapton 300H) After drying, the test piece was heat-cured at 16 ° C for 1 hour to prepare a test piece for evaluation. The test piece for evaluation was bent to 180 degrees, and the same portion was bent to 180 degrees on the opposite side. The state of the coating film at this time was judged based on the following criteria. 〇...No cracks were seen on the film surface. 323716 64 201241081 Δ...Some cracks were seen on the film surface. X································ The crack was clearly observed on the surface, (10) Flexibility The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75 #m in such a manner that the film thickness after drying became 3 〇em [Du PONT- TORAY (Kapton 300H) was dried, and the test piece was thermally cured at 160 ° C for 1 hour to prepare a test piece for evaluation. The test piece for evaluation was folded so that the surface of the cured coating film was folded outward by 180 degrees, and the state of the coating film at this time was evaluated by the following criteria. 〇......The crack is not seen on the film surface. △ ......There is a slight crack on the film surface. X... The film is cracked, and the crack is clearly seen on the film surface. Adhesiveness The thermosetting resin composition was uniformly coated on a polyimide film having a thickness of 75/m in a film thickness of 30 m after drying [DU PONT-TORAY (Kapton 300H) After drying, the test piece was heat-cured at 16 (TC for 1 hour to prepare a test piece for evaluation. Based on JIS K5400, a square of 1 size was made on the cured coating film. CELLOTAPE (registered trademark) was subjected to a film peeling test. The peeling state of the square was observed and evaluated according to the following criteria: 〇...no peeling △ ·· The following square peeling x...21% or more of the square peel evaluation The results are shown in the following Table 5. Z 65 323716 201241081 CM c\J ◎ ◎ 〇〇 0 〇 ◎ 〇〇〇〇 ◎ ◎ ◎ 〇〇 ◎ ◎ 〇〇〇〇 S ◎ ◎ 〇〇 © 〇 ◎ 〇〇〇 0 0) 本◎ ◎ 〇〇〇〇◎ 〇〇〇〇00 «Κ ◎ &lt; 〇〇〇◎ 〇〇〇〇i ◎ ◎ 〇〇〇 〇◎ 〇〇〇〇&lt;〇§ V 〇&lt;1 〇〇〇◎ ◎ 〇〇〇〇1D i 埃 ◎ 0 〇〇0 〇◎ 〇〇〇〇5 «Κ ◎ 〇〇〇〇〇◎ 〇〇 〇〇CO ◎ 〇〇〇◎ 〇◎ 〇〇〇〇csi ◎ 〇〇〇0 〇◎ 〇〇〇〇$ ◎ 〇〇〇◎ ◎ ◎ 〇〇〇〇〇f «Κ ◎ ο 0 〇〇〇◎ 〇 〇0 〇σ&gt; 诔◎ 〇〇〇〇〇@ 〇〇〇〇to ◎ 〇〇〇〇〇◎ 〇〇〇〇卜本◎ 〇〇〇〇〇◎ 〇〇〇〇(Ο本◎ 〇〇〇〇 〇◎ 〇〇〇〇in ◎ 〇〇◎ ◎ 〇◎ 〇0 〇〇◎ 〇〇ο 〇0 ◎ 〇〇〇〇P0 〇〇〇〇 〇〇〇〇 〇 ◎ 0 〇〇0 csj ◎ ◎ 〇〇〇 ◎ ◎ 〇〇〇〇r~ 本〇〇〇ο ◎ 〇◎ 〇〇〇〇屮Η 4 Τ 泄 泄 δ ίο tl 'ά 珑锇 attack tr suspect rx S t 9? ti S ti 鸯\r S « 2二m Γ· 5 本◎ ◎ 〇〇&lt; ◎ ◎ 〇〇〇0 CO inch ◎ ◎ 〇 〇〇〇〇 ◎ 〇〇〇〇 CM inch 舡 ◎ ◎ 〇〇〇〇 ◎ 〇〇〇〇 5 ◎ ◎ 〇〇 0 〇 ◎ 〇〇〇〇〇 5 鸯ψ. 〇 ◎ ◎ 〇〇 ◎ ◎ 〇 〇〇〇0) η 本◎ ◎ 〇〇 ◎ 〇 ◎ 〇〇〇〇 ω CO ◎ ◎ 〇 0 〇〇 ◎ 〇〇〇〇 5 ◎ ◎ 〇ο 〇〇 ◎ 〇〇〇〇to « 本◎ ◎ 〇 〇 ◎ ◎ ◎ 〇〇〇〇 1 &gt; η 本 ◎ ◎ 〇〇 1 1 1 ◎ ◎ ρ V ◎ 〇〇 0 0 0 本 本 本 本 本 本 本 本 〇 〇 〇 本 〇 ◎ 〇〇〇〇m ◎ 0 〇0 ◎ ◎ ◎ 〇0 〇〇η ◎ ◎ 〇〇〇〇◎ 〇〇〇〇〇C0 本璀V ◎ ◎ 〇〇◎ 〇◎ 〇〇〇〇S in ◎ &lt; &lt ◎ 〇 ◎ ◎ 〇〇〇〇〇Μ & & 〇 〇〇 〇〇 本 本 本 本 本 本 本 〇〇〇〇〇〇 〇〇〇〇〇〇 〇 〇 〇 J J J J J J J 3 3 3 3 3 3 〇◎ 〇〇〇0 S in ◎ &lt; 0 〇 ◎ ◎ ◎ 〇〇〇〇S ◎ ◎ 〇〇〇〇 ◎ 〇 0 〇〇 C3 CM ◎ ◎ 〇 ο 〇〇 〇 〇〇Μ 〇〇Μ 〇〇Μ 〇〇Μ 〇〇Μ CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO S tl T&quot;· inch (0 5 雀 ◎ 〇〇〇Ο ◎ Ο Ο 〇〇 &lt;0 (0 $ 〇&lt; 〇0 〇 ◎ ◎ 〇Ο 〇〇S ◎ &lt; 〇〇 ◎ ◎ ◎ 〇〇 〇〇(0 本◎ Θ ◎ 〇〇◎ ◎ 〇〇〇〇§ 本◎ Θ 〇〇◎ 〇◎ 〇〇〇〇ω in 本◎ Ο 〇〇〇〇◎ 〇〇〇〇C0 (Ο本〇0 〇 〇◎ 〇◎ 〇〇〇〇m ◎ Ο 〇〇〇〇◎ 〇Ο 〇〇(0 U) 本◎ Ο 〇〇@ ◎ ◎ 〇0 〇〇◎ Ο 〇〇〇〇◎ 〇〇〇0 U3 竺◎ 0 〇〇〇◎ ο 〇〇〇η u&gt; 本〇Ο 〇〇&lt; 〇◎ 〇ο 〇〇本&lt; 0 ◎ 〇〇&lt;3 ◎ 〇ο ο 〇U) ◎ 0 〇〇◎ ◎ ◎ ο 〇〇〇S in shame ◎ ◎ 0 〇&lt; ◎ ◎ 〇ο ο 〇a $ ◎ 0 〇〇〇 ◎ ◎ 〇 0 ο 〇 CQ I ◎ ◎ ◎ ◎ ο ο ο 〇 £ £ £ ◎ ◎ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο W ί¥ Η -1 «-•s τ— N««« Ϊ Ϊ t « i¥ S St 2 «ϋ 想珅53? 突«1 tr iron & m 4 utm ti € Sf Jr α tl sea\rs Ti 菊 Τ quot&quot; 0) 〇〇X &lt; XXXXX &lt;1 o CO 〇〇X &lt;&lt; XXXX &lt;J 〇id 〇&lt;〇&lt;&lt; XX &lt;〇〇&lt; (0 «1 〇&lt; 〇X &lt; XX &lt;1 〇〇〇in 5 *1 〇〇&lt;1 &lt; XXX &lt;1 &lt; 〇〇 id 0 &lt;&lt;&lt; XXX &lt;1 〇〇〇CO 〇&lt;〇&lt; X &lt;1 X &lt; X 0 〇CVJ 〇X &lt;&lt;3 XXX &lt;1 &lt; 〇〇T_ 〇〇〇'&lt; XXX &lt; 〇o &lt; «1 by A &lt;-κ think but S you male W \^yt N «ί suspect 53? 5 m 5» 珑fX m long ω ti class je6 tl tea If st platinum tr &gt;-ss «1 mother 5i two t s mc 66 323716 201241081 'About Table 5' as seen from the examples and comparative examples 'Comparative Example 1 • to 4 The resin used in the seventh and the ninth, the ester resin (c) B containing a carboxyl group is formed. The at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride is used, and thus the insulating reliability is obtained. After soldering, the strength and the resistance of the humidified fresh tin bath deteriorated. Further, in the resin used in Comparative Examples 5 to 7, the at least one acid anhydride group-containing compound (b) selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride was not used in the formation of the carboxyl group-containing modified ester resin (A). Therefore, the reliability of the insulation, the strength after soldering, and the resistance of the humidifying solder bath are remarkably deteriorated. On the other hand, in the examples, at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride is used, so that the three physical properties are not only improved, but also the balance of all the physical properties is maintained. Get good results. It is considered that this is greatly affected by the characteristics of the present invention described below. The polyol compound (a) is subjected to at least one compound (b) containing an acid anhydride group selected from the group consisting of an alicyclic polyester and an aromatic polybasic acid anhydride. The ester bond group in the carboxyl group-containing ester resin (c) obtained by the reaction is protected by a large number of substituents, and the modified ester resin (e) having a side chain hydroxyl group is selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride. The ester bond group in the carboxyl group-containing modified ester resin (A) obtained by reacting at least one acid anhydride group-containing compound (b) is protected by a large number of substituents. Further, the modified ester resin (A) having a carboxyl group obtained by the production example not only maintains solder bath resistance but also exhibits high adhesion strength. This is because the polyol compound (a) and the compound (b) containing at least one acid anhydride group selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride are used as starting materials, compared with the conventional 67 323716 201241081 dibasic acid. The resin used as the main chain of the polyester skeleton of the raw material can impart flexibility, workability, and the like derived from the polyol compound (a). Further, this is considered to be because the polarity derived from the ester skeleton still functions even if the ester bond group is protected by a large number of substituents. As is understood from the examples and the comparative examples, in the examples, at least one compound (b) synthetic resin containing at least one acid group containing an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride was used, and all of the physical properties showed good results. Further, by adding the thermosetting assistant (C), it is possible to improve the workability, the wet solder resistance, and the adhesion strength after soldering without lowering the bonding strength, the insulating reliability, and the like. This is considered to be due to the synergistic effect of the hydrolysis resistance and the thermosetting assistant (C) due to the protection of the ester bond group via a large number of substituents. [Simple description of the diagram] None. [Main component symbol description] None 0 68 323716

S

Claims (1)

201241081 • VII. Patent application scope: 1. A thermosetting resin composition comprising: (A) a modified ester resin containing a carboxyl group; (B) a compound selected from the group consisting of a thiophenoxy group, containing a different acid a vine-based compound, and at least one compound comprising a compound having a blocked isocyanate group; and (C) a thermosetting assistant; (Α) a modified ester resin containing a carboxyl group is produced by the following steps The (a) polyol compound is reacted with (b) at least one acid anhydride group-containing compound selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid anhydride to form (c) a carboxyl group-containing ester resin; a carboxyl group-containing ester resin is reacted with (d) an epoxy compound having at least two epoxy groups in one molecule to form (e) a modified ester resin containing a side chain hydroxyl group; and further, (e) is contained The side chain-based modified ester resin is reacted with (b) at least one acid anhydride group-containing compound selected from the group consisting of an alicyclic polybasic acid anhydride and an aromatic polybasic acid liver. 2. The thermosetting resin composition according to claim 1, wherein the (a) polyol compound is selected from the group consisting of polyester polyols, polycarbonate polyols, polyether polyols, and polybutylenes. There is only one compound in the group formed by the olefin polyol and the polyoxygenated polyol. 3. The thermosetting resin composition according to claim 1, wherein the (b) acid anhydride group-containing compound is selected from the group consisting of a mercaptotetrahydrofuran acid needle, a tetrahydro sulphuric acid, and a hexahydrogen pulse. Acid needle, mercapto hexahydrostyrene anhydride, 1 323716 201241081 Nadic anhydride, fluorenyl dic anhydride, hydrogenated quinone diacyl anhydride, styrylstyrene tetrahydrophthalic anhydride, 3,6-endomethylene four At least one selected from the group consisting of hydroquinone anhydride, mercaptoindenyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, decanoic anhydride, tetrabromic anhydride, trimellitic anhydride, and pyromellitic dianhydride Compound. 4. The thermosetting resin composition according to claim 1, wherein the acid value of the (A) carboxyl group-containing modified ester resin is from 1 to 100 mgKOH/g. 5. The thermosetting resin composition according to claim 1, wherein the (A) carboxyl group-containing modified ester resin has a weight average molecular weight of 5,000 to 500,000. 6. The thermosetting resin composition according to claim 1, wherein the '(C) thermosetting assistant is selected from the group consisting of an aziridine compound, a compound containing a carbodiimide group, and a benzofluorene compound. At least one of the group consisting of a sputum compound, an anthraquinone resin, an imidazole, and a dicyandiamide. 7. A cured product obtained by curing the thermosetting resin composition according to any one of the above-mentioned items of the present invention. A printed wiring board having a layer formed of the cured product described in claim 7 of the patent application. 323716 S 201241081 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: No. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: There is no chemical formula in this case. 3 323716