JP2013159762A - Thermosetting adhesive composition and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting adhesive composition which is excellent in adhesiveness, heat resistance and flexibility, and particularly can maintain insulation reliability even after exposed to a high-humidity atmosphere for a long period.SOLUTION: A thermosetting adhesive composition includes: an acrylic resin (A) having a weight average molecular weight of 100,000-2,000,000; an addition polyester resin (B) having a cyclic structure in the main chain; and at least one compound (C) selected from the group consisting of epoxy-containing compounds, isocyanate-containing compounds and blocked isocyanate-containing compounds.

Description

  The present invention relates to a thermosetting adhesive composition that can be used for electronic materials including printed wiring boards, and an adhesive sheet.

In recent years, with the development of the electronics field, electronic devices have become smaller, lighter, and more dense, and these demands have been further increased. In addition, electronic materials such as printed wiring boards mounted on electronic devices are also being actively studied for thinning, multilayering, and high definition. Therefore, the adhesive used for these electronic materials, for example, when used in flexible printed wiring boards, etc., high flexibility, as was not required for thick rigid substrates represented by conventional glass epoxy, Adhesion and heat resistance are required. The following (1) to (4) can be cited as uses of such an adhesive.
(1) Interlayer adhesive: Used to bond circuit boards together, and is in direct contact with copper or silver circuit. It is used between the layers of a multilayer substrate, and there are liquid and sheet-like ones.
(2) Coverlay film adhesive: used to bond a coverlay film (such as a polyimide film used for the purpose of protecting the outermost surface of a circuit) and an underlying circuit board; In many cases, the adhesive layer is integrated.
(3) Adhesive for copper clad laminate (CCL): used to bond a polyimide film and a copper foil together. Processing such as etching is performed when the copper circuit is formed.
(4) Adhesive for reinforcing plate: For the purpose of complementing the mechanical strength of the wiring board, it is used to fix a part of the wiring board to a reinforcing plate made of metal, glass epoxy, polyimide or the like.
Various studies have been made to satisfy the above requirements, but none of them satisfy all the characteristics sufficiently.

  Then, the adhesive composition which has the polyester polyurethane which has a specific acid value, and an epoxy resin as a main component is disclosed (refer patent document 1).

  Moreover, the adhesive composition containing a urethane modified carboxyl group containing polyester resin, an epoxy resin, and a hardening | curing agent is disclosed (refer patent document 2).

  Moreover, the resin composition containing a polyimidesiloxane, both terminal epoxysiloxane, and a hardening | curing agent is disclosed (refer patent document 3).

  In addition, a thermosetting resin composition containing an epoxy resin, an NBR rubber containing as little ionic impurities as possible, and a nitrogen-containing phenol novolac resin as a main component is disclosed (see Patent Document 4).

  Moreover, the resin composition containing an epoxy resin, a phenol resin, the hardening accelerator for epoxy resins, and an elastomer is disclosed (refer patent document 5).

  Further, a carboxyl group-containing modified epoxy resin having a chain structure by an ester bond is disclosed (see Patent Document 6).

JP-A-11-116930 JP 2007-51212 A JP 2004-91648 A JP 2003-165898 A JP 2007-161811 A JP 2005-60662 A

  However, although the adhesive of patent document 1 shows the favorable adhesiveness derived from a urethane bond, since the distance between the crosslinking points of a main ingredient and a hardening | curing agent is separated, it is said that heat resistance is scarce because the crosslinking density is low. There was a problem. In order to compensate for this, when the blending amount of the epoxy resin is increased, there is a problem that wettability to the substrate is lowered and adhesive strength is lowered. Further, since the polyester skeleton is used as the main chain, there is a problem that the insulation reliability is low when exposed to a high temperature and high humidity atmosphere for a long time.

  Moreover, although the adhesive of patent document 2 shows the favorable adhesiveness derived from a urethane bond similarly to the adhesive of patent document 1, since heat resistance is lacking and also polyester skeleton is used as a principal chain, it is high temperature high There was a problem that the insulation reliability was low when exposed to a humid atmosphere for a long time. In addition, since the molecular weight of the urethane resin is low, there is a problem that the processability is low, such as the adhesive protruding when the adhesive is cured by thermocompression bonding.

  Moreover, the adhesive agent of patent document 3 has the softness | flexibility peculiar to siloxane resin, and the outstanding heat resistance. However, since the siloxane skeleton itself has poor adhesion to the substrate, there is a problem that sufficient adhesion strength cannot be obtained because the crosslinking point is only the molecular end and the crosslinking density is low. Moreover, there existed a problem that workability was low, such as the adhesive protruding when the adhesive was cured by thermocompression bonding.

  Further, since the adhesives of Patent Documents 4 and 5 contain NBR rubber or elastomer, there is a problem that the processability is low, such as the adhesive protruding when the adhesive is cured by thermocompression bonding. On the other hand, when the amount of the epoxy resin or phenol is increased to compensate for this, there is a problem that the adhesive strength is lowered.

  Moreover, the adhesive agent of patent document 6 has favorable adhesive strength and heat resistance with respect to copper and various base materials. However, since an ester skeleton that is easily hydrolyzed exists in the main chain, there is a problem that insulation reliability is low when exposed to a high temperature and high humidity atmosphere for a long time. In addition, there is a problem that the flexibility of the film is low compared to other adhesives.

  An object of the present invention is to provide a thermosetting adhesive composition that is excellent in adhesiveness, heat resistance, and flexibility, and in particular, can maintain insulation reliability even after being exposed to a high humidity atmosphere for a long period of time.

  The thermosetting adhesive composition of the present invention comprises an acrylic resin, an addition type polyester resin in which a cyclic structure such as an aromatic ring or an aliphatic ring is directly incorporated next to the ester bond of the main chain, and a curing agent. It is the composition which includes.

  According to the present invention configured as described above, the thermosetting adhesive composition has good solder heat resistance due to the addition of the addition-type polyester resin. In addition, since the ester bond of the main chain is protected by a bulky cyclic structure, it is difficult to be hydrolyzed when exposed to a high temperature atmosphere, so that insulation reliability can be maintained. Furthermore, excellent adhesion and flexibility were realized by the combination of an addition type polyester resin and an acrylic resin having a specific molecular weight.

  According to the present invention, a thermosetting adhesive composition that is excellent in adhesiveness, heat resistance, and flexibility and that can maintain insulation reliability even after being exposed to a high humidity atmosphere for a long period of time can be provided.

  The thermosetting adhesive composition of the present invention comprises an acrylic resin (A) having a weight average molecular weight of 100,000 to 2,000,000, an addition type polyester resin (B) having a cyclic structure in the main chain, an epoxy group-containing compound, and an isocyanate content. And a compound (C) that is at least one selected from the group consisting of a compound and a blocked isocyanate group-containing compound. In the present invention, by including an addition type polyester resin (B) having a cyclic structure in the main chain, in addition to having good solder heat resistance, it is used at a solder melting temperature after being exposed to high humidity for a long period of time. Even in such a case, the bulky cyclic structure in contact with the ester bond is difficult to hydrolyze to protect the ester bond. That is, since a good coating state can be maintained, insulation reliability can be maintained.

  The acrylic resin (A) has a weight average molecular weight of 100,000 to 2,000,000. Adhesion and flexibility can be improved by blending the acrylic resin (A). In the present invention, the weight average molecular weight means a polystyrene equivalent weight average molecular weight by GPC measurement unless otherwise specified.

  The acrylic resin (A) is a polymer of an ethylenically unsaturated monomer containing a (meth) acrylic acid ester monomer. In the present invention, the (meth) acrylic acid ester monomer means both an acrylic acid ester monomer and a methacrylic acid ester monomer. The acrylic resin (A) of the present invention uses a resin obtained by copolymerizing an ethylenically unsaturated monomer that does not have a functional group that becomes a crosslinking point and an ethylenically unsaturated monomer that has a functional group that becomes a crosslinking point. Is preferred.

There is no restriction | limiting in particular as an ethylenically unsaturated monomer which does not have the functional group used as a crosslinking point, For example, the C1-C20 (meth) acrylic-acid alkylester monomer and vinyl group containing monomer whose ester group alkyl group is 1-20 Can be mentioned.
Examples of (meth) acrylic acid ester monomers having 1 to 20 carbon atoms in the alkyl group of the ester moiety include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic. Butyl acid, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Dodecyl acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Among these compounds, ethyl (meth) acrylate and butyl (meth) acrylate are preferable in that an appropriate adhesion performance is easily obtained and an acrylic resin having a weight average molecular weight of 100,000 or more can be easily produced.

  Examples of the ethylenically unsaturated monomer having a functional group serving as a crosslinking point include a carboxyl group-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and an amino group-containing ethylenically unsaturated monomer. Monomers and the like can be used. The amount of the ethylenically unsaturated monomer having a functional group serving as a crosslinking point is preferably 10 parts by weight or less in a total of 100 parts by weight of the ethylenically unsaturated monomer. If it exceeds 10 parts by weight, it becomes difficult to achieve both cohesion and adhesion.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, (meth ) 4-carboxybutyl acrylate, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, glutaconic acid, citraconic acid , Mesaconic acid, itaconic acid, tiglic acid, angelic acid, senetic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronellic acid, 4-acrylamidobutane Acid, 6-acrylamidohexanoic acid, Or by repeating ring-opening addition of lactone ring such as ω-carboxypolycaprolactone mono (meth) acrylate, polylactone type (meth) acrylic acid ester having a carboxyl group at the terminal or alkylene oxide such as ethylene oxide or propylene oxide was repeatedly added. Carboxyl group-containing aliphatic ethylenically unsaturated carboxylic acids such as alkylene oxide-added succinic acid (meth) acrylate having a carboxyl group at the end; 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth ) Acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) Acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 4-isopropenylbenzenecarboxylic acid, cinnamic acid, 7-amino-3- Examples thereof include ethylenically unsaturated carboxylic acids having a carboxyl group-containing alicyclic ring or aromatic ring such as vinyl-3-cephem-4-carboxylic acid.

  The hydroxyl group-containing ethylenically unsaturated monomer is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate [2-hydroxyethyl acrylate and 2-methacrylic acid 2- Together with hydroxyethyl, it is expressed as “(2-hydroxyethyl) (meth) acrylate”. The same applies below. ], 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxy (meth) acrylate Butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy (meth) acrylate Decyl, 12-hydroxylauryl (meth) acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylate glycerol, or (meth) acrylate glycidyl laurate, (meth) acryl Acid glycidyl oleate, (meth) acte Fatty acid ester (meth) acrylic acid esters such as glycidyl stearate ester, polylactone (meth) acrylic acid esters having a hydroxyl group at the terminal by ring-opening addition of a lactone ring, or alkylene oxides such as ethylene oxide and propylene oxide A hydroxyl group-containing aliphatic (meth) acrylic acid ester such as an alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal repeatedly added, or (meth) acrylic acid 2-hydroxyethyl phosphate;

  (Meth) acrylic acid 1,2-cyclohexanedimethanol, (meth) acrylic acid 1,3-cyclohexanedimethanol, (meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid cyclohexyl glycidyl ether, (meta ) Phenyl glycidyl ether acrylate, 2-hydroxy-3-phenoxymethyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ( 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate , (Meta) 2- (4-benzoyl-3-hydroxyphenoxy) ethyl oxalate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Hydroxyl-containing alicyclic or aromatic (meth) acrylic acid esters such as propyl) benzene;

For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2′-hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole and 2 Combined with-(2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole, "2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole" Is written. The same applies below. ], 2- (2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -2H-benzotriazole,
2- (2′-hydroxy-5 ′-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(meth) Hydroxyl content such as acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole Benzotriazole-based (meth) acrylic acid esters;

  For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl group-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 24-bis (2-methylphenyl) -6- [2-hydroxy- 4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}] -S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2- Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy- 4 {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy} ] -S-triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine and other hydroxyl-containing triazines (Meth) acrylic acid esters;

  For example, glucose ring system (meth) acrylate esters such as glycosyl methyl (meth) acrylate, glycosyl ethyl (meth) acrylate, glycosyl propyl (meth) acrylate, glycosyl butyl (meth) acrylate;

  For example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3- Hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4, Hydroxyl group-containing aromatic vinyl compounds such as 6-trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

  For example, N-hydroxyethyl (meth) acrylamide [N-hydroxyethyl acrylamide and N-hydroxyethyl methacrylamide are collectively referred to as “N-hydroxyethyl (meth) acrylamide”. The same applies below. ], Hydroxyl-containing (meth) acrylamides such as N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide;

  Examples thereof include monomers having a hydroxyl group and an alkenyl group such as hydroxystyrene and vinyl alcohol.

  Examples of the epoxy group-containing ethylenically unsaturated monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 6-methyl-3 (meth) acrylate. , 4-epoxycyclohexylmethyl and the like.

  The amino group-containing ethylenically unsaturated monomer is not particularly limited as long as it has an amino group in its structure. For example, monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, Examples thereof include monomethylaminopropyl (meth) acrylate and monoethylaminopropyl (meth) acrylate.

  These ethylenically unsaturated monomers having a functional group serving as a crosslinking point can be used alone or in combination of two or more.

  The vinyl group-containing monomer may be any monomer that can be copolymerized with the ethylenically unsaturated monomer. For example, vinyl chloride, vinylidene chloride, styrene, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, vinyl acetate, vinyl crotonate, (meth) acrylonitrile and the like are preferable.

  In the present invention, the acrylic resin (A) can be synthesized by a known method. For example, solution polymerization, suspension polymerization, bulk polymerization, high pressure radical polymerization, emulsion polymerization and the like are preferable, and solution polymerization is more preferable. It is common to use a polymerization initiator for this solution polymerization.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile) and 2,2 '-Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate), 4 , 4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And azo compounds such as

  Benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy Organic such as 2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide A peroxide is mentioned.

  In the synthesis, mercaptans such as lauryl mercaptan and n-dodecyl mercaptan, and chain transfer agents such as α-methylstyrene dimer and limonene may be used.

  The polymerization initiator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer.

  The addition type polyester resin (B) has a cyclic structure in the main chain. Since a bulky cyclic structure exists next to the ester bond in the main chain, the ester bond is not easily decomposed even when the adhesive is exposed to high humidity. Therefore, heat resistance, insulation reliability, and the like can be greatly improved as compared with the case where a conventional condensation-type polyester resin is used.

  Since it is important that the addition-type polyester resin (B) has a cyclic structure in the main chain, the synthesis method is not particular. Therefore, as an example of the synthesis method, for example, an addition type polyester resin (B-1) obtained by reacting a polyol compound (a) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is used. It is preferable to use it.

  The polyol compound (a) has two or more hydroxyl groups and has a repeating unit having a polymerization degree of 2 or more in its structure. Specific examples include polyester polyols, polycarbonate polyols, polyether polyols, polybutadiene polyols, and polysiloxane polyols. Polyurethane polyols using these polyols are preferred. The polyol compound (a) preferably has a weight average molecular weight of 500 to 50,000. In the present invention, the weight average molecular weight means a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (hereinafter also referred to as “GPC”).

  As the polyester polyol, for example, a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component is preferable. Of the polyfunctional alcohol components, the diol is ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol. 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol And 2-ethyl-1,3-hexanediol, cyclohexanediol, and bisphenol A. Polyfunctional alcohol components having three or more hydroxyl groups are trimethylolethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol. And arabitol, xylitol, galactitol, glycerin and the like. A polyester polyol having a phosphorus atom is also preferred. Specifically, 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl) methylsuccinic acid or an acid anhydride thereof and a polycondensate of ethylene glycol, or 2- (9 , 10-dihydro-9-oxa-10-oxide-10-phosphaphenanthrene-10-yl) methylsuccinic acid-bis- (2-hydroxyethyl) -ester, or a polyester polyol obtained by polycondensation thereof.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and anhydrides thereof.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  Polycarbonate polyols have a structure represented by the following general formula (1) in the molecule.

General formula (1)
− [— O—R ⁸ —O—CO—] _m —
(In the formula, R ⁸ represents a divalent organic residue, and m represents an integer of 1 or more.)

  The polycarbonate polyol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Specific examples of the glycol or bisphenol used in the production methods of (1) and (2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanedio- 2-methyl-1,8-octanediol, 3,3'-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3 -Hexanediol, cyclohexanediol It can be used bisphenols such as bisphenol A, bisphenol F, ethylene oxide to the bisphenols, also bisphenols obtained by adding an alkylene oxide such as propylene oxide. These compounds can be used as one kind or a mixture of two or more kinds.

  Polyether polyols include, for example, polymers, copolymers, and graft copolymers of alkylene oxides such as tetrahydrofuran, ethylene oxide, propylene oxide, butylene oxide; hexanediol, methylhexanediol, heptanediol, octanediol. Polyether polyols obtained by condensation of benzene or a mixture thereof; aromatic diols such as bisphenols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to bisphenol A and bisphenol F; and trimethylo -Ruethane, polytrimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabi Polyethylene oxide, polypropylene oxide, ethylene oxide or propylene oxide block copolymer and random copolymer synthesized using polyalcohols such as polyol, xylitol, galactitol, glycerin, etc. as part of the raw material Those having two or more hydroxyl groups such as polyether polyols such as coalescence, polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol, or random copolymer can be used.

  The polybutadiene polyol includes, for example, hydrogenated unsaturated bonds in the molecule, and examples thereof include polyethylene polyols, polypropylene polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, and the like. It is done.

Examples of polysiloxane polyols include compounds represented by general formulas (2) and (3).
General formula (2)

(X represents a hydroxyl group, R ¹ and R ² each represent an alkylene group having 1 to 6 carbon atoms, and n represents an integer of 5 or more.)
General formula (3)

(Y represents a hydroxyl group, R ³ is an alkyl group having 1 to 6 carbon atoms, R ⁴ , R ⁵ and R ⁶ are each an alkylene group having 1 to 6 carbon atoms, and R ⁷ is a hydrogen atom or 1 to 1 carbon atoms. 6 represents an alkyl group, and n represents an integer of 5 or more.)

  The polyurethane polyol is, for example, a product obtained by reacting the above polyol compound with a diisocyanate, and a polyurethane polyol using a polyester polyol as a raw material, a polyurethane polyol using a polycarbonate polyol as a raw material, a polyurethane polyol using a polyether polyol as a raw material, and a polybutadiene polyol as a raw material. And polyurethane polyols using polysiloxane polyol as a raw material.

  Examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate and the like.

  Aliphatic diisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2, Examples include 4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.

  In order to further improve the heat resistance of the thermosetting adhesive composition, it is preferable to use an aromatic diisocyanate or an araliphatic diisocyanate. Moreover, when improving the softness | flexibility and adhesiveness of a thermosetting adhesive composition more especially, it is preferable to use aliphatic diisocyanate and alicyclic diisocyanate. Moreover, the diisocyanate compound can use together 1 type, or 2 or more types.

  Among the above polyol compounds (a), polyester polyols consisting of 1,4-cyclohexanedicarboxylic acid and 3-methyl-1,5-pentanediol, and 1,6-hexanediol only are used as glycols. Polycarbonate polyols, polycarbonate polyols using 1,6-hexanediol and 3-methyl-1,5-pentanediol as glycol, 1,9-nonanediol and 2-methyl-1 Polycarbonate diol, polytetramethylene glycol, polypropylene glycol, or a copolymer polyether polyol of tetramethylene glycol and neopentyl glycol, polybutadiene polyol, hydrogenated polybutadiene polyol using 1,8-octanediol as glycol Polysiloxane polyols, etc., the main chain skeleton is flexible and good heat resistance, because the ester bond is difficult to hydrolyze, it is preferable to use, for example, in an adhesive sheet.

  In addition to the above polyols, it is also preferable to use a trifunctional polyol as the polyol compound (a). As a result, the addition-type polyester resin (B) has a branched structure. Therefore, when used as an adhesive layer of an adhesive sheet, the cohesive force of the adhesive layer is increased, thereby improving the adhesiveness and heat resistance. It can be improved.

  Trifunctional polyols include, for example, polyhydric alcohols such as trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin and the like. Compounds. Among these, trimethylolpropane and pentaerythritol are preferable in terms of reaction control.

  In the present invention, the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring [hereinafter sometimes referred to as compound (b)] is preferably a compound having an alicyclic ring or a compound having an aromatic ring. Cyclic dibasic acid anhydrides and aromatic dibasic acid anhydrides are more preferred. When the compound (b) is used, since the ester bond is not easily decomposed even under severe conditions such as high temperature and high humidity (for example, temperature: 85 ° C., humidity: 85%), insulation reliability and heat resistance are further improved.

Compounds having an alicyclic ring are, for example, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, still end. Examples thereof include styrene tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and trialkyltetrahydrophthalic anhydride.
Examples of the compound having an aromatic ring include phthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, and the like.

  Among these compounds (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methyl Nadic anhydride, hydrogenated methyl nadic anhydride, and the like are particularly preferable from the viewpoints of insulation reliability and heat resistance because they can protect the ester bond more effectively.

  The addition type polyester resin (B) is preferably an addition type polyester resin (B-1). That is, the synthesis of the addition-type polyester resin (B-1) is carried out by using a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring when the total hydroxyl group of the polyol compound (a) is 1 mol. ) Is preferably reacted at a ratio of 0.7 mol to 1.3 mol, more preferably 0.9 mol to 1.1 mol. When the sum of the acid anhydride groups is 0.7 mol or more, appropriate crosslinking is likely to occur and heat resistance is easily obtained. On the other hand, by being 1.3 mol or less, reaction control and reaction when reacting with the compound (c) having two or more epoxy groups are facilitated.

  The addition type polyester resin (B-1) can be synthesized by a known method. For example, a polyol compound (a) and a solvent are charged into a flask and dissolved uniformly by heating and stirring at 20 to 120 ° C. in a nitrogen stream, and then a compound having a saturated or unsaturated cyclic structure and an acid anhydride ring. Addition-type polyester resin (B-1) can be obtained by charging (b) and heating at 50 to 150 ° C. with stirring. In addition, before adding the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring, the polyol compound (a) and the solvent charged in the flask in advance are heated and stirred at 100 ° C. or higher, and the solvent A part of the solvent may be removed. This operation is usually performed to remove water (dehydration treatment) in the system, and when the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is reacted by this operation, The ring opening reaction of the acid anhydride group due to can be suppressed.

  The addition-type polyester resin (B) is more preferably an addition-type polyester resin (B-2) obtained by reacting the addition-type polyester resin (B-1) with a compound (c) having two or more epoxy groups. preferable. Adhesive strength can be further improved by appropriately selecting the compound (c) having two or more epoxy groups.

  The compound (c) having two or more epoxy groups may be a compound containing two epoxy groups in the molecule. Specifically, the compound (c) having two or more epoxy groups is, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin. Type epoxy resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, glycerin / epichlorohydrin adduct polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone Diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A-type diglycidyl ether, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol-furful orange glycidyl ether, bis Phenoxyethanol full orange glycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidylaniline, N, N-diglycidyl toluidine, JP 2004-156024 A, special Epoxy compounds excellent in flexibility disclosed in Japanese Unexamined Patent Application Publication Nos. 2004-315595 and 2004-323777, and the following formula ( ) - (epoxy compounds represented by structure 3) and the like.

Chemical formula (4)

Chemical formula (5)

Chemical formula (6)

  Among these, 1,6-hexanediol diglycidyl ether can further improve the flexibility of the addition-type polyester resin (B-2). In addition, the bisphenol A / epichlorohydrin type epoxy resin can further improve the heat resistance of the addition type polyester resin (B-2). The compound (c) having two or more epoxy groups can be selected according to the purpose, and these may be used alone or in combination.

  When synthesizing the addition-type polyester resin (B-2), the proportion of the addition-type polyester resin (B-1) and the compound (c) having two or more epoxy groups is reacted with the addition-type polyester resin (B-). When the total of the carboxyl groups in 1) is 1 mol, it is preferable to react the epoxy groups in the compound (c) having two or more epoxy groups in a proportion of 0.5 mol to 1.5 mol, It is more preferable to make it react in the ratio of 0.7 mol-1.3 mol. When the ratio of the epoxy group in the compound (c) having two or more epoxy groups is 0.5 mol or more with respect to 1 mol of the carboxyl group of the addition-type polyester resin (B-1), an appropriate molecular weight is obtained. It becomes easy and heat resistance improves more. On the other hand, since the amount of the terminal epoxy group can be more appropriately adjusted to 1.5 mol or less, the reaction control is also possible when reacting the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. It becomes easy to do.

  The addition type polyester resin (B-2) can be synthesized by a known method. For example, an addition type polyester resin (B-1), a compound (c) having two or more epoxy groups, and a solvent are charged in a flask and heated at 100 to 150 ° C. while stirring to add the addition type polyester resin (B- 2) can be obtained. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.

  The addition type polyester resin (B) is the addition type polyester resin (B-2), a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring (hereinafter sometimes referred to as the compound (b)). More preferred is an addition-type polyester resin (B-3) obtained by reacting with. The addition-type polyester resin (B-2) has a hydroxyl group in the side chain, and a carboxyl group is generated in the side chain by reacting the hydroxyl group with the acid anhydride group of the compound (b). The heat resistance can be further improved by a crosslinking reaction between the carboxyl group and the epoxy curing agent. In addition, the presence of a bulky cyclic structure next to the ester bond in the side chain makes it difficult for the ester bond in the side chain to be decomposed at high temperatures, thereby improving the heat resistance.

  When the addition type polyester resin (B-3) is synthesized, the addition type polyester resin (B-2) is reacted with the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. When the total number of hydroxyl groups of the polyester resin (B-2) is 1.0 mol, the acid anhydride group in the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is changed to 0.05. It is preferable to make it react in the ratio of mol-0.95 mol, and it is more preferable to make it react in the ratio of 0.10 mol-0.90 mol. The ratio of the acid anhydride group in the compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring is 0.05 with respect to 1.0 mol of the hydroxyl group in the addition type polyester resin (B-2). When the amount is less than a mole, the amount of carboxyl groups that can be introduced into the main chain is small, and the heat resistance improvement effect after the crosslinking reaction tends to be difficult to find. On the other hand, when the amount is more than 0.95 mol, the amount of carboxyl groups in the finally obtained addition-type polyester resin (B) tends to be excessive and the adhesive strength tends to decrease. In the present invention, adhesiveness is a concept including adhesive strength.

  The addition type polyester resin (B-3) can be synthesized by a known method. For example, an addition type polyester resin (B-2), a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring, and a solvent are charged into a flask and heated at 50 to 100 ° C. while stirring. An addition type polyester resin (B) can be obtained. This reaction proceeds even in the absence of a catalyst, but a catalyst such as a tertiary amino group-containing compound may be used if necessary.

  The acid value of the addition type polyester resin (B) is preferably 1 to 100 mgKOH / g, more preferably 5 to 90 mgKOH / g. When the acid value is less than 1 mgKOH / g, since there are few carboxyl groups, various physical properties after curing may be reduced. On the other hand, if the acid value exceeds 100 mgKOH / g, the cured product becomes too hard and the adhesive strength may be insufficient. Moreover, when designing in the range close | similar to 1 mgKOH / g in the range whose acid value is 1-100 mgKOH / g, it exists in the tendency for the flexibility and adhesiveness of the coating film obtained to improve. On the other hand, when designing in a range close to 100 mgKOH / g, the heat resistance is further improved because the number of crosslinking points increases.

  The weight average molecular weight of the addition-type polyester resin (B) is preferably 5,000 to 500,000, and more preferably 10,000 to 300,000. If the weight average molecular weight is less than 5,000, sufficient heat resistance may not be obtained. On the other hand, when a weight average molecular weight exceeds 500,000, there exists a possibility that the applicability | paintability of a thermosetting adhesive fat composition may fall. In addition, when designing with a value close to 5000 within the range of 5000 to 500,000 in the weight average molecular weight, since the terminal of the resulting resin (that is, carboxyl group) is large, a resin rich in crosslinkability can be obtained. There is a tendency for the heat resistance of the to improve. On the other hand, when designing with the value close | similar to 500000, adhesiveness and a softness | flexibility improve more about hardened | cured material.

The addition-type polyester resin (B) is a compound having one or more hydroxyl groups other than the polyol compound (a) as an optional component or a compound having a functional group other than a hydroxyl group when synthesizing an ester bond of the main chain. Can be used.
The compound having one or more hydroxyl groups other than the polyol compound (a) includes a monoalcohol compound (a-1-1) and a diol compound (a-1-2) having two hydroxyl groups in the molecule. ), A compound (a-1-3) having 3 or more hydroxyl groups in the molecule is preferred. These compounds may have a crosslinkable functional group other than a hydroxyl group in the molecule.

  The monoalcohol compound (a-1-1) includes, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol. Aliphatic monoalcohols such as lauryl alcohol and stearyl alcohol; alicyclic monoalcohols such as cyclohexanol; aromatic monoalcohols such as benzyl alcohol and fluorenol; phenol; Phenols such as methoquinone; monoalcohol compounds having functional groups other than hydroxyl groups, such as hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, 2-hydroxyethyl (meth) acrylate ("2-hydroxy “Ethyl acrylate” and “2-hydroxyethyl methacrylate” are combined to form “2-hydroxyethyl (medium ) Acrylate ”, the same applies hereinafter), hydroxyl group-containing (meth) acrylate compounds such as 4-hydroxybutyl (meth) acrylate, hydroxyl group-containing epoxy compounds such as glycidyl, oxetane alcohol And hydroxyl group-containing oxetane compounds such as Other examples include oligomer-type monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and caprolactone addition polymer using monoalcohol as an initiator. Among these, considering the reactivity of hydroxyl group and reaction control, lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidyl, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate is preferred.

  When the monoalcohol compound (a-1-1) is used, the end of the addition-type polyester resin (B) can be sealed, and therefore, when the addition-type polyester resin (B) having a low molecular weight is synthesized, the weight average is obtained. The molecular weight can be easily adjusted. Moreover, when the monoalcohol compound (a-1-1) has a crosslinkable functional group other than a hydroxyl group, a functional group other than a carboxyl group can be introduced at the end of the addition-type polyester resin (B). It can be suitably used when terminal modification of the addition type polyester resin is required.

  Diol compounds (a-1-2) having two hydroxyl groups in the molecule are, for example, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, 2-methyl-2- Ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-methyl -1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol -Methyl, 2-methyl-2,4-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylol Luheptane, propanediol, 1,3 Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, 3-butyl-3- Ethyl-1,5-pentanediol, 2-ethyl-1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclopentadiene dimethanol, dimer Aliphatic or alicyclic diols such as diol, hydrogenated bisphenol A, spiroglycol; 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 4,4 ′-(2-norbornylidene) Diphenol, 4,4′-dihydroxybiphenol, o-, m-, and p-dihydroxybenzene, 4,4′-isopropylidenephenol, 1,2-indandiol, 1,3-naphthalenediol, 1 , 5-naphthalenediol, 1,7-naphthalenediol, 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (3-methyl-4-hydroxyphenyl) fluorene, etc. Aromatic diols can be mentioned. Other examples include sulfur atom-containing diols and bromine atom-containing diols.

A compound having a functional group other than a hydroxyl group is preferably a tertiary amino group, a carboxyl group or the like as the functional group.
Examples of the compound containing a tertiary amino group include N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2-hydroxyethyl) aniline, and N, N-bis (2-hydroxyethyl) methyl. Amine, N, N-bis (2-hydroxyethyl) propylamine, N, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N, N-bis (2 And tertiary amino group-containing diol compounds such as -hydroxyethyl) octylamine, N, N-bis (2-hydroxyethyl) benzylamine, and N, N-bis (2-hydroxyethyl) cyclohexylamine. Among these, when N, N-bis (2-hydroxypropyl) aniline or the like is used, it is preferable in that the heat resistance can be further improved by increasing the cohesive force of the cured product.

  Examples of the compound containing a carboxyl group include dimethylolbutanoic acid, dimethylolpropionic acid, 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol and the like. Is mentioned. Among these, when dimethylolbutanoic acid or dimethylolpropionic acid is used, the number of carboxyl groups at the end of the main chain of the addition-type polyester resin (B) can be increased. Therefore, when the addition type polyester resin (B-1) is reacted with the compound (c) having at least two epoxy groups in one molecule, it tends to be able to synthesize a higher weight average molecular weight.

  Here, the polyol compound (a) and the hydroxyl group-containing compound (a-1) can be used in any ratio according to the purpose in the present invention, and with respect to 1 mol of the hydroxyl group in the polyol compound (a), The hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of 0.01 mol to 1 mol, preferably 0.05 mol to 0.5 mol. When the hydroxyl group in the hydroxyl group-containing compound (a-1) is used in a proportion of less than 0.01 mol with respect to 1 mol of the hydroxyl group in the polyol compound (a) (that is, the polyol compound (a) is used alone. In the case of the polyol compound (a) alone, sufficient insulation reliability, heat resistance and adhesive strength can be easily obtained, but higher heat resistance is difficult to obtain. Moreover, when more than 1 mol, the cohesive force of the coating film finally obtained will increase too much, and it exists in the tendency for adhesive strength to fall.

  One or a plurality of addition-type polyester resins (B) may be used in combination. The use amount of the addition type polyester resin (B) may be determined in consideration of the use of the thermosetting adhesive composition, etc., for example, 1 to 200 weights with respect to 100 parts by weight of the acrylic resin (A). It is preferable to add in the ratio of parts, and it is more preferable to add in the ratio of 10 to 100 parts by weight. When the addition amount of the addition type polyester resin (B) with respect to the acrylic resin (A) is less than 1 part by weight, the heat resistance is hardly improved. Moreover, when there are more compounding quantities than 200 weight part, adhesiveness cannot improve easily.

  In the present invention, the compound (C) has at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound [hereinafter also simply referred to as “compound (C)”. ]. This compound (C) functions as a curing agent.

In the present invention, the epoxy group-containing compound is not particularly limited as long as it is a compound containing two or more epoxy groups in the molecule.
Examples of the compound containing two or more epoxy groups in the molecule include the epoxy group-containing compounds described as the compound (c) constituting the addition type polyester resin (B).

  Further, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, "Epicoat 1031S", "Epicoat 1032H60", "Epicoat 604", "Epicoat 630" manufactured by Mitsubishi Chemical Corporation In addition, a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin disclosed in JP-A No. 2001-240654, a polyglycidyl of an ethylene glycol / epichlorohydrin adduct And ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

  In particular, when an isocyanurate ring-containing epoxy compound such as trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate is used in the present invention, the adhesive strength tends to be improved with respect to polyimide or copper. ,preferable. In addition, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, and “Epicoat 630” manufactured by Mitsubishi Chemical Corporation are multifunctional and have excellent heat resistance. It is very preferable in the invention, and an epoxy compound of an aliphatic type or an epoxy compound described in JP-A No. 2004-156024, JP-A No. 2004-315595, or JP-A No. 2004-323777 is flexible. Since it is excellent in property, it is preferable. In addition, the dicyclopentadiene type epoxy compound, the phenol novolak type epoxy resin, the cresol novolak type epoxy resin, the biphenol / epichlorohydrin type epoxy resin, etc. described in JP-A No. 2001-240654 are used in the present invention. It is preferable from the viewpoint of durability of the cured coating film including curability, hygroscopicity and heat resistance.

  In the present invention, for the purpose of adjusting the crosslink density of the cured product, a compound having one epoxy group in the molecule may be used in combination with the compound (C). Specific examples include compounds such as N-glycidyl phthalimide, glycidyl, and glycidyl (meth) acrylate.

The isocyanate group-containing compound is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Examples of the diisocyanate compound include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates.
Aromatic diisocyanates include, for example, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate. Range isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 " -Triphenylmethane triisocyanate etc. are mentioned.
Aliphatic diisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2, Examples include 4,4-trimethylhexamethylene diisocyanate.
Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate and 1,3-tetramethylxylylene diisocyanate.
Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.

  Specifically, the isocyanate group-containing compound having one or three or more isocyanate groups in the molecule includes (meth) acryloyloxyethyl isocyanate, 1, as a monofunctional isocyanate having one isocyanate group in one molecule. Examples include 1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having three or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. And a trimethylolpropane adduct of diisocyanate described above, a burette reacted with water, and a trimer having an isocyanurate ring.

  The blocked isocyanate group-containing compound is not particularly limited as long as the isocyanate group is an isocyanate group-containing compound protected with ε-caprolactam, MEK oxime, or the like. Specific examples include those obtained by blocking the isocyanate group of the isocyanate group-containing compound with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like.

  In the present invention, compound (C) may be used alone or in combination. The amount of compound (C) used may be determined in consideration of the application of the thermosetting adhesive composition of the present invention, and is particularly limited. However, when the total of the acrylic resin (A) and the addition-type polyester resin (B) is 100 parts by weight, it is preferably added at a ratio of 0.5 to 100 parts by weight. More preferably, it is added at a ratio of from 80 parts by weight to 80 parts by weight. Since the crosslinking density of the thermosetting adhesive composition of the present invention can be adjusted to an appropriate value by using the compound (C), various physical properties of the cured coating film can be further improved. it can. When the usage-amount of a compound (C) is less than 0.5 weight part, there exists a possibility that the crosslinked density of hardened | cured material may run short and adhesive strength and heat resistance may run short. On the other hand, when the amount used is more than 100 parts by weight, the crosslink density of the cured product becomes excessive, and the adhesive strength may be lowered.

The thermosetting adhesive composition of the present invention can further contain a thermosetting aid. The thermosetting aid is a compound that directly contributes to the curing reaction or a compound that contributes catalytically when the compound (C), the acrylic resin (A), and the addition-type polyester resin (B) are cured. is there. Examples of the compound that directly contributes to the curing reaction include dicyandiamide, carboxylic acid hydrazide, and acid anhydride. Examples of the compounds that contribute catalytically include tertiary amine compounds, phosphine compounds, and imidazole compounds.
Examples of the compound that directly contributes to the curing reaction include succinic hydrazide and adipic hydrazide as carboxylic acid hydrazide. Examples of the acid anhydride include hexahydrophthalic anhydride and trimellitic anhydride.

  As compounds that contribute catalytically to the curing reaction, tertiary amine compounds include triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-7, 1,5-diazabicyclo (4.3.0). Nonen-5 etc. are mentioned. Examples of the phosphine compound include triphenylphosphine and tributylphosphine. Further, in the imidazole compound, imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenylimidazole, and the imidazole compounds A latent curing accelerator with improved storage stability such as a type in which an epoxy resin is reacted to insolubilize in a solvent or a type in which an imidazole compound is encapsulated in microcapsules is preferable.

  Two or more of these thermosetting aids may be used in combination, and the amount added is 0.1 to 0.1 parts by weight when the total of the acrylic resin (A) and the addition-type polyester resin (B) is 100 parts by weight. A range of 30 parts by weight is preferred.

  If necessary, the thermosetting adhesive composition of the present invention further includes a solvent, a silane coupling agent, a dye, a pigment, a flame retardant, an antioxidant, a polymerization inhibitor, an antifoaming agent, a leveling agent, and an ion scavenger. , Moisturizers, viscosity modifiers, antiseptics, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic shielding agents, fillers, and the like can be added. In particular, it is preferable to add a filler for the purpose of controlling the heat resistance and the fluidity of the adhesive.

  Examples of the filler include inorganic fillers such as silica, alumina, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium carbonate, titanium oxide, zinc oxide, antimony trioxide, magnesium oxide, talc, montmorillonite, kaolin, and bentonite. And metal fillers such as aluminum, gold, silver, copper and nickel. Among these, silica, alumina, and aluminum hydroxide are preferable from the viewpoint of dispersibility. In particular, hydrophobic silica obtained by modifying a silanol group on the silica surface with a halogenated silane can be used in the thermosetting adhesive composition of the present invention because it can reduce water absorption and improve heat resistance. When the total amount of the acrylic resin (A) and the addition type polyester resin (B) is 100 parts by weight, the amount of the filler is preferably 0.1 to 100 parts by weight, and 0.2 to 50 parts by weight. It is more preferable that

  The thermosetting resin composition of the present invention can be produced by stirring and mixing the acrylic resin (A), the addition type polyester resin (B), the compound (C), and, if necessary, the above optional components.

  For the stirring and mixing, for example, a scandex, a paint conditioner, a sand mill, a raking machine, a triple roll and a bead mill can be used, or a combination thereof can be performed. Furthermore, vacuum defoaming is preferably performed to remove bubbles from the thermosetting adhesive resin composition after stirring and mixing.

  The adhesive sheet of the present invention is a sheet having an adhesive layer formed by applying a thermosetting adhesive composition on a substrate and drying it. The adhesive sheet of the present invention is preferably a thermosetting adhesive sheet. That is, in the adhesive layer, the acrylic resin (A), the addition-type polyester resin (B), and the compound (C) are unreacted and are preferably cured by thermocompression bonding of the adherend. Specifically, for example, it is preferable that the crosslinking reaction starts when thermocompression bonding is performed on the printed wiring board. The unreacted means that, for example, an adhesive sheet is aggregated in an adhesive layer by cross-linking a part of the compound (C) in order to prevent the adhesive layer from flowing during transport and causing procking. It does not prevent you from giving power.

  The coating method is preferably knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure coating, flexo coating, dip coating, spray coating, spin coating, or the like.

  As the substrate, a polyester film, a polyethylene film, a polypropylene film, a polyimide film, a polyethylene laminated fine paper, a film subjected to release treatment (hereinafter also referred to as a release film), and the like can be used. Furthermore, metals such as aluminum, copper, stainless steel, and beryllium copper, and foils of these alloys can be used as a substrate.

  The thickness of the adhesive layer can be appropriately determined, but is usually 5 to 500 μm, preferably 10 to 100 μm, from the viewpoints of adhesive properties and heat resistance.

  Next, the manufacturing method of the printed wiring board using a thermosetting adhesive composition is demonstrated. On the plastic film having flexibility and insulation such as polyester and polyimide, the thermosetting adhesive composition of the present invention is overlaid so as to cover the conductor pattern of the flexible printed wiring board formed by the printing technique, A flexible printed wiring board can be obtained by hardening a thermosetting adhesive composition by heating and pressurizing. In addition, an adhesive layer using the thermosetting adhesive composition of the present invention is sandwiched between a plurality of flexible printed wirings, and the thermosetting adhesive composition is cured by heating and pressurizing, so that a multi-layer flexible A printed wiring board can also be obtained. Copper foil and a heat-resistant insulating flexible base material can also be laminated | stacked using the thermosetting adhesive composition of this invention. Furthermore, the flexible printed wiring board with a reinforcing material can also be obtained using the thermosetting adhesive composition of the present invention. A flexible printed wiring board with a reinforcing material sandwiches an adhesive layer made of the thermosetting adhesive composition of the present invention between a flexible printed wiring board and a reinforcing material such as glass epoxy, metal, polyimide, etc. The thermosetting adhesive composition is cured by pressing, and a flexible printed wiring board is provided with a reinforcing material.

  The thermosetting adhesive composition and the thermosetting adhesive sheet of the present invention include a multilayer printed wiring board interlayer adhesive, an adhesive for a coverlay film, an adhesive for a copper-clad laminate, an adhesive for fixing a reinforcing plate, As an electromagnetic wave shielding adhesive, a heat conductive adhesive, and a conductive adhesive, it can be preferably used in the electronics field such as a rigid wiring board, a rigid flexible wiring board, and a flexible printed wiring board.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, and Mw means a weight average molecular weight.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, the column temperature. It carried out on the conditions of 40 degreeC, and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.

[Synthesis example 1 of acrylic resin]
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer was charged with 98 parts of 2-ethylhexyl acrylate, 2 parts of acrylic acid, and 350 parts of acetone. The flask was heated to 80 ° C., 0.05 part of 2,2′-azobisisobutyronitrile was added, and the mixture was reacted for 2 hours. Further, 0.05 part of 2,2′-azobisisobutyronitrile was added, followed by reaction for 5 hours. After completion of the reaction, the reaction mixture was cooled and 100 parts of ethyl acetate was added to obtain an acrylic resin solution having a weight average molecular weight of 1,500,000.

[Synthesis Examples 2-6 of Acrylic Resin]
An acrylic resin was synthesized in the same manner as in Synthetic Example 1 except that the raw material of Synthesis Example 1 of acrylic resin was replaced with the raw material described in Table 1. The results of the weight average molecular weight of the synthesized acrylic resin solution are shown in Table 1.

2EHA: 2-ethylhexyl acrylate BA: butyl acrylate AA: acrylic acid MAA: methacrylic acid HEA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate

[Synthesis example 1 of addition type polyester]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, polycarbonate diol (Kuraray polyol C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanedio- Copolymer polycarbonate diol of 9/1 (molar ratio): hydroxyl value = 56 mgKOH / g, Mw = 2000) 292.1 parts, containing acid anhydride group for main chain Tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44.9 parts as a compound and 350 parts of toluene as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 62.9 parts of bisphenol A type epoxy resin (YD-8125: manufactured by Nippon Steel Chemical Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to form 110 parts. The temperature was raised to 0 ° C. and reacted for 8 hours. After cooling to room temperature, the non-volatile content was adjusted to 35% with ethyl acetate to obtain an addition type polyester solution. The weight average molecular weight of the addition-type polyester resin (B-2) obtained in this synthesis example was 12600, and the acid value of the resin non-volatile content measured was 9.3 mgKOH / g.

[Synthesis examples 2 to 10 of addition type polyester]
Synthesis was performed in the same manner as in Synthesis Example 1 except that the raw material in Synthesis Example 1 of Addition Polyester was replaced with the raw material described in Table 2, and an addition polyester resin (B-2) was obtained.

  The molar ratio in the table indicates the functional group ratio of each raw material when the hydroxyl group of the polyol compound (a) is 1 mol.

[Additional Polyester Synthesis Example 11]
To a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, polycarbonate diol (Kuraray polyol C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanedio- Copolymer polycarbonate diol of 9/1 (molar ratio): hydroxyl value = 56 mgKOH / g, Mw = 2000) 292.1 parts, containing acid anhydride group for main chain Tetrahydrophthalic anhydride (Licacid TH: manufactured by Shin Nippon Rika Co., Ltd.) 44.9 parts as a compound and 350 parts of toluene as a solvent were charged, heated to 60 ° C. with stirring under a nitrogen stream, and dissolved uniformly. Subsequently, the flask was heated to 110 ° C. and reacted for 3 hours. Then, after cooling to 40 ° C., 62.9 parts of bisphenol A type epoxy resin (YD-8125: manufactured by Nippon Steel Chemical Co., Ltd .: epoxy equivalent = 175 g / eq) and 4 parts of triphenylphosphine as a catalyst were added to form 110 parts. The temperature was raised to 0 ° C. and reacted for 8 hours. After cooling to room temperature, 11.8 parts of tetrahydrophthalic anhydride was added as an acid anhydride group-containing compound for the side chain, and reacted at 110 ° C. for 3 hours. After cooling to room temperature, it was adjusted with toluene so that the non-volatile content was 35% to obtain a polyester resin solution. The weight average molecular weight of addition type polyester resin (B-3) obtained by this synthesis example was 12600, and the acid value of the resin non-volatile part by measurement was 15.3 mgKOH / g.

[Synthesis Examples 12 to 20 of addition-type polyester resin]
Synthesis was performed in the same manner as in Synthesis Example 11 except that the raw material of Synthesis Example 11 of Addition Polyester was replaced with the raw materials described in Table 3, to obtain Addition Polyester Resin (B-3).

[Comparative Synthesis Examples 1 to 5 of Addition Polyester Resin]
The addition type polyester resin was obtained by synthesizing in the same manner except that the raw material of the addition type polyester was changed to the raw material described in Table 4.

C-2090: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / 1,6-hexanediol = 9/1 (molar ratio) copolymer polycarbonate polyol (weight average molecular weight about 2000)
P-2020: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / terephthalic acid-based polyester polyol (weight average molecular weight of about 2000)
P-2041 manufactured by Kuraray Co., Ltd .: polyester polyol based on 3-methyl-1,5-pentanediol / 1,4-cyclohexanedicarboxylic acid (weight average molecular weight of about 2000)
P-2011: Kuraray Co., Ltd .: 3-methyl-1,5-pentanediol / adipic acid / terephthalic acid copolymer polyester polyol (weight average molecular weight of about 2000)
T-5562: Asahi Kasei Chemicals Corporation: C ₅ C ₆ copolymer polycarbonate diol (number average molecular weight about 2000)
UM90 (3/1): Ube Industries, Ltd .: 1,4-cyclohexanedimethanol / 1,6-hexanediol = 3/1 (molar ratio) copolymer polycarbonate polyol (weight average molecular weight about 1000)
UC-100: manufactured by Ube Industries, Ltd .: 1,4-cyclohexanedimethanol base polycarbonate polyol weight average molecular weight of about 1000)
TH: Shin Nippon Rika Co., Ltd .: Tetrahydrophthalic anhydride HNA-100: Shin Nippon Rika Co., Ltd .: Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride anhydrous TMA: Trimellitic anhydride SA: Shin Nippon Rika Co., Ltd .: Succinic anhydride YD-8125: Nippon Steel Chemical Co., Ltd .: Bisphenol A type epoxy resin EX-212L: Nagase ChemteX Corporation: 1,6-hexanediol diglycidyl ether

Example 1
Addition-type polyester resin (B) solution obtained in synthesis example 1 of addition-type polyester resin with respect to 70 parts of non-volatile components of acrylic resin (A) with a weight average molecular weight of 1.5 million obtained in synthesis example 1 of acrylic resin The thermosetting adhesive composition was obtained by adding 30 parts of the non-volatile content (total 100 parts) and 7 parts of a polyfunctional glycidyl ether type epoxy resin (manufactured by Mitsubishi Chemical Corporation, EP 1031S). The obtained thermosetting adhesive composition was applied to a release-treated sheet (a release-treated polyethylene terephthalate film having a thickness of 75 μm) using a comma coater, and heated and dried at 100 ° C. for 2 minutes. An adhesive sheet having a dry film thickness of 30 μm was obtained.

(Examples 2-38, Comparative Examples 1-7)
Except having changed the raw material of Example 1 into the raw material described in Table 5-Table 7, it carried out similarly to Example 1 and obtained the adhesive sheet.

1031S: Mitsubishi Chemical Corporation: Multifunctional glycidyl ether type epoxy resin 828: Mitsubishi Chemical Corporation: bisphenol A type epoxy resin 806: Mitsubishi Chemical Corporation: bisphenol F type epoxy resin BL3175: Sumika Bayer Urethane Co., Ltd. , Isocyanurate type blocked isocyanate

  For the adhesive sheets obtained in Examples and Comparative Examples, the adhesive strength after adhesion, solder bath heat resistance after adhesion, and solder bath heat resistance after humidification after adhesion were evaluated by the following methods. The results are shown in Table 7.

(1) Adhesive strength Peel off the release-treated sheet from an adhesive sheet with a width of 10 mm and a length of 60 mm, and use two polyimide films (“Kapton 200EN” manufactured by Toray DuPont Co., Ltd.) as the adhesive layer. I caught it. Further, after pressure bonding under conditions of 150 ° C. and 1.0 MPa for 2 minutes, heat treatment was performed in an electric oven at 160 ° C. for 120 minutes. The composition of “Kapton 200EN / adhesive layer / Kapton 200EN” thus obtained was subjected to a T-peel peel test at a pulling rate of 50 mm / min in an atmosphere of 23 ° C. and 50% relative humidity. (N / cm).
◎ ・ ・ ・ Adhesive strength is 15 N / cm or more ○ ・ ・ ・ Adhesive strength is 8 or more and less than 15 N / cm Δ ・ ・ ・ Adhesion strength is 5 or more and less than 8 N / cm × ・ ・ ・ Adhesion strength is less than 5 N / cm

(2) Solder bath heat resistance An adhesive layer having a width of 10 mm and a length of 60 mm, from which the peel-treated polyester film covering both sides of the adhesive sheet has been removed, is a polyimide film having a thickness of 75 μm (Toray DuPont Co., Ltd.) “Kapton 300H”) and two-layer material (50 μm thick polyimide film (“Kapton 200EN” manufactured by Toray DuPont Co., Ltd.) were vacuum-deposited (sputtered), and then electroplated with copper foil. Between the polyimide side of the formed printed wiring board substrate) and heat laminating at 100 ° C., followed by pressure bonding at 150 ° C. and 1.0 MPa for 2 minutes, and then an electric oven at 160 ° C. The composition for heat resistance evaluation of “Kapton 300H / adhesive layer / 2-layer material” obtained in this way was obtained.Kapton 300 of this evaluation composition The evaluation component was floated on molten solder at 260 ° C. for 1 minute so that the H surface was in uniform contact with the solder, and the appearance of the evaluation component after floating on the molten solder was visually observed. It is as follows.
◎ ・ ・ ・ “No change in appearance”
○ ・ ・ ・ “Almost no change in appearance”
△ ... "Bubbling is observed"
× ・ ・ ・ "Strong foaming and peeling are observed"

(3) Solder bath heat resistance after humidification A test piece was prepared in the same manner as in (1) above, and was left to humidify in an atmosphere of 40 ° C. and 90% relative humidity for 72 hours. The composition for evaluation was floated on molten solder at 260 ° C. for 1 minute so that the surface of Kapton 300H was in uniform contact with the solder. The appearance of the evaluation composition after floating on the molten solder was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the adhesive layer was evaluated. This test evaluates the thermal stability of the adhesive layer at the time of solder contact of a humidified test piece by appearance. Those having good heat resistance after humidification do not change the appearance, but those having poor heat resistance after humidification cause foaming or peeling after soldering. The insulation reliability is judged by evaluating the solder bath heat resistance after the humidification. The evaluation criteria are as follows.
◎ ・ ・ ・ “No change in appearance”
○ ・ ・ ・ “Almost no change in appearance”
△ ... "Bubbling is observed"
× ・ ・ ・ "Strong foaming and peeling are observed"

  As is apparent from Table 7, Examples 1 to 38 of the present invention satisfy all the adhesive properties and heat resistance. On the other hand, Comparative Examples 1 to 6 are inferior in heat resistance and insulation reliability because the main chain of the addition-type polyester resin does not have a cyclic structure. Moreover, since the comparative example 7 does not contain the compound (C) which is a hardening | curing agent, heat resistance and insulation reliability are inferior.

Claims (8)

  A group consisting of an acrylic resin (A) having a weight average molecular weight of 100,000 to 2,000,000, an addition type polyester resin (B) having a cyclic structure in the main chain, an epoxy group-containing compound, an isocyanate-containing compound, and a blocked isocyanate group-containing compound. The thermosetting adhesive composition containing the compound (C) which is at least 1 type chosen from more.   The addition type polyester resin (B) is an addition type polyester resin (B-2) formed by reacting the addition type polyester resin (B-1) with a compound (c) having two or more epoxy groups. The thermosetting adhesive composition according to claim 1.   The addition type polyester resin (B) is obtained by reacting the addition type polyester resin (B-2) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring (B). The thermosetting adhesive composition according to claim 2, which is -3).   The addition type polyester resin (B-1) is obtained by reacting a polyol compound (a) with a compound (b) having a saturated or unsaturated cyclic structure and an acid anhydride ring. 3. The thermosetting adhesive composition according to 3.   The thermosetting adhesive composition according to any one of claims 1 to 4, wherein the acid value of the addition-type polyester resin (B) is 1 to 100 mgKOH / g.   The thermosetting adhesive composition according to any one of claims 1 to 5, wherein the addition-type polyester resin (B) has a weight average molecular weight of 5,000 to 500,000.   The adhesive sheet containing the adhesive bond layer formed from the thermosetting adhesive composition in any one of Claims 1-6.   A printed wiring board comprising a layer made of a cured product of the thermosetting adhesive composition according to claim 1.