JP2014141603A - Adhesive agent composition excellent in dielectric property, adhesive agent sheet using the same and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly thermostable adhesive agent composition having a low dielectric constant and a low dielectric dissipation factor, and further excellent in adhesiveness to metals, an adhesive sheet obtained by molding the adhesive agent composition into a sheet shape, and an insulation film with an adhesive sheet in which the adhesive sheet consisting of the adhesive agent composition is arranged on a single-side of the insulation film.SOLUTION: The problem is solved by an adhesive agent composition containing an epoxy compound having at least one or more tertiary nitrogen atoms in a molecule (A) and a carboxyl group-containing polymer (B).

Description

  The present invention relates to a high heat-resistant adhesive composition having a low dielectric constant and a low dielectric loss tangent and excellent in adhesion to metal, and is formed by molding this adhesive composition into a sheet shape. The object is to provide an adhesive sheet and an insulating film with an adhesive sheet in which an adhesive sheet made of the adhesive composition is provided on one side of the insulating film.

  In recent years, the development of the electronics field has been remarkable, and it has become necessary to process a large amount of information at a high speed, and the frequency band of signals used for printed wiring boards used in electronic devices, communication devices, etc. ranges from megahertz to gigahertz. It is moving to. However, there is a problem that the transmission loss of the electric signal increases as the frequency of the electric signal increases. To cope with such a problem, an electronic material having excellent dielectric characteristics in a high frequency band and a print using the same There is a strong demand for the development of wiring boards.

  In general, transmission loss of electrical signals is said to be composed of dielectric loss due to dielectric properties of insulation layers around wiring and conductor loss due to conductor shape, skin resistance, characteristic impedance, etc. In this case, the influence of the dielectric loss is large, and the dielectric loss increases in proportion to the product of the square root of the relative dielectric constant of the material and the dielectric loss tangent of the material. Therefore, a material having a small relative dielectric constant and dielectric loss tangent is required. ing. For this reason, adhesives and coating agents around the wiring of printed wiring boards are required to have low dielectric properties in addition to the high flexibility, adhesiveness, high electrical insulation, thermal stability, etc. that have been conventionally required. The current situation is.

  Various studies have been conducted to meet the high demands for adhesives and coating agents around printed wiring boards through which such high-frequency electrical signals propagate, but those that fully satisfy all the characteristics have been obtained. Absent.

  For example, a composition comprising a siloxane-modified imide and a maleimide compound is disclosed (Patent Document 1). Although this system has flexibility specific to the siloxane skeleton and excellent heat resistance, the siloxane skeleton itself has poor adhesion to the substrate, so that sufficient adhesive strength cannot be obtained, and heat such as press Poor processability such as the occurrence of protrusion during curing has been a problem. Further, since the compatibility with other components is remarkably poor, there is a problem that the degree of freedom in designing the composition is poor and the coating film has insufficient resistance as a composition.

  Moreover, the resin composition containing the polybutadiene which is a flexible frame | skeleton is disclosed (patent documents 2-6). However, polybutadiene has a low dielectric constant, but if the amount of polybutadiene increases, the butadiene skeleton oxidizes, causing intramolecular cross-linking, causing the resin to gel during the reaction or significantly reducing the storage stability of the composition. There are problems with basic characteristics as insulating materials for general electric circuit boards, such as electrical insulation and chemical resistance at high temperature humidification.

  Moreover, the adhesive composition containing the cyanate ester resin with the lowest dielectric constant among thermosetting resins is disclosed (patent documents 7 to 11). Compositions containing polyphenylene ether resins and other resins have been studied, but since these use cyanate esters, the dielectric constant is relatively better than other compositions, but the dielectric loss tangent is the dielectric constant. There is a problem that it is relatively high and high-frequency characteristics are insufficient, and there is also a problem in versatility that the compatibility between resins is poor and the solvent solubility is poor.

  Moreover, the adhesive composition containing polyolefin is disclosed (patent document 12). Polyolefin does not have a large polar group, so its electrical properties, especially its relative permittivity and dielectric loss tangent, are small and excellent, but it has a large coefficient of linear expansion and is not sufficiently heat resistant, such as being deformed by heating. There is a drawback. Furthermore, the composition which mix | blended the organic peroxide with respect to the thermoplastic hydrogenated ring-opening norbornene-type resin is also disclosed (patent document 13). However, the present situation is that a cross-linked molded product having a balance between dielectric characteristics in the high frequency region and solder heat resistance cannot be obtained with such a blend.

  Moreover, the adhesive composition containing an epoxy compound as resin with comparatively favorable heat resistance is disclosed. In general, the epoxy resin satisfies the required performance with respect to electrical insulation and heat resistance, but a highly polar hydroxyl group is generated by the reaction of the epoxy group and active hydrogen, resulting in a high relative dielectric constant of 3 or more, Satisfactory properties have not been obtained. Then, the combination with a phenol novolak resin, a vinyl triazine resin, etc. is examined for the purpose of improvement of an epoxy resin (patent documents 14-18). However, these can improve the dielectric properties by reducing the proportion of epoxy, but when used as a film, the wettability to the substrate is reduced, the adhesive strength is reduced, and low molecular compounds Due to the large amount, there is a problem of poor workability that a lot of protrusion occurs when thermosetting with a press or the like.

JP 2000-143734 A JP 1998-77387 A Japanese Patent Laid-Open No. 1994-248074 JP 1995-157559 A JP 2004-161828 A JP 2008-81678 A JP 2002-339997 A JP 2005-120173 A JP 2003-138133 A JP 2002-317085 A JP 2011-252152 A Japanese Patent Laid-Open No. 2003-238761 JP-A-6-248164 JP 1995-157540 A JP-A-2005-187800 JP 2009-227992 A JP-A-6-192393 JP-A-8-325355

  The present invention relates to a high heat-resistant adhesive composition having a low dielectric constant and a low dielectric loss tangent and excellent in adhesion to metal, and is formed by molding this adhesive composition into a sheet shape. The object is to provide an adhesive sheet and an insulating film with an adhesive in which an adhesive sheet made of the adhesive composition is provided on one side of the insulating film. That is, as an adhesive and coating agent used around electronic materials such as printed wiring boards, in addition to the high flexibility, adhesiveness, high electrical insulation, thermal stability, etc. that have been conventionally required, It is an object of the present invention to provide an adhesive composition having dielectric properties.

In order to solve the above-mentioned problems, the present inventors have intensively studied to complete the present invention.
That is, this invention relates to the adhesive composition characterized by containing the epoxy compound (A) which has an at least 1 or more tertiary nitrogen atom in a molecule | numerator, and a carboxyl group-containing high molecular compound (B).
In the present invention, the carboxyl group-containing polymer compound (B) is at least one resin selected from the group consisting of acrylic resins, urethane resins, ester resins, phenoxy resins, amide resins, and imide resins. It relates to the adhesive composition.
The present invention also relates to the adhesive composition, wherein the carboxyl group-containing polymer compound (B) has an acid value of 1 to 100 KOHmg / g.
The present invention also relates to the adhesive composition, wherein the carboxyl group-containing polymer compound (B) has a weight average molecular weight of 5,000 to 500,000.
Moreover, this invention relates to the said adhesive composition characterized by containing a filler (C).
The present invention also relates to a cured product obtained by curing the adhesive composition by heating, having a frequency of 1 GHz, a dielectric constant of 3.0 or less, and a dielectric loss tangent of 0.03 or less.
Moreover, this invention relates to the adhesive sheet characterized by having the layer which consists of the said hardened | cured material.
Furthermore, this invention relates to the printed wiring board characterized by having the layer which consists of the said hardened | cured material.

  According to the present invention, an adhesive composition comprising an epoxy compound having at least one nitrogen atom in a molecule and a carboxyl group-containing polymer compound as an adhesive and coating agent used around an electronic material such as a printed wiring board By using the product, it was possible to achieve both low dielectric properties and high flexibility, adhesion, high electrical insulation, thermal stability, and the like.

The adhesive composition having excellent dielectric properties of the present invention can be obtained by including an epoxy compound (A) having at least one nitrogen atom in the molecule and a carboxyl group-containing polymer compound (B),
By using this adhesive composition, it is possible to remarkably improve high flexibility, adhesion, high electrical insulation, thermal stability, etc., as well as dielectric properties, which are very important for printed wiring boards that propagate high-frequency electrical signals. it can. This is because the epoxy compound (A) having at least one nitrogen atom in the molecule is used for the thermosetting composition. Compared with the composition having the conventional epoxy compound, the nitrogen atom and copper are used. This is because adhesion using interaction can be imparted. In addition, since the carboxyl group-containing polymer compound (B) is used as a binder resin for the epoxy compound (A) having at least one nitrogen atom in the molecule, the crosslinking speed, crosslinking density, and cohesive force can be adjusted. Therefore, various physical properties can be remarkably improved.

<Epoxy compound (A) having at least one tertiary nitrogen atom in the molecule>
The epoxy compound (A) having at least one tertiary nitrogen atom in the molecule of the present invention will be described in detail.

The adhesive composition having excellent dielectric properties according to the present invention is characterized in that the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule is used as the epoxy compound. By using an epoxy compound (A) having at least one tertiary nitrogen atom, a dielectric constant, dielectric loss tangent, metal which is very important as an adhesive and coating agent around a printed wiring board through which a high-frequency electric signal propagates Adhesiveness and heat resistance can be remarkably improved.
This is because of the high reactivity that is characteristic of an epoxy compound having a tertiary nitrogen atom, the reaction rate under a predetermined curing condition can be increased, the crosslinking density of the cured product is improved, and a high elastic modulus is obtained. This is because, as a result, the water absorption that affects the dielectric characteristics can be suppressed. In addition, since nitrogen atoms can take various coordination forms, it is presumed that they strongly support adhesion between metals and organic compounds, and are excellent in terms of adhesion to metals such as copper. A thermosetting resin compound can be obtained.

  For example, an epoxy compound that does not belong to an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule instead of an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule In general, heat resistance of the cured product and adhesion to the substrate due to the polarity derived from the hydroxyl group generated after curing of the epoxy compound can provide some heat resistance and adhesion, but high temperature humidification, etc. Under severe conditions, the deterioration of dielectric properties due to water absorption becomes remarkable, and the dielectric properties and various properties required for adhesives and coating agents around printed wiring boards, which are the subject of the present invention, propagate high-frequency electrical signals. Can not be satisfied.

On the other hand, when the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule of the present invention is used, the reaction rate under a predetermined curing condition is increased by the nitrogen atom contained in the compound (A). Therefore, it is possible to suppress a decrease in elastic modulus and an increase in water absorption rate due to unreacted low molecular weight compounds, and further, it is possible to improve metal adhesion derived from nitrogen atoms, so that it has good dielectric properties and various properties. Can be satisfied at the same time.
In the present invention, the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule may have at least one nitrogen compound in the compound containing an epoxy group in the molecule, It is not particularly limited. Specific examples of the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule include N-glycidylphthalimide and epoxy compounds having a structure represented by the following formulas (11) to (21). It is done.

Formula (11)

Formula (12)

Formula (13)

Formula (14)

Formula (15)

Formula (16)

Formula (17)

Formula (18)

Formula (19)

Formula (20)

Formula (21)

X represents an aliphatic group having 0 to 6 carbon atoms or an aromatic group, and Y represents a methylene group, an ethylene group, a trimethylene group, an ethylidene group, an isopropylidene group, a vinylene group, a vinylidene group, an oxy group, It represents any of an imino group, a thio group, and a sulfonyl group, R _{1 to} R ₃ represent a hydrogen atom or an aliphatic group having 1 to 6 carbon atoms, and j represents an integer of 0 to 4.

  Both are excellent in terms of dielectric properties from the viewpoints of thermosetting and low hygroscopicity, and are particularly preferable. In particular, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N'-tetraglycidyl-m-xylenediamine, triglycidyl-m-aminophenol, triglycidyl-p-aminophenol, 4,4'-methylenebis [N, N-bis (oxiranylmethyl) aniline] is multifunctional When used in the present invention, the heat resistance of the cured coating film tends to improve in addition to the dielectric properties, which is particularly preferable. N, N-diglycidyl aniline and N, N-diglycidyl toluidine are bifunctional, and when used in the present invention, in addition to dielectric properties, the flexibility of the cured coating and the adhesion to polyimide and copper are improved. This is preferable. Thus, in the present invention, the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule can be selected according to the purpose, and these may be used alone, It is also preferable to use a plurality.

Moreover, in this invention, you may use together the epoxy compound which does not have a nitrogen compound in a molecule | numerator in order to adjust the crosslinking density of hardened | cured material in the range which does not impair a physical property. Specifically, for example, compounds having one epoxy group in the molecule include compounds such as glycidol and glycidyl (meth) acrylate.
Examples of the compound having two epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, poly Tetramethylene 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, hydro Non diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenyl sulfone Diglycidyl ether, dihydroxybenzophenone diglycidyl ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol full orange glycidyl ether, biscresol full orange glycidyl ether, bisphenoxyethanol full orange glycidyl ether, JP 2004-156024 A, JP No. 2004-315595 And an epoxy compound excellent in flexibility disclosed in JP 2004-323777 A, an epoxy compound having a structure represented by the following formulas (1) to (3), and the like.

Formula (1)

Formula (2)

さらに、分子中に３個以上のエポキシ基を有する化合物としては、三菱化学株式会社製「エピコート１０３１Ｓ」、「エピコート１０３２Ｈ６０」の他、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、特開２００１-２４０６５４号公報に開示されているジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、エチレングリコール・エピクロルヒドリン付加物のポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル等が挙げられる。また、エポキシ基以外の他の熱硬化性基を併有する化合物も使用できる。例えば、特開２００１−５９０１１号公報や、２００３−４８９５３号公報に開示されているシラン変性エポキシ樹脂が挙げられる。 Formula (3)

Further, examples of the compound having three or more epoxy groups in the molecule include “Epicoat 1031S” and “Epicoat 1032H60” manufactured by Mitsubishi Chemical Corporation, phenol novolac type epoxy resins, cresol novolac type epoxy resins, Examples thereof include dicyclopentadiene type epoxy resins, naphthalene type epoxy resins, polyglycidyl ethers of ethylene glycol / epichlorohydrin adducts, pentaerythritol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers and the like disclosed in Japanese Patent No. 240654. 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.

  As described above, in the present invention, for the purpose of adjusting the crosslinking density of the cured product, an epoxy compound having no nitrogen compound in the molecule is used in combination with an epoxy compound (A) having at least one nitrogen atom in the molecule. It is possible to select according to the purpose. Moreover, the epoxy compound which does not have a nitrogen compound in a molecule | numerator may use a single kind, and may use multiple.

<Carboxyl group-containing polymer compound (B)>
Next, the carboxyl group-containing polymer compound (B) of the present invention will be described in detail.

  The carboxyl group-containing polymer compound (B) used in the low dielectric constant adhesive composition of the present invention is at least one selected from the group consisting of acrylic resins, urethane resins, ester resins, phenoxy resins, amide resins, and imide resins. As long as it is a compound of By using these resins, in addition to dielectric properties that can be imparted by using an epoxy compound (A) having at least one nitrogen atom in the molecule, adhesion, flexibility, electrical insulation, heat resistance Therefore, a cured product having an excellent balance with various properties such as properties can be obtained, and the flexible printed wiring board can be protected from physical and chemical stresses.

  Specifically, when only an epoxy compound (A) having at least one nitrogen atom in the molecule is used, the dielectric properties, heat resistance, and adhesion to various substrates are remarkably improved, but the cured product as a whole Therefore, the flexibility and handling properties as an adhesive sheet are not good. However, by using the carboxyl group-containing polymer compound (B), these problems can be solved, and a cured product having an excellent balance of dielectric properties, adhesiveness, flexibility, electrical insulation, and heat resistance. Can be obtained.

<Carboxyl group-containing acrylic resin>
Examples of the method for producing a carboxyl group-containing acrylic resin in the present invention include the following synthesis methods including those conventionally known. For example, a method in which an ethylenically unsaturated monomer having a carboxyl group is copolymerized with another monomer, or a hydroxyl group in a polymer obtained by copolymerizing a hydroxyl group-containing ethylenically unsaturated monomer with another monomer is converted to a polybasic acid. It can be produced by reacting with an acid anhydride group in an anhydride. In the present invention, the (meth) acrylic acid ester monomer means both an acrylic acid ester monomer and a methacrylic acid ester monomer.

  There is no restriction | limiting in particular as an ethylenically unsaturated monomer which has a carboxyl group, For example, (meth) acrylic acid, (meth) acrylic acid 2-carboxyethyl, (meth) acrylic acid 2-carboxypropyl, (meth) acrylic acid 3 -Carboxypropyl, 4-carboxybutyl (meth) 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, senecioic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid, citronel Acid, 4-acrylamidobutanoic acid, 6-a Rylamidohexanoic acid or polylactone (meth) acrylic acid ester having a carboxyl group at the terminal by ring-opening addition of lactone ring such as ω-carboxypolycaprolactone mono (meth) acrylate, or alkylene oxide such as ethylene oxide or propylene oxide A carboxyl group-containing aliphatic ethylenically unsaturated carboxylic acid such as an alkylene oxide-added succinic acid (meth) acrylate having a carboxyl group at the terminal to which the compound is repeatedly added; 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 And ethylenically unsaturated carboxylic acids having a carboxyl group-containing alicyclic ring or aromatic ring such as 7-amino-3-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;

2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole [2- (2′-hydroxy-5′-acryloyloxyethylphenyl) -2H-benzotriazole and 2- ( 2′-Hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole and “2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole” To do. The same applies hereinafter. ], 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;

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

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- Hydroxyl-containing triazine (meth) such as triazine, 2,4-bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine Acrylic esters;

Glucose ring system (meth) acrylates such as glycosylmethyl (meth) acrylate, glycosylethyl (meth) acrylate, glycosylpropyl (meth) acrylate, glycosylbutyl (meth) acrylate;

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, 2,4,6- Hydroxyl group-containing aromatic vinyl compounds such as trihydroxystyrene and 2-hydroxy-6-vinylnaphthalene;

N-hydroxyethyl (meth) acrylamide [N-hydroxyethylacrylamide and N-hydroxyethylmethacrylamide 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.

  There is no restriction | limiting in particular as another ethylenically unsaturated monomer which does not have a carboxyl group or a hydroxyl group, for example, the (meth) acrylic-acid alkylester monomer whose carbon number of the alkyl group of an ester part is 1-20, and vinyl group containing Mention may be made of monomers. 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.

  Examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride And polybasic acid anhydrides.

  When an acrylic resin is used as the carboxyl group-containing polymer compound (B), the carboxyl group-containing ethylenically unsaturated monomer and / or the hydroxyl group-containing ethylenically unsaturated monomer is used in a total of 100 ethylenically unsaturated monomers. It is preferable to use 10 parts by weight or less in parts by weight. By using it at 10 weight part or less, it becomes easy to make cohesion force and adhesiveness compatible.

<Carboxyl group-containing urethane resin>
Examples of the method for producing a carboxyl group-containing urethane resin in the present invention include the following synthesis methods including those conventionally known. For example, it can be produced by reacting a polyol compound, a diisocyanate compound and a diol compound having a carboxyl group. In addition, when synthesizing the carboxyl group-containing urethane resin, an excess of diisocyanate compound is synthesized, a carboxyl group-containing urethane prepolymer having an isocyanate group at the terminal is synthesized, and then a urea group is introduced by reacting with a diamine compound. Urea resins can also be produced.

In the present invention, the polyol compound means a compound having a weight average molecular weight of 500 or more and having two or more hydroxyl groups. Specifically, for example, polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol, or random copolymer Polyether polyols such as coalescence;
Polyester polyols which are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Polycarbonate polyols obtained by reaction of glycol or bisphenol with a carbonic acid ester or reaction of phosgene with glycol or bisphenol in the presence of alkali;
Examples thereof include caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin polyol, polybutadiene polyol such as hydrogenated polybutadiene polyol, and polyol such as silicone polyol.
These polyol compounds may be used alone or in combination of two or more.

The diol compound having a carboxyl group is not particularly limited as long as it is a compound having two hydroxyl groups and one or more carboxyl groups in the molecule. For example, dimethylolbutanoic acid, dimethylolpropionic acid, and these Derivatives (caprolactone adducts, ethylene oxide adducts, propylene oxide adducts, etc.), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol and the like can be mentioned.
These diol compounds having a carboxyl group may be used alone or in combination of two or more.

  Examples of the diisocyanate compound include aromatic diisocyanate, aliphatic diisocyanate, araliphatic diisocyanate, and alicyclic diisocyanate.

  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.
These diisocyanate compounds may be used alone or in combination of two or more.

The diamine compound serves as a chain extender, for example, diaminobenzene, diaminotoluene, diaminodimethylbenzene, diaminomesitylene, diaminochlorobenzene, diaminonitrobenzene, diaminoazobenzene, diaminonaphthalene, diaminobiphenyl, diaminodimethoxybiphenyl, diaminodiphenyl ether, Diaminodimethyldiphenyl ether, methylenedianiline, methylenebis (methylaniline), methylenebis (dimethylaniline), methylenebis (methoxyaniline), methylenebis (dimethoxyaniline), methylenebis (ethylaniline), methylenebis (diethylaniline), methylenebis (ethoxyaniline), Methylenebis (diethoxyaniline), methylenebis (dibromoaniline) Isopropylidene aniline, hexafluoro isopropylidene aniline, diaminobenzophenone, diamino dimethyl benzophenone, diaminoanthraquinone, diaminodiphenyl thioether, diaminodiphenyl dimethyl diphenyl thioether, diaminodiphenyl sulfone, and diaminodiphenyl sulfoxide, aromatic such as diaminofluorene polyamine;
Ethylene polyamine, propane polyamine, hydroxypropane polyamine, butane polyamine, heptane polyamine, hexane polyamine, diaminodiethylamine, diaminodipropylamine, azapentane polyamine, triazaundecane polyamine, nonamethylene polyamine, undecamethylene polyamine, dodecamethylene polyamine, Aliphatic polyamines such as methylpentamethylene polyamine, 2,2,4 (or 2,4,4) -trimethylhexamethylene polyamine and polyamine compounds having 20 to 48 carbon atoms;
Use alicyclic polyamines such as bis- (4,4'-aminocyclohexyl) methane, metaxylylene polyamine, paraxylylene polyamine, isophorone polyamine, norbornane polyamine, cyclopentane polyamine, cyclohexane polyamine, piperazine, homopiperazine Can do.

  When a urethane resin is used as the carboxyl group-containing polymer compound (B), it is preferable to use a urethane urea resin into which a urea group has been introduced. By introducing a urea group, it becomes easy to improve adhesiveness and flexibility.

<Carboxyl group-containing ester resin>
Examples of the method for producing a carboxyl group-containing ester resin in the present invention include the following synthesis methods including those conventionally known. For example, a compound having two carboxyl groups in the molecule and a compound having two hydroxyl groups in the molecule are subjected to a polycondensation reaction under conditions where the number of moles of carboxyl groups is excessive relative to the number of moles of hydroxyl groups. Or by synthesizing a side chain hydroxyl group-containing ester resin by polyaddition reaction of a compound having two carboxyl groups in the molecule and a compound having two epoxy groups in the molecule, There is a method obtained by modification to a carboxyl group with an acid anhydride.

The compound having two carboxyl groups in the molecule is not particularly limited as long as it is a compound having two carboxyl groups in the molecule. For example, a polybasic acid compound having a cyclic or acyclic hydrocarbon group having 20 to 48 carbon atoms;
Phthalic acid, isophthalic acid, terephthalic acid, xylylene dicarboxylic acid, benzenedipropionic acid, biphenyl polybasic acid, oxydibenzoic acid, thiodibenzoic acid, dithiodibenzoic acid, dithiobis (nitrobenzoic acid), carbonyldibenzoic acid, sulfonyldi Aromatic polybasic compounds such as benzoic acid, naphthalenedicarboxylic acid, methylenedibenzoic acid, isopropylidenedibenzoic acid, hexafluoroisopropylidenedibenzoic acid, pyridine polybasic acid;
Oxalic acid, malonic acid, methylmalonic acid, succinic acid, glutaric acid, adipic acid, 2,2,4-trimethyladipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, (meth) acryloyloxysuccinic acid, di ( (Meth) acryloyloxysuccinic acid, (meth) acryloyloxymalic acid, (meth) acrylamide succinic acid, (meth) acrylamide malic acid, thiomalic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexadecane Aliphatic polybasic acid compounds such as dionic acid, eicosandioic acid and diglycolic acid;
Examples include alicyclic polybasic acid compounds such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid.

  The compound having two epoxy groups in the molecule is not particularly limited as long as it is a compound having two epoxy groups in the molecule, and includes the above-mentioned compounds.

  As the polybasic acid anhydride, the above-mentioned polybasic acid anhydrides can be used.

  When using an ester resin as the carboxyl group-containing polymer compound (B), it is preferable to use an ester resin obtained by polyaddition reaction. Since the ester resin obtained by the polyaddition reaction can finally introduce a carboxyl group into the side chain, the electrical insulation and heat resistance of the cured product are further improved during the crosslinking reaction with the compound (A). .

<Carboxyl group-containing phenoxy resin>
Examples of the method for producing a carboxyl group-containing phenoxy resin in the present invention include the following synthesis methods including those conventionally known. For example, after reacting a compound having two phenolic hydroxyl groups in the molecule with a compound having two epoxy groups in the molecule to synthesize a side chain hydroxyl group-containing phenoxy resin, the hydroxyl group is converted into a polybasic acid anhydride. Can be produced by modification to a carboxyl group.

The compound having two phenolic hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two phenolic hydroxyl groups in the molecule. For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example, and in addition to the central carbon such as bis (4-hydroxyphenol) methane (also known as bisphenol F). Bisphenols to which hydrogen atoms are bonded;
Bisphenols in which one methyl group is bonded to the central carbon such as 2,2-bis (4-hydroxyphenyl) -n-butane;
2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C)
Bisphenols in which two methyl groups are bonded to a central carbon such as
Bisphenols which are diphenylmethane derivatives such as bis (4-hydroxyphenyl) -1,1-diphenylmethane;
Bisphenols which are cyclohexane derivatives such as 1,1-bis (4-hydroxyphenyl) cyclohexane (commonly called bisphenol Z);
Bisphenols which are -3,3,5-trimethylcyclohexane derivatives such as 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane;
9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-
Bisphenols which are fluorene derivatives such as hydroxyphenyl) fluorene;
Bisphenols that are cycloalkane derivatives such as 1,1-bis (4-hydroxyphenyl) -cyclopentane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bisphenols which are sulfone derivatives such as bis (4-hydroxyphenyl) sulfone;
Bisphenols having an ether bond such as bis (4-hydroxyphenyl) ether;
Bisphenols having a sulfide bond such as bis (4-hydroxyphenyl) sulfide;
Bisphenols which are sulfoxide derivatives such as bis (4-hydroxyphenyl) sulfoxide;
Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Examples thereof include bisphenols having a carbon-fluorine bond, such as 2,2-bis (4-hydroxyphenyl) hexafluoropropane.
And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.

  The compound having two epoxy groups in the molecule is not particularly limited as long as it is a compound having two epoxy groups in the molecule. Mention may be made of the compounds mentioned above.

  As the polybasic acid anhydride, the above-mentioned polybasic acid anhydrides can be used.

  When a phenoxy resin is used as the carboxyl group-containing polymer compound (B), it is preferable to use tetrahydrophthalic anhydride or hexahydrophthalic anhydride as the polybasic acid anhydride. This makes it easier to improve the electrical insulation and heat resistance of the cured product.

<Carboxyl group-containing amide resin>
Examples of the method for producing a carboxyl group-containing amide resin in the present invention include the following synthesis methods including those conventionally known. For example, dehydration condensation of a compound having two carboxyl groups in the molecule and a compound having two amino groups in the molecule under conditions where the number of moles of carboxyl groups is excessive relative to the number of moles of amino groups The method obtained by reacting the compound having two carboxyl groups in the molecule and the compound having two isocyanate groups in the molecule causes the number of moles of the carboxyl groups to be excessive with respect to the number of moles of the isocyanate groups. There is a method obtained by decarboxylation under conditions.

<Carboxyl group-containing imide resin>
Similarly, as the carboxyl group-containing imide resin in the present invention, those synthesized conventionally including those known in the art can be used. Specifically, the carboxyl group-containing imide resin was used when producing the carboxyl group-containing amide resin. It can be obtained by replacing part or all of a compound having two carboxyl groups in the molecule with a polybasic acid anhydride.

  Examples of the polybasic acid anhydride include tetrabasic acid anhydrides in addition to the above-mentioned compounds, such as pyromellitic anhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4- Dicarboxyphenyl) ethane Dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3 , 4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3, 6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, phenanthrene-1,8, 9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, bis (3,4 -Zika Boxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester acid anhydride), ethylenetetracarboxylic dianhydride, 1 , 2,3,4-butanetetracarboxylic dianhydride, decahodronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 , 7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3 4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride) Sulfone, bicyclo- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoro Propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride , 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene Bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetra Examples thereof include carboxylic dianhydrides.

  In the present invention, the carboxyl group-containing polymer compound (B) may be used alone or in combination. The amount of the carboxyl group-containing polymer compound (B) used may be determined in consideration of the application of the curable resin composition of the present invention, and is not particularly limited. It is preferable to add at a ratio of 100 parts by weight to 5000 parts by weight, and more preferably 200 parts by weight to 3000 parts by weight with respect to 100 parts by weight of the epoxy compound (A) having at least one. If the amount of the carboxyl group-containing polymer compound (B) used is less than 10 parts by weight, the crosslinking density of the coating after heat curing becomes high, the cured product becomes brittle, and the flexibility and handling as an adhesive sheet are significantly deteriorated. There is a case to let you. On the other hand, when the amount used is more than 5000 parts by weight, the cross-linking density of the coating after heat curing becomes too low, and the dielectric properties, adhesiveness, and heat resistance may be insufficient. Thus, since the crosslinking density of the curable resin composition of the present invention can be adjusted to an appropriate value by using the carboxyl group-containing polymer compound (B), the dielectric properties of the coating film after curing can be adjusted. The balance of adhesiveness, flexibility, electrical insulation and heat resistance can be further improved.

  The acid value of the carboxyl group-containing polymer compound (B) of the present invention is preferably 1 to 100 KOHmg / g, more preferably 5 to 90 KOHmg / g. When the acid value is less than 1 KOHmg / g, there are few carboxyl groups that function as curable groups, and sufficient resistance may not be imparted to the cured coating film. On the other hand, when the acid value exceeds 100 KOHmg / g, the hardness of the coating film increases and sufficient adhesiveness may not be obtained. In addition, when the acid value is designed in the range of 1 to 100 KOHmg / g and in the range close to 1 KOHmg / g, the flexibility and adhesion of the resulting coating are improved, while the design is made in the range close to 100 KOHmg / g. In that case, since the number of crosslinking points increases, the heat resistance of the finally obtained coating film is improved. Thus, in this invention, the acid value of a carboxyl group-containing high molecular compound (B) can be adjusted according to the objective within the range of 1-100 KOHmg / g.

  The weight average molecular weight of the carboxyl group-containing polymer compound (B) of the present invention is preferably in the range of 5,000 to 500,000, more preferably 10,000 to 300,000. If the weight average molecular weight is less than 5000, sufficient flexibility and heat resistance may not be obtained. Moreover, when the weight average molecular weight exceeds 500,000, the viscosity at the time of coating and handling may become a subject. In addition, when the weight average molecular weight is designed to be close to 5000 within the range of 5,000 to 500,000, the mobility of the carboxyl group-containing polymer compound becomes high and the resin becomes rich in crosslinkability. On the other hand, when designing with a value close to 500,000, the finally obtained coating film is excellent in flexibility and adhesiveness. Thus, in this invention, the weight average molecular weight of a carboxyl group-containing high molecular compound (B) can be adjusted according to the objective within the range of 5000-500000.

<Filler (C)>
Next, the filler (C) of the present invention will be described in detail.
The adhesive composition of the present invention can contain a filler (C) for the purpose of imparting flame retardancy and controlling the fluidity of the adhesive.

Although it does not specifically limit as a filler (C), As a shape, spherical shape, powdery shape, fibrous shape, needle shape, scale shape, etc. are mentioned.
Examples of fillers include polytetrafluoroethylene powder, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, silicone, acrylic, styrene butadiene rubber, butadiene rubber, etc. Polymer filler such as core shell of multilayer structure used;
(Poly) phosphates such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium amidophosphate, carbamate phosphate, carbamate polyphosphate Compounds, organophosphate ester compounds, phosphazene compounds, phosphonic acid compounds, diethyl diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphorus flame retardant fillers such as acid compounds, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds;
Nitrogen-based flame retardant fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea;
Silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, sulfuric acid Magnesium, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, carbonic acid Examples include inorganic fillers such as zinc, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate.

Among them, as the filler (C), it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant filler or a nitrogen flame retardant filler, which has been recently taken into consideration, considering the influence on the environment. It is preferable to use a phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, etc., which are more effective in flame retardancy, in combination with the adhesive composition. In addition, it is preferable to use polytetrafluoroethylene powder in terms of further reducing the dielectric constant and dielectric loss tangent, and it has excellent balance not only with dielectric properties but also with adhesion, flexibility, electrical insulation, and heat resistance. You can get things.
In the present invention, these fillers (C) can be used alone or in combination.

  The average particle size of these fillers (C) is preferably 0.1 μm to 25 μm. When a filler having an average particle diameter close to 0.1 μm is used, a modification effect by the filler is easily obtained, and further, dispersibility and stability of the dispersion liquid are easily improved. Moreover, when the filler which shows the average particle diameter near 25 micrometers is used, the mechanical characteristic of a cured film becomes easy to improve.

  The addition amount of the filler (C) is preferably 0.01 part to 500 parts with respect to the epoxy compound (A) having at least one tertiary nitrogen atom in the molecule. If the amount of filler added is below this range, the modification effect by the filler is difficult to obtain, and if it exceeds this range, the mechanical properties of the cured film may be greatly impaired.

  The addition method of the filler (C) is not particularly limited, and any conventionally known method may be used. Specifically, a method of adding to the polymerization reaction solution before or during the polymerization, a three roll, etc. And a method of kneading the filler using, and a method of preparing a dispersion containing the filler and mixing them. Further, in order to disperse the filler satisfactorily and stabilize the dispersion state, a dispersant, a thickener and the like can be used as long as the physical properties of the adhesive sheet are not affected.

<Heat curing aid>
Furthermore, in the present invention, in addition to the epoxy compound (A) having at least one nitrogen atom in the molecule and the carboxyl group-containing polymer compound (B), a compound that directly contributes to the curing reaction or a catalytic contribution. A thermosetting aid can be used. For example, the thermosetting auxiliary agent that directly contributes to the curing reaction includes an aziridine compound, a carbodiimide group-containing compound, a benzoxazine compound, a phenol resin, a maleimide compound, dicyandiamide, a carboxylic acid hydrazide, an acid anhydride, and a β-hydroxyalkylamide group. Examples thereof include compounds and blocked isocyanates. In addition, examples of thermosetting aids that contribute catalytically include amine compounds and phosphine compounds.

[Aziridine compound]
The aziridine compound in the present invention is not particularly limited as long as it is a compound containing an aziridine group in the molecule.

  Examples of the aziridine compound include N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxite), N, N′-toluene-2,4-bis (1-aziridinecarboxite), bisiso Phthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxite), trimethylolpropane-tri-β -Aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [ 3- (1-aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) butyrate ], Trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate], 2,2′-bishydroxy Methylbutanol tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N′-ethyleneurea, 1,6-hexamethylene Bis-N, N′-ethylene urea, 2,4,6- (triethyleneimino) -Syn-triazine, bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylic acid amide and the like can be mentioned. .

  In particular, 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], when used in the present invention, can suppress protrusion during hot pressing and retain the flexibility of the cured coating film. Since heat resistance can be improved as it is, it is preferably used in the present invention.

[Carbodiimide group-containing compound]
Examples of the carbodiimide group-containing compound include the Carbodilite series of Nisshinbo Industries, Ltd. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

[Benzoxazine compounds]
As the benzoxazine compound, described in Macromolecules, 36, 6010 (2003), “P-a”, “P-alp”, “P-ala”, “B-ala”, described in Macromolecules, 34, 7257 (2001). “P-appe”, “B-appe”, “Ba type benzoxazine”, “Fa type benzoxazine”, “Bm type benzoxazine” manufactured by Shikoku Kasei Co., Ltd. and the like can be mentioned.

[Phenolic resin]
Examples of the phenol resin include addition compounds of compounds such as phenol, cresols, and bisphenols with formaldehyde, or partial condensates thereof. Specifically, phenol resin, cresol resin, t-butylphenol resin, dicyclopentadiene cresol resin, dicyclopentadiene phenol resin, xylylene-modified phenol resin, tetrakisphenol resin, bisphenol A resin, poly-p-vinylphenol resin resole Mold resin and novolac resin. Other examples include naphthol compounds, trisphenol compounds, phenol aralkyl resins, and the like. Among them, the resol type resin of phenol resin is very excellent in terms of heat resistance and curability and can be suitably used in the present invention.

[Maleimide compound]
The maleimide compound has at least one maleimide group in the molecule. For example, phenylmaleimide, 1-methyl-2,4-bismaleimidebenzene, N, N′-m-phenylenebismaleimide, N , N′-p-phenylene bismaleimide, N, N′-4,4-biphenylene bismaleimide, N, N′-4,4- (3,3-dimethylbiphenylene) bismaleimide, N, N′-4, 4- (3,3-dimethyldiphenylmethane) bismaleimide, N, N′-4,4- (3,3-diethyldiphenylmethane) bismaleimide, N, N′-4,4-diphenylmethane bismaleimide, N, N ′ -4,4-diphenylpropane bismaleimide, N, N'-4,4-diphenyl ether bismaleimide, N, N'-4,4-diphenylsulfone bis Maleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl-3,4- (4-maleimidophenoxy) phenyl] propane, 1,1- Bis [4- (4-maleimidophenoxy) phenyl] decane, 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) phenoxy] -2-cyclohexylbenzene, 2,2-bis [4- ( 4-maleimidophenoxy) phenyl] hexafluoropropane and the like, and may be used alone or in admixture of two or more.

[Carboxylic acid hydrazide]
Examples of the carboxylic acid hydrazide include various compounds including succinic acid hydrazide and adipic acid hydrazide.

[Β-Hydroxyalkylamide group-containing compound]
Examples of the β-hydroxyalkylamide group-containing compound include various compounds including N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Ems Chemie). .

[Block isocyanate]
The blocked isocyanate is not particularly limited as long as it is an isocyanate group-containing compound in which an isocyanate group is protected with ε-caprolactam, MEK oxime, or the like. Specifically, the above-mentioned diisocyanate compound, trimethylolpropane adduct of the diisocyanate compound, a burette reacted with water, and a trimer having an isocyanurate ring are converted into ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol. And the like blocked.

[Amine compound]
As the amine compound, any compound having at least one primary amino group, secondary amino group or tertiary amino group in the molecule may be used.
Tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, and salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] Imidazoles such as ethyl-S-triazine, 2-ethyl-4-methylimidazole tetraphenylborate, and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, , 8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like.

[Phosphine compound]
Examples of the phosphine compound include phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, and tris (cyanoethyl) phosphine;
Examples thereof include phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, and methyltricyanoethylphosphonium tetraphenylborate.

  Only one type of these thermosetting aids may be used, or two or more types may be used in combination. The amount of the thermosetting aid used may be determined in consideration of the cured material properties of the adhesive composition, and is not particularly limited, but is an epoxy having at least one nitrogen atom in the molecule of the present invention. The amount is preferably in the range of 1 to 50 parts by weight and more preferably in the range of 10 to 50 parts by weight with respect to 100 parts by weight of the compound (A). Thereby, it is possible to adjust the curing rate, the crosslinking density, and the cohesive force of the adhesive composition of the present invention, and various physical properties can be further improved. When the amount of the thermosetting aid used is close to 10 parts by weight, an epoxy compound (A) having at least one nitrogen atom in the molecule and a carboxyl group-containing polymer compound (B) without impairing desired physical properties. ), And when the amount used is close to 50 parts by weight, the epoxy compound (A) having at least one nitrogen atom in the molecule and the carboxyl group-containing polymer compound (B) ), The cross-linking density of the coating film can be made denser, so that the electrical insulation and heat resistance can be further improved.

<Other additives>
In addition to the above, the adhesive composition of the present invention further includes optional components as long as the purpose is not impaired. Solvent, dye, pigment, antioxidant, polymerization inhibitor, antifoaming agent, leveling agent, ion scavenger, moisturizing agent An agent, a viscosity modifier, an antiseptic, an antibacterial agent, an antistatic agent, an antiblocking agent, an ultraviolet absorber, an infrared absorber, an electromagnetic shielding agent, and the like can be added.

  Examples of the antifoaming agent and leveling agent include silicone-based, hydrocarbon-based, and acrylic resin-based compounds.

  As the ion scavenger, inorganic or organic ion exchangers are preferably used. Specifically, inorganic ion exchangers Exe from Toa Gosei Co., Ltd. and ion exchange resin diion from Mitsubishi Chemical Corporation are used, but are not limited to these as long as they have ion collection ability.

  The adhesive composition of the present invention comprises an epoxy compound (A) having at least one nitrogen atom in the molecule and a carboxyl group-containing polymer compound (B) and, if necessary, the thermosetting aid or additive. It is obtained by mixing arbitrary components.

<Adhesive sheet>
The adhesive sheet comprising the adhesive composition of the present invention is prepared on at least one surface of the release substrate by a conventionally known method, for example, comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing. It is produced by applying an adhesive composition by flexographic printing, screen printing, dip coating, spray coating, spin coating or the like and then drying at 40 to 150 ° C. The dry film thickness of the adhesive layer is preferably 5 μm to 500 μm, more preferably 10 μm to 100 μm from the viewpoint of ease of handling in order to exhibit sufficient adhesion and solder heat resistance.

<Insulating film with adhesive sheet>
The insulating film with an adhesive sheet made of the adhesive composition of the present invention is produced by applying the adhesive composition to at least one surface of the insulating film by the above-described method and then usually drying at 40 to 150 ° C. Examples of the insulating film used in the present invention include, but are not limited to, those made of polyimide, polyester, polyphenylene sulfide, polyether sulfone, polycarbonate, polyether ether ketone, polyarylate, and the like. . The insulating film with an adhesive sheet of the present invention can be used as a coverlay film similar to that in the prior art, and the film thickness of the insulating film with an adhesive sheet at this time is, for example, in the range of 10 μm to 500 μm. Things can be mentioned. The surface of the insulating film to which the adhesive composition is applied may be subjected to surface treatment such as corona discharge treatment, constant temperature plasma treatment, physical surface roughening, etc., if necessary.

<Printed wiring board>
Next, the manufacturing method of the printed wiring board using the adhesive composition of this invention is demonstrated. The adhesive composition of the present invention is overlaid on a flexible and insulating plastic film such as polyester or polyimide so as to cover the conductive pattern of the flexible printed wiring board in which the conductive pattern is formed by printing technology, and heated and pressurized. Thus, the adhesive composition can be cured to obtain a flexible printed wiring board provided with a protective layer.

  As a method for providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper-clad plate in which a copper foil is provided on a base film with or without an adhesive layer. Expose the conductive circuit from the copper foil by exposing it through a mask film with a pattern, curing only the exposed area, then removing the unexposed area of the copper foil by etching, and then peeling off the remaining resist layer. Can be formed. Alternatively, only a necessary circuit may be provided on the base film by means such as sputtering or plating.

  Moreover, by sandwiching a curable adhesive layer formed by peeling the peelable substrate from the adhesive composition of the present invention between a plurality of flexible printed wirings, the adhesive composition is cured by heating and pressing, A multilayer flexible printed wiring board can also be obtained. Furthermore, copper foil and a heat resistant insulating flexible base material can also be laminated | stacked using the adhesive composition of this invention.

  According to the present invention, an adhesive composition having particularly excellent dielectric properties in addition to the high flexibility, adhesiveness, high electrical insulation, thermal stability and the like that have been conventionally required has been obtained. These can be suitably used as coverlay films, electromagnetic wave shielding adhesives, interlayer electrical insulation materials for printed wiring boards, optical waveguides and the like as adhesives and coating agents around printed wiring boards through which high-frequency electrical signals propagate. .

  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.

<Measurement of acid value>
About 1 g of the purified product was precisely weighed and completely dissolved in 100 ml of THF, and then a 0.1 wt% alcoholic phenolphthalein solution was added and titrated with a 0.1 N alcoholic potassium hydroxide solution. The end point of titration was when the red discoloration of phenolphthalein did not disappear for 30 seconds. The acid value was determined by the following formula. Moreover, the acid value was made into the numerical value of the dry state of resin (unit: KOHmg / g).
Acid value (KOHmg / g) = (5.611 × a × F) / S
However, S: Amount of sample purified product (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

[Synthesis Example 1 of Acrylic Resin]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 100 parts of MEK was placed and heated to 80 ° C. while injecting nitrogen gas into the container. A mixture of 45 parts of ethylhexyl, 55 parts of butyl acrylate, 5 parts of acrylic acid and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of 2,2′-azobisisobutyronitrile dissolved in 50 parts of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour. A group-containing acrylic resin solution was obtained. The weight average molecular weight was 39,000, and the acid value was 37 KOHmg / g.

[Synthesis Example 2 of Acrylic Resin]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 100 parts of MEK was placed and heated to 80 ° C. while injecting nitrogen gas into the container. A mixture of 20 parts of ethylhexyl, 78 parts of ethyl acrylate, 2 parts of acrylic acid and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of 2,2′-azobisisobutyronitrile dissolved in 50 parts of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour. A group-containing acrylic resin solution was obtained. The weight average molecular weight was 42,000, and the acid value was 16 KOHmg / g.

[Synthesis example 1 of urethane resin]
Mw = 2000 obtained from adipic acid and 3-methyl-1,5-pentanediol and 1,6-hexanediol in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer. 313 parts of polyester diol, 11 parts of dimethylolbutanoic acid, 51 parts of isophorone diisocyanate, and 300 parts of toluene were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 0.16 part of dibutyltin dilaurate was added thereto as a catalyst and reacted at 100 ° C. for 3 hours to obtain a carboxyl group-containing urethane resin solution. The weight average molecular weight was 200,000, and the acid value was 12 KOHmg / g.

[Synthesis example 2 of urethane resin]
Polycarbonate diol based on 1,4-cyclohexanedimethanol (“ETERRNACOLL UC100” manufactured by Ube Industries, Ltd.) 96.8 is added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, and thermometer. Parts, 6.87 parts of dimethylol butanoic acid, 41.9 parts of isophorone diisocyanate, and 70.0 parts of toluene were reacted at 90 ° C. for 4 hours in a nitrogen atmosphere, and 250 parts of toluene was added thereto to contain isocyanate groups. A urethane prepolymer solution was then obtained, and the above isocyanate was then added to a mixture of 6.26 parts isophoronediamine, 0.61 part di-n-butylamine, 112.5 parts 2-propanol, and 184.5 parts toluene. 418.999 parts of a group-containing urethane prepolymer solution was added and reacted at 85 ° C. for 4 hours. .0 parts, was diluted with 2-propanol 27.0 parts, to obtain a carboxyl group-containing urethane urea resin solution. The weight average molecular weight 110,000, acid value was 11KOHmg / g.

[Synthesis Example 1 of Ester Resin]
1,4-cyclohexanedimethanol-based polycarbonate diol ("ETERRNACOLL UC100" manufactured by Ube Industries, Ltd.) 106.6 was added to a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer. Part, 33.4 parts of tetrahydrophthalic anhydride and 70 parts of toluene were heated to 110 ° C. with stirring under a nitrogen stream and reacted for 3 hours. Thereafter, after cooling to 40 ° C., 35.2 parts of a bisphenol A type epoxy resin (“YD-8125” manufactured by Nippon Steel Chemical Co., Ltd.), 10 parts of toluene, and 1 part of triphenylphosphine as a catalyst were added to form 110 ° C. The temperature was raised to 8 hours and reacted for 8 hours. After cooling to room temperature, 6.7 parts of tetrahydrophthalic anhydride and 90 parts of MEK were added and reacted at 80 ° C. for 3 hours to obtain a carboxyl group-containing ester resin solution. The weight average molecular weight was 31,000, and the acid value was 20 KOHmg / g.

[Synthesis Example 2 of Ester Resin]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 203.7 parts of an aromatic polyester diol (“P2020” manufactured by Kuraray Co., Ltd.), tetrahydrophthalic anhydride 30. 4 parts and 70 parts of toluene were charged, and the temperature was raised to 110 ° C. with stirring under a nitrogen stream, and the reaction was performed for 3 hours. Then, after cooling to 40 ° C., 31.1 parts of bisphenol A type epoxy resin (“YD-8125” manufactured by Nippon Steel Chemical Co., Ltd.), 10 parts of toluene, and 1 part of triphenylphosphine as a catalyst were added to form 110 ° C. The temperature was raised to 8 hours and reacted for 8 hours. After cooling to room temperature, 11.6 parts of tetrahydrophthalic anhydride and 90 parts of MEK were added and reacted at 80 ° C. for 3 hours to obtain a carboxyl group-containing ester resin solution. The weight average molecular weight was 34,000, and the acid value was 24 KOHmg / g.

[Synthesis Example 1 of Phenoxy Resin]
A 4-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, bisphenol A 91.3 parts, bisphenol A epoxy resin (“YD-8125” manufactured by Nippon Steel Chemical Co., Ltd.) 80.5 parts, 82.5 parts of polyethylene glycol type epoxy resin (“EX830” manufactured by Nagase ChemteX Corporation), 130 parts of toluene, 2 parts of triphenylphosphine as catalyst, and 2 parts of N, N-dimethylbenzylamine are charged. The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours. After cooling to room temperature, 18.1 parts of tetrahydrophthalic anhydride and 150 parts of MEK were added and reacted at 80 ° C. for 3 hours to obtain a carboxyl group-containing phenoxy resin solution. The weight average molecular weight was 20,000, and the acid value was 25 KOHmg / g.

[Synthesis Example 2 of Phenoxy Resin]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, bisphenol F 80.1 parts, bisphenol A type epoxy resin (“YD-8125” manufactured by Nippon Steel Chemical Co., Ltd.) 53.7 parts, 123.8 parts of polyethylene glycol type epoxy resin (“EX830” manufactured by Nagase ChemteX Corporation), 130 parts of toluene, 2 parts of triphenylphosphine and 2 parts of N, N-dimethylbenzylamine as a catalyst The mixture was heated to 110 ° C. with stirring under a nitrogen stream and reacted for 8 hours. After cooling to room temperature, 24.2 parts of tetrahydrophthalic anhydride and 150 parts of MEK were added and reacted at 80 ° C. for 3 hours to obtain a carboxyl group-containing phenoxy resin solution. The weight average molecular weight was 25,000, and the acid value was 32 KOHmg / g.

[Synthesis Example 1 of Amide Resin]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 115.7 parts of dimer acid (“Priol 1009” manufactured by Croda Japan Co., Ltd.), Dimeramine (Croda Japan Co., Ltd.) ) "Preamine 1074")) 9.8 parts, norbornanediamine 25.2 parts, and ion-exchanged water 100 parts were charged and stirred until the temperature of the exotherm became constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reaches 230 ° C., the reaction is continued for 3 hours at the same temperature, kept under a vacuum of about 2 kPa for 1 hour, the temperature is lowered, diluted with 75 parts of toluene and 75 parts of 2-propanol, A containing amide resin was obtained. The weight average molecular weight was 24,000, and the acid value was 15 KOHmg / g.

[Imide resin synthesis example 1]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 20.2 parts of sebacic acid, 21.8 parts of pyromellitic anhydride, dimeramine (manufactured by Croda Japan Co., Ltd., “ 97.6 parts of preamine 1074 ") were charged and stirred until the temperature of the exotherm was constant. When the temperature was stabilized, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. after 30 minutes, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. . When the temperature reaches 230 ° C., the reaction is continued for 3 hours at the same temperature, kept under a vacuum of about 2 kPa for 1 hour, the temperature is lowered, diluted with 75 parts of toluene and 75 parts of 2-propanol, A containing imide resin was obtained. The weight average molecular weight was 35,000 and the acid value was 22 KOHmg / g.

Example 1
As an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule, 100 parts of jER604 (manufactured by Mitsubishi Chemical Corporation, polyfunctional glycidylamine compound), a carboxyl group-containing polymer compound (B), 1000 parts of resin solid content obtained in Synthesis Example 1 of acrylic resin and 10 parts of Chemitite PZ (manufactured by Nippon Shokubai Co., Ltd., polyfunctional aziridine compound) as a heat curing aid were mixed to obtain an adhesive composition. This adhesive composition was uniformly applied onto a release-treated polyester film so that the film thickness after drying was 30 μm and dried to provide an adhesive layer. Next, another release-treated polyester film was laminated on the adhesive layer side to obtain an adhesive sheet with a double-sided protective film.

(Examples 2 to 30, Comparative Examples 1 to 10)
Except having changed the raw material of Example 1 into the raw material described in Table 1, it carried out similarly to Example 1 and created the adhesive sheet.

(Example 31)
As an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule, 100 parts of GAN (manufactured by Mitsubishi Gas Chemical Co., Ltd., bifunctional glycidylamine compound), a carboxyl group-containing polymer compound (B) Resin solid content obtained in Synthesis Example 1 of ester resin 2000 parts, Filler (C) as KTL-500F (manufactured by Kitamura Co., Ltd., polytetrafluoroethylene powder), and thermosetting aid Ep1031s (Mitsubishi) 50 parts of Chemical Co., Ltd., polyfunctional epoxy compound) was mixed to obtain an adhesive composition. This adhesive composition was uniformly applied onto a release-treated polyester film so that the film thickness after drying was 30 μm and dried to provide an adhesive layer. Next, another release-treated polyester film was laminated on the adhesive layer side to obtain an adhesive sheet with a double-sided protective film.

(Examples 32-40, Comparative Examples 11-15)
Except having changed the raw material of Example 31 into the raw material described in Table 1, it carried out similarly to Example 31 and created the adhesive sheet.

jER604: Mitsubishi Chemical Corporation, polyfunctional glycidylamine compound jER630: Mitsubishi Chemical Corporation, polyfunctional glycidylamine compound TETRAD-C: Mitsubishi Gas Chemical Co., Ltd., multifunctional glycidylamine compound GAN: Nippon Kayaku Bifunctional glycidylamine compound GOT manufactured by Nippon Kayaku Co., Ltd. Bifunctional glycidylamine compound KTL-500F: manufactured by Kitamura Co., Ltd., polytetrafluoroethylene powder SS50F: manufactured by Tosoh Silica Co., Ltd., hydrophobic Silica filler OP935: Clariant Japan Co., Ltd., aluminum phosphinate compound Ep1031s: Mitsubishi Chemical Corporation, polyfunctional aromatic epoxy compound jER806: Mitsubishi Chemical Corporation, bisphenol F type epoxy compound Chemitite PZ: Nippon Shokubai Co., Ltd., polyfunctional aziridine compound D2131: DIC (Ltd.), phenol novolak resin CARBODILITE V07: Nisshinbo Co., polycarbodiimide compound

<Evaluation>
With respect to the adhesive sheets obtained in the examples and comparative examples, the solder bath resistance and post-solder adhesive strength were evaluated by the following methods as indices of dielectric properties, flexibility, adhesion, electrical insulation, and thermal stability. The evaluation results are shown in Tables 2 and 3.

(1) Dielectric constant After removing the protective film on one side of the adhesive sheet with the double-sided protective film prepared in Examples and Comparative Examples, vacuum-laminating the adhesive sheets to produce a test piece having a thickness of 1 mm, A test piece for evaluation was prepared by thermosetting for 1 hour under the condition of 1.0 MPa. About this test piece, the dielectric constant and dielectric loss tangent in the measurement temperature of 23 degreeC and the measurement frequency of 1 GHz were calculated | required with the coaxial resonator method using the dielectric constant measuring apparatus by AET Co., Ltd.
◎ ・ ・ ・ Dielectric constant is 2.8 or less ○ ・ ・ ・ Dielectric constant is larger than 2.8 and 3.0 or less Δ ・ ・ ・ Dielectric constant is larger than 3.0 and is 3.2 or less × ... Dielectric constant greater than 3.2

(2) Dielectric loss tangent: The dielectric loss tangent is 0.02 or less. O: The dielectric loss tangent is larger than 0.02 and smaller than 0.03. Δ: The dielectric loss tangent is larger than 0.03. Less than 05 × ・ ・ ・ Dielectric loss tangent is larger than 0.05

(3) Flexibility The adhesive composition is uniformly coated on a 75 μm thick polyimide film [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.] so that the film thickness after drying is 30 μm. The test piece was further heat-cured at 160 ° C. for 1 hour to prepare a test piece for evaluation. The test specimen for evaluation was bent 180 degrees, and the same part was bent 180 degrees on the opposite side. The state of the coating film at that time was judged according to the following criteria.
○ ・ ・ ・ No cracks are observed on the film surface △ ・ ・ ・ Slight cracks are observed on the film surface × ・ ・ ・ The film is cracked, and cracks are clearly seen on the film surface

(4) Adhesiveness An adhesive sheet having a size of 65 mm × 65 mm, from which the protective film on one side of the adhesive sheet with a double-sided protective film prepared in Examples and Comparative Examples has been removed, is a polyimide film [Toray Dupont with a thickness of 75 μm. It was sandwiched between “Kapton 300H” manufactured by Co., Ltd.] and a copper-clad laminate having a thickness of 45 μm, laminated at 80 ° C., and then subjected to pressure bonding treatment at 160 ° C. and 1.0 MPa for 5 minutes. Further, this test piece was heat-cured at 160 ° C. for 1 hour to prepare an evaluation test piece. This test piece was cut into a width of 10 mm and a length of 65 mm, and a T peel peel test was performed at an elongation rate of 300 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%, and the adhesive strength (N / cm) was measured. This test evaluates the adhesive strength of the adhesive layer when used at room temperature, and the results were judged according to the following criteria.
◎ ・ ・ ・ Adhesive strength is 15 (N / cm) or more ○ ・ ・ ・ Adhesive strength is 10 (N / cm) or more and less than 15 (N / cm) △ ・ ・ ・ Adhesive strength is 5 (N / cm) cm) or more and less than 10 (N / cm).
X: Adhesive strength is less than 5 (N / cm).

(5) Electrical insulation The adhesive sheet with a size of 65 mm × 65 mm, from which the protective film on one side of the adhesive sheet with a double-sided protective film prepared in Examples and Comparative Examples was removed, is a polyimide film [Toray “Kapton 100H” manufactured by DuPont Co., Ltd.] and a printed circuit board (copper pattern width / space width = 50 μm / 50 μm) in which a copper circuit is formed on polyimide, and laminated at 80 ° C. Subsequently, pressure bonding was performed for 5 minutes at 160 ° C. and 1.0 MPa. Further, this test piece was heat-cured at 160 ° C. for 1 hour to prepare an evaluation test piece. A DC voltage of 50 V was continuously applied to the conductor circuit of this test piece for 100 hours in an atmosphere of 130 ° C. and 85% relative humidity, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are as follows.
◎ ・ ・ ・ Insulation resistance value is 10 ⁸ Ω or more ○ ・ ・ ・ Insulation resistance value is 10 ⁷ or more and less than 10 ⁸ Ω △ ・ ・ ・ Insulation resistance value is 10 ⁶ or more and less than 10 ⁷ Ω × ・ ・ ・Insulation resistance value is less than 10 ⁶ Ω

(6) Resistance to Solder Bath Similar to the above (4), a test piece cut out to a width of 10 mm and a length of 65 mm was floated for 1 minute by bringing the polyimide film surface into contact with molten solder at 260 ° C. Thereafter, the appearance of the test piece 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 with the appearance. Those with good heat resistance have poor heat resistance, whereas the appearance does not change before and after soldering. Things are subject to foaming and peeling after soldering. These evaluation results were judged according to the following criteria.
◎ ・ ・ ・ No change in appearance ○ ・ ・ ・ Slight foaming is observed △ ・ ・ ・ Foaming is observed × ・ ・ ・ Strong foaming or peeling is observed

(7) Adhesiveness after soldering For the test piece after the evaluation of solder bath resistance in (6) above, the adhesive strength was measured by the same method as in (4) above, and the adhesive strength before soldering and the adhesive strength after soldering. And compared. This test is to evaluate the thermal stability of the adhesive layer at the time of solder contact by the change in the adhesive strength before and after the soldering treatment, and the one having good heat resistance does not change the adhesive strength before and after the soldering treatment. On the other hand, those having poor heat resistance have a marked decrease in adhesive strength after soldering. These evaluation results were judged according to the following criteria.
◎ ・ ・ ・ Adhesive strength does not change at all ○ ・ ・ ・ Adhesive strength hardly changes △ ・ ・ ・ Adhesive strength slightly decreases × ・ ・ ・ Adhesive strength decreases remarkably

(8) Flame Retardant A 65 mm × 65 mm adhesive sheet obtained by removing the protective film on one side of the double-sided protective film-attached adhesive sheet prepared in Examples 31-40, and a polyimide film having a thickness of 12.5 μm [ A sample for flame retardancy test was obtained by pressure bonding to “Kapton 50H” manufactured by Toray DuPont Co., Ltd. under the conditions of 150 ° C., 1 MPa, and 30 min. Flame retardancy was evaluated based on whether UL94 standard V-0 and VTM-0 grades could be achieved.
A: UL94 standard V-0 grade can be achieved.
A: UL94 standard VTM-0 grade can be achieved.
X: UL94 standard VTM-0 grade cannot be achieved.

As can be seen from Examples and Comparative Examples in Tables 2 and 3, Comparative Examples 1 to 10 do not use an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule, The rate and dielectric loss tangent deteriorated significantly. On the other hand, in Examples 1-30, since the epoxy compound (A) which has at least 1 or more tertiary nitrogen atom in a molecule | numerator was used, it is calculated | required conventionally in the adhesive agent and coating agent which are used for a printed wiring board. All of the required adhesives and coatings around printed circuit boards that can improve the dielectric properties without sacrificing flexibility, adhesion, high electrical insulation, and thermal stability. Good results with a good balance in physical properties were obtained. These have high reactivity, which is a characteristic characteristic of an epoxy compound having a tertiary nitrogen atom, so that the reaction rate under a predetermined curing condition can be increased, the crosslinking density of the cured product is improved, and a high elastic modulus is obtained. Therefore, it can be considered that the result is that the water absorption rate that affects the dielectric characteristics can be suppressed. In addition, since nitrogen atoms can take various coordination forms, it is presumed that they strongly support adhesion between metals and organic compounds, and are excellent in terms of metal adhesion including copper. It is considered that the effect was exhibited and good results were shown in electrical insulation and post-solder adhesion.
In addition, Examples 31 to 40 were able to improve electrical insulation and heat resistance by adding the filler (C), and furthermore, good results were stably obtained in the flame retardancy test.

Claims (8)

  An adhesive composition comprising an epoxy compound (A) having at least one tertiary nitrogen atom in the molecule and a carboxyl group-containing polymer compound (B).   2. The carboxyl group-containing polymer compound (B) is at least one resin selected from the group consisting of acrylic resins, urethane resins, ester resins, phenoxy resins, amide resins, and imide resins. Adhesive composition.   The adhesive composition according to claim 1 or 2, wherein the carboxyl group-containing polymer compound (B) has an acid value of 1 to 100 KOHmg / g.   The weight average molecular weight of a carboxyl group-containing high molecular compound (B) is 5000-500000, The adhesive composition in any one of Claims 1-3 characterized by the above-mentioned.   Filler (C) is contained, The adhesive composition in any one of Claims 1-4 characterized by the above-mentioned.   A cured product obtained by curing the adhesive composition according to any one of claims 1 to 5 by heating, having a frequency of 1 GHz, a dielectric constant of 3.0 or less, and a dielectric loss tangent of 0.03 or less.   An adhesive sheet comprising a layer made of the cured product according to claim 6.   A printed wiring board comprising a layer made of the cured product according to claim 6.