WO2022085563A1

WO2022085563A1 - Resin composition, bonding film, laminate with resin composition layer, laminate, and electromagnetic wave shield film

Info

Publication number: WO2022085563A1
Application number: PCT/JP2021/038077
Authority: WO
Inventors: 雅弘鳥居; 勝安藤; 祐弥沖村; 真平川
Original assignee: 東亞合成株式会社
Priority date: 2020-10-23
Filing date: 2021-10-14
Publication date: 2022-04-28
Also published as: KR20230113299A; CN116390855A; JPWO2022085563A1; TW202222977A

Abstract

A resin composition comprising a polyester-polyurethane resin (A) and an epoxy resin (B), in which an isocyante component constituting the polyester-polyurethane resin (A) comprises an isocynate compound that has a hydrocarbon group having 8 to 14 carbon atoms; and a bonding film, a laminate with a resin composition layer, a laminate, or an electromagnetic wave shield film, in which the resin composition is used.

Description

Resin composition, bonding film, laminate with resin composition layer, laminate, and electromagnetic wave shielding film

INDUSTRIAL APPLICABILITY According to the present invention, a printed wiring board, particularly a flexible printed wiring board or a build-up method multi-layer printing, which has high adhesive strength to a polyimide film or metal, has heat resistance and moisture heat resistance of a cured product, and has excellent liquid stability and workability. The present invention relates to a polyester polyurethane resin composition as an effective member for manufacturing a wiring board. Further, it has a bonding film in which the resin composition is attached to a release film, a laminate with a resin composition layer in which the resin composition is attached to a base film, and a layer formed by curing the resin composition. The present invention relates to an electromagnetic wave shielding film that is attached to a laminate, a flexible printed wiring board, or the like and is suitably used for shielding electromagnetic noise generated from an electric circuit.

Flexible printed wiring boards can be mounted three-dimensionally and at high density even in a limited space, so their applications are expanding. In recent years, along with the miniaturization and weight reduction of electronic devices, related products of flexible printed wiring boards have been diversified, and the demand for them is increasing. As such related products, a flexible copper-clad laminate in which a copper foil is bonded to a polyimide film, a flexible printed wiring board in which an electronic circuit is formed on a flexible copper-clad laminate, and a flexible printed wiring board and a reinforcing plate are bonded. There are flexible printed wiring boards with reinforcing plates, flexible copper-clad laminates, multi-layer boards made by stacking and joining flexible printed wiring boards, and for example, when manufacturing flexible copper-clad laminates, the polyimide film and copper foil are bonded together. For this purpose, an adhesive is usually used.

As a conventional adhesive composition or a conventional laminated body, the methods described in Patent Documents 1 to 3 are known.
Patent Document 1 describes (A) a solvent-soluble polyamide resin solid at 25 ° C., (B) a phenoxy resin, (C) an epoxy resin containing no halogen atom, and (D) a structure represented by the following general formula (1). The epoxy resin (C) is an epoxy resin having three or more epoxy groups in one molecule, and the content of the phenoxy resin (B) is the polyamide resin (C). A) It is 100 to 450 parts by mass with respect to 100 parts by mass, and the content of the epoxy resin (C) is 1 to 450 parts by mass with respect to the total of 100 parts by mass of the polyamide resin (A) and the phenoxy resin (B). It is 60 parts by mass, and the content of the phosphorus-based flame retardant (D) is 5 to 100 parts by mass with respect to a total of 100 parts by mass of the polyamide resin (A) and the phenoxy resin (B). A halogen-free flame-retardant adhesive composition is described.

Further, Patent Document 2 contains two or more carboxyl groups in the molecule, has a number average molecular weight of 5,000 to 100,000, and has a molecular weight of 1,500 to 10,000 per carboxyl group. It contains a polyester polymer (a), an epoxy resin (b) containing two or more epoxy groups in the molecule, and an epoxy resin curing accelerator (c), and retains thermoplasticity at 5 ° C. for a period of 5 months or more. A laminate characterized by having a curable resin composition laminated on at least one surface of a polyimide film, a polyester film, or a metal foil, and a curable resin composition of the laminate are cured. A laminate laminated on a metal foil (including a metal circuit) is described.

Further, Patent Document 3 contains a carboxyl group, has an acid value (unit: equivalent / ¹⁰⁶ g) of 100 or more and 1000 or less, and has a number average molecular weight of 5.0 × 10 ³ or more and 1.0 × 10 ⁵ . It contains a polyurethane resin (a) having a glass transition temperature of −10 ° C. or higher and 70 ° C. or lower, an epoxy resin (b) containing a nitrogen atom, and an epoxy resin (c) having a dicyclopentadiene skeleton. Described is a resin composition for an adhesive in which the blending ratio of the resin (b) is 0.1% by mass or more and 20% by mass or less of the entire epoxy resin contained in the resin composition.

Japanese Patent No. 5846290 Japanese Unexamined Patent Publication No. 2005-125724 Japanese Unexamined Patent Publication No. 2010-84005

The problem to be solved by the present invention is that the obtained cured product is stored in a high temperature and high humidity environment (85 ° C. 85% RH) for a long period of time (1,000 hours) and in a cold cycle test (for example, −40 ° C./125). It is an object of the present invention to provide a resin composition having excellent conductivity regardless of which test is performed after 1,000 cycles of ° C.).
Another problem to be solved by the present invention is to provide a bonding film using the resin composition, a laminate with a resin composition layer, a laminate, or an electromagnetic wave shielding film.

The means for solving the above-mentioned problems include the following aspects.
<1> A resin containing a polyester polyurethane resin (A) and an epoxy resin (B), and the diisocyanate component constituting the polyester polyurethane resin (A) contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms. Composition.
<2> The resin composition according to <1>, which further contains a resin (C) having a carboxy group or a carboxylic acid anhydride structure.
<3> The resin composition according to <1> or <2>, wherein the polyester polyurethane resin (A) has a molecular weight of 200 to 8,000 per urethane bond.
<4> The polyester polyurethane resin (A), the epoxy resin (B), the resin (C) having a carboxy group or a carboxylic acid anhydride structure in the resin composition, and the imidazole silane compound which may be contained as an optional component ( The content of the polyester polyurethane resin (A) is 10% by mass to 90% by mass with respect to the total amount of D), and the content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is The resin composition according to any one of <1> to <3>, which is 5% by mass to 70% by mass.
<5> The resin composition according to any one of <1> to <4>, which further contains the inorganic filler (E).
<6> The resin composition according to any one of <1> to <5>, which further contains an organic filler (F).
<7> The resin composition according to any one of <1> to <6>, wherein the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms has an alicyclic structure.
<8> The resin composition according to any one of <1> to <7>, wherein the diol component constituting the polyester polyurethane resin (A) contains a diol compound having a hydrocarbon group having 5 to 32 carbon atoms.
<9> The resin composition according to <8>, wherein the diol compound having a hydrocarbon group having 5 to 32 carbon atoms contains a diol compound having an alicyclic structure or two or more side chains.
<10> The resin composition according to any one of <1> to <9>, wherein the polyester polyurethane resin (A) contains a polyester polyurethane resin having a polyester structure having a number average molecular weight of 8,000 to 30,000. ..
<11> The resin composition according to any one of <1> to <10>, wherein the polyester polyurethane resin (A) has a number average molecular weight of 10,000 to 80,000.
<12> The resin composition according to any one of <1> to <11>, wherein the polyester polyurethane resin (A) has an acid value of 0.1 mgKOH / g to 20 mgKOH / g.
<13> The resin composition according to any one of <1> to <12>, wherein the polyester polyurethane resin (A) has a glass transition temperature of 30 ° C to 150 ° C.
<14> The resin according to any one of <1> to <13>, wherein the content of the epoxy resin (B) is 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the polyester polyurethane resin (A). Composition.
<15> The resin composition according to any one of <1> to <14>, wherein the epoxy resin (B) contains a bisphenol A type epoxy resin and / or a novolak type epoxy resin.
<16> The content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the polyester polyurethane resin (A) <1> to <15>. The resin composition according to any one of the above.
<17> The resin (C) having a carboxy group or a carboxylic acid anhydride structure contains at least one of a polyamide resin having an acid value and a resin having an acid-modified polyolefin structure <1> to <16>. The resin composition according to any one of the above.
<18> The resin composition according to any one of <1> to <17>, which further contains a metal filler (G).
<19> The content of the metal filler (G) is the polyester polyurethane resin (A), the epoxy resin (B), the resin (C) having a carboxy group or a carboxylic acid anhydride structure, and an optional component in the resin composition. The resin composition according to <18>, which is 10 parts by mass to 350 parts by mass with respect to 100 parts by mass of the total amount of the imidazole silane compound (D) which may be contained as.
<20> The resin composition according to <18> or <19>, wherein the metal filler (G) is a conductive filler.
<21> A B-stage-shaped resin composition layer obtained by partially curing the resin composition according to any one of <1> to <20> and contacting at least one surface of the resin composition layer. A bonding film with a release film.
<22> A resin composition layer made of the resin composition according to any one of <1> to <20>, a B-stage resin composition layer obtained by partially curing the resin composition, or a B-stage resin composition layer. A laminate with a resin composition layer comprising a cured layer obtained by curing the resin composition and a base film in contact with at least one surface of the resin composition layer, the B-stage resin composition layer, or the cured layer. ..
<23> A laminate provided with a cured layer obtained by curing the resin composition according to any one of <1> to <20>.
<24> A flexible copper-clad laminate comprising a copper foil, a cured layer obtained by curing the resin composition according to any one of <1> to <20>, and a base material.
<25> A flexible flat cable including a copper wiring, a cured layer obtained by curing the resin composition according to any one of <1> to <20>, and a coating material.
<26> A resin composition layer made of the resin composition according to any one of <1> to <20>, a B-stage resin composition layer obtained by partially curing the resin composition, or a B-stage resin composition layer. An electromagnetic wave shielding film having a cured layer obtained by curing the resin composition.

According to the present invention, the obtained cured product is stored in a high temperature and high humidity environment (85 ° C. 85% RH) for a long period of time (1,000 hours) and in a cold cycle test (for example, -40 ° C./125 ° C.). It is possible to provide a resin composition having excellent conductivity even after 000 cycles).
Further, according to the present invention, it is possible to provide a bonding film using the resin composition, a laminate with a resin composition layer, a laminate, or an electromagnetic wave shielding film.

The description of the constituent elements described below may be based on a representative embodiment of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, "-" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present invention, the amount of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. do.
In the present invention, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
In the present invention, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present invention, the combination of two or more preferred embodiments is a more preferred embodiment.
Further, in the present specification, "(meth) acrylic" means both acrylic and methacrylic, or either of them.
Further, in some of the compounds in the present specification, the hydrocarbon chain may be described by a simplified structural formula omitting the symbols of carbon (C) and hydrogen (H).
Hereinafter, the contents of the present invention will be described in detail.

(Resin composition)
The resin composition of the present invention contains a polyester polyurethane resin (A) and an epoxy resin (B), and the diisocyanate component constituting the polyester polyurethane resin (A) has a hydrocarbon group having 8 to 14 carbon atoms. Contains diisocyanate compounds.
The resin composition of the present invention can be suitably used as an adhesive composition, more preferably as an adhesive composition for polyimide adhesion or metal adhesion, and an adhesive composition for adhesion between polyimide and metal. It can be particularly preferably used as a product.

The present inventors have found that the obtained cured product does not have sufficient conductivity in a high temperature and high humidity environment and after a cold cycle test.
As a result of diligent studies by the present inventors, the diisocyanate component containing two kinds of resins, the polyester polyurethane resin (A) and the epoxy resin (B) and constituting the polyester polyurethane resin (A), has 8 to 14 carbon atoms. Although the detailed mechanism is unknown due to the inclusion of the diisocyanate compound having a hydrocarbon group, these two resins act synergistically with each other and complement each other to further constitute the polyester polyurethane resin (A). Since the isocyanate component to be formed contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms, the hydrophobicity of the resin is improved and the moisture resistance is improved, so that the obtained cured product is under high temperature and high humidity. It was also found that the resin composition having excellent conductivity can be provided even after the thermal cycle test due to the stress relaxing effect of the resin components of the polyester polyurethane resin (A) and the epoxy resin (B). ..

Further, the resin composition of the present invention contains two types of resins, a polyester polyurethane resin (A) and an epoxy resin (B), and the molecular weight per urethane bond in the polyester polyurethane resin (A) is 200 to 8. The diisocyanate component constituting the polyester polyurethane resin (A) is 000, and contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms, so that it is excellent in flame retardancy, initial and post-solder treatment. Also, it has excellent heat resistance.

Hereinafter, the present invention will be described in detail.
Further, in the present specification, "polyester polyurethane resin (A)" and the like are also referred to as "component (A)" and the like.

<Polyester polyurethane resin (A)>
The resin composition of the present invention contains a polyester polyurethane resin (A), and the diisocyanate component constituting the polyester polyurethane resin (A) contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms.
The polyester polyurethane resin (A) may be a resin having two or more ester bonds and two or more urethane bonds, but is preferably a resin having a polyester chain and two or more urethane bonds.
Further, the polyester polyurethane resin (A) is preferably a resin obtained by at least reacting a polyester polyol, a polyisocyanate, and a chain extender as a raw material thereof, and a polyester polyol, a polyisocyanate, and a diol compound are used. It is more preferable that the resin is at least reacted.

The polyester portion of the polyester polyurethane resin (A) is preferably formed from an acid component and an alcohol component.
As the acid component, a polyvalent carboxylic acid compound is preferable, and a dicarboxylic acid compound is more preferable. Further, as the acid component, a sulfocarboxylic acid compound or the like can also be used. Further, as the acid component, an aromatic acid is preferably mentioned.
As the alcohol component, a polyhydric alcohol compound is preferable, and a diol compound is more preferable.
Further, the polyester portion may be formed of a hydroxycarboxylic acid compound.
When the total amount of the total acid components constituting the polyester portion of the polyester polyurethane resin (A) is 100 mol%, the aromatic acid is 30 among the total acid components from the viewpoint of adhesiveness, heat resistance and moisture heat resistance. It is preferably mol% or more, more preferably 45 mol% or more, and particularly preferably 60 mol% or more.

Examples of aromatic acids include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and 5-hydroxyisophthalic acid. Also, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, sulfoterephthalic acid, their metal salts, and their metals. Aromatic dicarboxylic acid having a sulfonic acid group or a sulfonic acid base such as an ammonium salt of, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4 -Aromatic oxycarboxylic acids such as bis (p-hydroxyphenyl) valeric acid can be mentioned. Among these, from the viewpoint of adhesiveness, the acid component preferably contains terephthalic acid and / or isophthalic acid, and is particularly preferably terephthalic acid and / or isophthalic acid.
Further, the acid component may be a derivative of an acid compound such as an ester at the time of resin synthesis.

Other acid components include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its acid anhydride, succinic acid, and adipic acid. , Azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and other aliphatic dicarboxylic acids can be mentioned.

On the other hand, as the polyhydric alcohol component, an aliphatic diol compound, an alicyclic diol compound, an aromatic-containing diol compound, an ether bond-containing diol compound and the like are preferably mentioned.
Examples of aliphatic diol compounds include ethylene glycol, 1,2-propylene diol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexane. Diol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalate neopentyl glycol ester, dimethylol heptane, 2,2 , 4-trimethyl-1,3-pentanediol and the like.
Examples of alicyclic diol compounds include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecanedimethylol, spiroglycol, hydrogenated bisphenol A, and ethylene of hydrogenated bisphenol A. Examples thereof include an oxide adduct and a propylene oxide adduct.
Examples of aromatic-containing diol compounds include paraxylene glycol, methaxylene glycol, orthoxylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, and ethylene of bisphenol A. Examples thereof include glycols obtained by adding 1 to several mols of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols such as an oxide adduct and a propylene oxide adduct.
Examples of the ether bond-containing diol compound include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, neopentyl glycol propylene oxide adduct, and the like. ..
Among these diols, a diol having a side chain such as neopentyl glycol or 2-butyl-2-ethyl-1,3-propanediol is a phase with an epoxy resin, a carboxy group, a resin having a carboxylic acid anhydride structure, or the like. Preferred for solubility and solution stability reasons.
That is, the diol component constituting the polyester polyurethane resin (A) contains a diol having a side chain from the viewpoint of compatibility with an epoxy resin, a resin having a carboxy group or a carboxylic acid anhydride structure, and solution stability. Is preferable.
Among them, as the chain extender constituting the polyester polyurethane resin (A), from the viewpoint of compatibility with an epoxy resin, a resin having a carboxy group or a carboxylic acid anhydride structure, solution stability, and conductivity, the side It is more preferable to include a diol having a chain. That is, the polyester polyurethane resin (A) is made of a polyester polyol and a poly as raw materials from the viewpoints of compatibility with an epoxy resin, a resin having a carboxy group or a carboxylic acid anhydride structure, solution stability, and conductivity. More preferably, it is a resin obtained by reacting isocyanate with at least a diol having a side chain.
The side chain in the diol having a side chain is preferably an alkyl group, and the number of carbon atoms of the alkyl group may be, for example, 1, 2, 3, 4, or 5. This also applies to the diols having side chains described below.
Examples of the diol having a side chain include neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylol propionic acid.

The polyester polyurethane resin (A) is preferably composed of at least a diol component from the viewpoint of conductivity after the initial stage of the obtained cured product, after soldering, after a long-term reliability test, or after a thermal cycle test.
The diol component constituting the polyester polyurethane resin (A) is a hydrocarbon having 5 to 32 carbon atoms from the viewpoint of conductivity at the initial stage of the obtained cured product, after soldering, after a long-term reliability test or after a thermal cycle test. It is preferable to contain a diol compound having a group, more preferably to contain a diol compound having a hydrocarbon group having 5 to 16 carbon atoms, and particularly preferably to contain a diol compound having a hydrocarbon group having 7 to 12 carbon atoms. ..
The diol compound having a hydrocarbon group having 5 to 32 carbon atoms has an alicyclic structure or two from the viewpoint of conductivity at the initial stage of the obtained cured product, after soldering, after a long-term reliability test or after a thermal cycle test. It is preferable to include a diol compound having the above side chains, more preferably to contain a diol compound having two or more side chains, and particularly preferably to contain a diol compound having two side chains.
Further, the diol compound having a hydrocarbon group having 5 to 32 carbon atoms may be a diol component constituting the polyester moiety or a diol component constituting the polyurethane moiety, but in the initial stage of the obtained cured product, From the viewpoint of conductivity after soldering, after a long-term reliability test, or after a thermal cycle test, the diol component constituting the polyurethane portion is preferable.

Further, a hydroxycarboxylic acid compound having a hydroxy group and a carboxy group in the molecular structure can also be used as a raw material for polyester, and 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenityl alcohol, p. Examples thereof include -hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis (p-hydroxyphenyl) valeric acid and the like.

As a component constituting the polyester portion of the polyester polyurethane resin (A), 0.1 mol% to 5 mol with respect to the total acid component or the total polyhydric alcohol component constituting the polyester portion for the purpose of introducing a branched skeleton as necessary. % Or more trifunctional or higher polycarboxylic acids and / or polyols may be copolymerized. In particular, when a cured layer is obtained by reacting with a curing agent, the introduction of a branched skeleton increases the terminal group concentration (reaction point) of the resin, and a cured layer having a high crosslink density can be obtained. Examples of trifunctional or higher functional polycarboxylic acids include trimellitic acid, trimesic acid, ethylene glycol bis (anhydrotrimericate), glycerol tris (anhydrotrimericate), trimellitic anhydride, and pyromerit anhydride. Acid (PMDA), Oxydiphthalic Acid Dianhydride (ODPA), 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 3,3', 4,4'-diphenyltetracarboxylic acid di. Anhydride (BPDA), 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA), 2, Compounds such as 2'-bis [(dicarboxyphenoxy) phenyl] propane dianhydride (BSAA) can be used. On the other hand, as examples of trifunctional or higher functional polyols, glycerin, trimethylolpropane, trimethylolpropane, pentaerythritol and the like can be used. When a trifunctional or higher functional polycarboxylic acid and / or polyol is used, it is preferably 0.1 mol% to 5 mol%, more preferably 0.1 mol, based on the total acid component or the total polyhydric alcohol component. It is preferable to copolymerize in the range of% to 3 mol%.

About 0.1 mol% to 10 mol% with respect to the total acid component or the total polyhydric alcohol component constituting the polyester portion for the purpose of introducing a carboxy group into the polyester portion of the polyester polyurethane resin (A) if necessary. Acid addition can be performed. When a monocarboxylic acid, a dicarboxylic acid, or a polyfunctional carboxylic acid compound is used for acid addition, the molecular weight is lowered by the ester exchange, so that it is preferable to use an acid anhydride.
The acid anhydrides include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornnedicarboxylic acid anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic dianhydride. (ODPA), 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA), 3,3', 4,4'-diphenyltetracarboxylic acid dianhydride (BPDA), 3,3' , 4,4'-Diphenylsulfonate tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene) diphthalate dianhydride (6FDA), 2,2'-bis [(dicarboxyphenoxy) Phenyl] Compounds such as propane dianhydride (BSAA) can be used.
Acid addition can be performed directly in a bulk state after polycondensation of polyester, or can be added as a solution of polyester. The reaction in the bulk state is fast, but gelation may occur if a large amount of acid is added, and the reaction is at a high temperature, so care must be taken to block oxygen gas and prevent oxidation. be. On the other hand, acid addition in a solution state has a slow reaction, but a large amount of carboxy group can be stably introduced.

The polyurethane portion of the polyester polyurethane resin (A) is composed of at least a diisocyanate component.
Further, the diisocyanate component contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms. Here, the methylene group in the hydrocarbon group may be replaced with a non-reactive bond such as —O—, —S—, —CO—, —COO—, —OCO—. The amount of the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms in the diisocyanate component is usually 70 mol% or more, preferably 90 mol% or more, and may be 100 mol%.
Further, the polyurethane portion of the polyester polyurethane resin (A) may be composed of a monofunctional or trifunctional or higher functional isocyanate component in addition to the diisocyanate component.
The number of carbon atoms of the hydrocarbon group in the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms is 8 from the viewpoint of conductivity after soldering of the obtained cured product, after a long-term reliability test, and after a thermal cycle test. It is preferably ~ 12, and more preferably 8-10.
Further, the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms has an alicyclic structure from the viewpoint of conductivity after soldering of the obtained cured product, after a long-term reliability test, and after a thermal cycle test. Is preferable.

From the viewpoint of adhesiveness, the polyester polyurethane resin (A) preferably has a diisocyanate component in an amount of 5 to 50 molar equivalents with respect to 1 molar equivalent of the polyester portion. In other words, from the viewpoint of adhesiveness, the polyester polyurethane resin (A) preferably has 10 mol to 100 mol equivalents of urethane bonds with respect to 1 mol equivalent of the polyester portion.

The polyisocyanate used for producing the polyester polyurethane resin (A) is one of diisocyanates, its dimer (uretdione), its trimer (isocyanurate, triol adduct, burette), or two of them. The above mixture may be used. For example, as the diisocyanate component, diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylenediocyanate, 1,5-naphthalenediocyanate, 2,6-naphthalenediocyanate, 4,4'-diisocyanate diphenyl ether, m-xyli Examples thereof include range isocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, methylene bis (4-cyclohexyldiisocyanate), isophorone diisocyanate, norbornan diisocyanate, norbornene diisocyanate and the like.
Among them, an aliphatic or alicyclic diisocyanate compound is preferable, and an alicyclic diisocyanate compound is particularly preferable, from the viewpoints of transparency, after soldering of the obtained cured product, after a long-term reliability test, and after a thermal cycle test. .. In addition, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and methylenebis (4-cyclohexyl) are considered from the viewpoint of easy availability and conductivity after the thermal cycle test. Diisocyanate) or norbornane diisocyanate is preferable, and 1,3-bis (isocyanatomethyl) cyclohexane is particularly preferable.

In producing the polyester polyurethane resin (A), a chain extender may be used if necessary.
Examples of the chain extender include diol compounds already described as constituents of the polyester moiety, compounds having one carboxy group and two hydroxy groups such as dimethylolpropionic acid and dimethylolbutanoic acid.
Among them, as the chain extender, a diol compound is preferable from the viewpoint of conductivity, a diol compound having a side chain is more preferable, and a diol compound having a branched chain is particularly preferable.
The diol compound having a side chain is selected from the group consisting of neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid from the viewpoint of conductivity. It is preferable to contain at least one compound, and at least one compound selected from the group consisting of neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylol. It is particularly preferred to include propionic acid.
A polyamino compound may be used as the chain extender, but in one embodiment, the polyester polyurethane resin (A) may preferably contain no urea bond.

The method for producing the polyester polyurethane resin (A) is not particularly limited, and a known method can be used. For example, the polyester polyol, the polyisocyanate, and if necessary, the chain extender may be charged together in the reaction vessel, or may be charged separately. In any case, the ratio of the functional group of the isocyanate group / hydroxy group is preferably 0.9 or more with respect to the total hydroxyl value of the polyester polyol and the chain extender in the system and the total isocyanate group of the polyisocyanate. The reaction is carried out at 1 or less, more preferably 0.98 or more and 1.02 or less, and particularly preferably 1. Further, this reaction can be produced by reacting in the presence or absence of a solvent inert to the isocyanate group. The solvents include ester solvents (ethyl acetate, butyl acetate, ethyl butyrate, etc.), ether solvents (dioxane, tetrahydrofuran, diethyl ether, etc.), ketone solvents (cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc.), aromatic carbonization. Hydrogen-based solvents (benzene, toluene, xylene, etc.) and mixed solvents thereof can be mentioned, but ethyl acetate and methyl ethyl ketone are preferable from the viewpoint of reducing the environmental load. The reaction device is not limited to a reaction can equipped with a stirring device, and a mixing and kneading device such as a kneader or a twin-screw extruder can also be used.

To promote the urethane reaction, catalysts used in ordinary urethane reactions, such as tin-based catalysts (trimethyltin laurate, dimethyltindilaurate, trimethyltinhydroxide, dimethyltindihydroxide, stanas octoate, etc.), lead-based A catalyst (red oleate, red-2-ethylhexoate, etc.), an amine-based catalyst (triethylamine, tributylamine, morpholine, diazabicyclooctane, diazabicycloundecene, etc.) and the like can be used.

The glass transition temperature (Tg) of the polyester portion of the polyester polyurethane resin (A) is preferably 40 ° C. to 150 ° C., preferably 45 ° C. to 120 ° C. from the viewpoint of adhesiveness, conductivity, and heat resistance. More preferably, it is more preferably 50 ° C to 90 ° C, and particularly preferably 60 ° C to 70 ° C.
The glass transition temperature (Tg) of the polyester polyurethane resin (A) is preferably 30 ° C. to 150 ° C., preferably 40 ° C. to 140 ° C. from the viewpoint of adhesiveness, conductivity, and heat resistance. Is more preferable, 50 ° C to 90 ° C is further preferable, and 60 ° C to 70 ° C is particularly preferable.

The number average molecular weight (Mn) of the polyester polyurethane resin (A) is preferably 5,000 to 100,000, preferably 10,000 to 80,000 from the viewpoint of conductivity and heat resistance. More preferably, it is more preferably 20,000 to 60,000, and particularly preferably 25,000 to 50,000.
The values of the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin in the present invention can be obtained by gel permeation chromatography (GPC).

The molecular weight per urethane bond in the polyester polyurethane resin (A) is preferably 200 to 8,000, more preferably 200 to 5,000, from the viewpoint of conductivity and heat resistance. It is more preferably 300 to 2,000, particularly preferably 400 to 1,500, and most preferably 700 to 1,000.
For example, in the polyester polyurethane resin (A), when 40 urethane bonds are present per molecule and the number average molecular weight is 32,000, 32,000/40 = 800, and the molecular weight per urethane bond is 32,000. Is 800. As described above, when the polyester polyurethane resin (A) has X urethane bonds per molecule and the number average molecular weight is Y, the molecular weight per urethane bond in the polyester polyurethane resin (A) is Y /. It becomes X. When calculating from the raw material composition, the number of moles of isocyanate groups reacted with 1 mol of the polyester polyol which is the raw material of the polyester polyurethane resin (A) shall be regarded as "the number of urethane bonds in the polyester polyurethane resin (A)". You can also.

The acid value of the polyester polyurethane resin (A) is preferably 0 mgKOH / g to 50 mgKOH / g, more preferably 0.1 mgKOH / g to 20 mgKOH / g, from the viewpoint of adhesiveness and conductivity. , 0.1 mgKOH / g to 5 mgKOH / g, more preferably 1.0 mgKOH / g to 5.0 mgKOH / g.
The acid value of the polyester polyurethane resin (A) is preferably 20 mgKOH / g or less, and particularly preferably 5.0 mgKOH / g or less, from the viewpoint of heat resistance.
In the method for measuring the acid value of the resin in the present invention, the acid value is determined by neutralizing and titrating the sample with a potassium hydroxide benzyl alcohol solution using a phenolphthalein solution as an indicator.

Among them, the polyurethane polyurethane resin (A) preferably contains a polyester polyurethane resin having a polyester structure having a number average molecular weight of 1,000 to 50,000 from the viewpoints of adhesiveness, conductivity, and heat resistance. It is more preferable to contain a polyester polyurethane resin having a polyester structure having an average molecular weight of 2,000 to 40,000, and further preferably to contain a polyester polyurethane resin having a polyester structure having a number average molecular weight of 3,000 to 30,000. It is particularly preferable to contain a polyester polyurethane resin having a polyester structure having a number average molecular weight of 8,000 to 30,000, and a polyester polyurethane resin having a polyester structure having a number average molecular weight of 15,000 to 30,000 is most preferable.

The resin composition of the present invention may contain the polyester polyurethane resin (A) alone or in combination of two or more.
The content of the polyester polyurethane resin (A) is preferably 5% by mass to 90% by mass, preferably 10% by mass, based on the total solid content of the resin composition from the viewpoint of adhesiveness, conductivity, and heat resistance. It is more preferably% to 80% by mass, further preferably 20% by mass to 75% by mass, and particularly preferably 30% by mass to 70% by mass.
Further, the content of the polyester polyurethane resin (A) is the polyester polyurethane resin (A), the epoxy resin (B) and the carboxy group or the carboxylic acid in the resin composition from the viewpoint of adhesiveness, conductivity and heat resistance. It is preferably 5% by mass to 90% by mass, preferably 10% by mass or more, based on the total amount of the resin (C) having an anhydride structure and the imidazole silane compound (D) which may be contained as an optional component. It is more preferably 90% by mass, further preferably 10% by mass to 70% by mass, and particularly preferably 30% by mass to 70% by mass.

<Epoxy resin (B)>
The resin composition of the present invention contains an epoxy resin (B).
The epoxy resin (B) is a component that imparts adhesiveness, heat resistance in a cured portion after adhesion, and the like. The epoxy resin (B) in the present invention includes not only a polymer compound having an epoxy group but also a low molecular compound having an epoxy group. The number of epoxy groups in the epoxy resin (B) is preferably 2 or more.
Examples of the epoxy resin (B) include orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and succinic acid diglycidyl ester. Glycidyl esters such as adipic acid diglycidyl ester, sebacic acid diglycidyl ester, trimellitic acid triglycidyl ester; diglycidyl ether of bisphenol A and its oligomers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butane. Diol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, sorbitol polyglycidyl ether, polyglycerol poly Glycidyl ethers such as glycidyl ether; novolak type epoxy resins such as phenol novolac epoxy resin, o-cresol novolak epoxy resin, bisphenol A novolak epoxy resin and the like can be mentioned.
In addition, flame-retardant brominated bisphenol A type epoxy resin, phosphorus-containing epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, anthracene type epoxy resin, tertiary butyl catechol type epoxy resin, biphenyl type Epoxy resins, bisphenol S-type epoxy resins and the like can also be used.
Above all, the epoxy resin (B) preferably contains a bisphenol A type epoxy resin and / or a novolak type epoxy resin from the viewpoint of adhesiveness and heat resistance.

In the present invention, the epoxy resin (B) preferably contains a compound having three or more epoxy groups in one molecule in order to exhibit high heat resistance after curing. When such a compound is used, the cross-linking reactivity with the polyester urethane resin (A) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure is compared with the case where an epoxy resin having two epoxy groups is used. Is high, and sufficient heat resistance can be obtained.
The content of the compound having three or more epoxy groups in one molecule of the epoxy resin (B) is preferably 15% by mass or more with respect to the total mass of the epoxy resin (B) from the viewpoint of heat resistance. , 20% by mass or more is more preferable, and 25% by mass or more is particularly preferable.

The resin composition of the present invention may contain the epoxy resin (B) alone or in combination of two or more.
The content of the epoxy resin (B) is the polyester polyurethane resin (A), the epoxy resin (B) and the carboxy group or the carboxylic acid anhydride structure in the resin composition from the viewpoint of adhesiveness, conductivity and heat resistance. It is preferably 1% by mass to 60% by mass, and 2% by mass to 40% by mass, based on the total amount of the resin (C) having the above and the imidazole silane compound (D) which may be contained as an optional component. Is more preferable, and 3% by mass to 20% by mass is particularly preferable.

<Resin (C) having a carboxy group or a carboxylic acid anhydride structure>
The resin composition of the present invention contains a resin (C) having a carboxy group or a carboxylic acid anhydride structure from the viewpoint of conductivity after soldering of the obtained cured product, after a long-term reliability test, and after a thermal cycle test. Is preferable.
The resin (C) having a carboxy group or a carboxylic acid anhydride structure is preferably solid at 25 ° C.
The resin (C) having a carboxy group or a carboxylic acid anhydride structure is not particularly limited as long as it is a resin soluble in an organic solvent described later, and specific examples thereof include polyamide resins, polyolefin resins, and acrylic resins. Examples thereof include copolymers.
Among them, the resin (C) having a carboxy group or a carboxylic acid anhydride structure is a polyamide resin, a polyolefin resin and these from the viewpoint of conductivity after soldering of the obtained cured product, after a long-term reliability test and after a thermal cycle test. It is preferable to contain at least one resin selected from the group consisting of the copolymers of the above, and more preferably to contain at least one of a polyamide resin having an acid value and a resin having an acid-modified polyolefin structure. , It is particularly preferable to contain a polyamide resin having an acid value.

The polyamide resin is a condensed resin obtained by using a dibasic acid and a diamine as a monomer, and is preferably a resin obtained by using two or more kinds of dibasic acids and two or more kinds of diamines. Specific examples of the dibasic acid include adipic acid, sebacic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, dimer acid, isophthalic acid, terephthalic acid, and sodium 5-sulfoisophthalate. Specific examples of the diamine include hexamethylenediamine, heptamethylenediamine, p-diaminomethylcyclohexane, bis (p-aminocyclohexyl) methane, m-xylenediamine, piperazine, and isophorone diamine.
The polyamide resin may be a block copolymer.
It is preferable to include piperazine in the diamine component for the reason of improving the adhesiveness. The content thereof is preferably 1.0 mol% or more, preferably 20 mol, when the total amount of the diamine components constituting the resin (C) having a carboxy group or a carboxylic acid anhydride structure is 100 mol%. It is more preferable to contain% or more.
When the polyamide resin contains a structural unit derived from an aliphatic dibasic acid and a structural unit derived from an alicyclic diamine, the polyamide resin has excellent solubility in a solvent. Further, even if the adhesive composition containing such a polyamide resin is stored for a long period of time, there is almost no increase in viscosity and good adhesiveness to a wide range of adherends is exhibited, which is preferable.

The polyamide resin may appropriately contain structural units derived from aminocarboxylic acids, lactams and the like. Specific examples of the aminocarboxylic acid include 11-aminoundecanoic acid, 12-aminododecanoic acid, 4-aminomethylbenzoic acid, 4-aminomethylcyclohexanecarboxylic acid and the like, and examples of lactams include ε-. Examples thereof include caprolactam, ω-laurolactam, α-pyrrolidone, α-piperidone and the like.

Further, the polyamide resin may appropriately contain a structural unit derived from polyalkylene glycol for the purpose of imparting flexibility. Specific examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, a block or random copolymer of ethylene oxide and tetrahydrofuran, and the like. Can be mentioned. The structural unit derived from the polyalkylene glycol may be contained alone or in two or more kinds.

The polyamide resin is, for example, a nylon 6 / nylon 66 copolymer, a nylon 6 / nylon 6-10 copolymer, a nylon 6 / nylon 66 / nylon 6-10 copolymer, and a nylon 6 / nylon 66 / nylon 11 copolymer. Combined, Nylon 6 / Nylon 66 / Nylon 12 copolymer, Nylon 6 / Nylon 6-10 / Nylon 6-11 copolymer, Nylon 6 / Nylon 11 / Isophorone diamine copolymer, Nylon 6 / Nylon 66 / Nylon 6 It can have a composition such as a copolymer, nylon 6 / nylon 6-10 / nylon 12 copolymer and the like.

Next, the modified polyamide resin is made into an alcohol-soluble nylon resin by adding formaldehyde and alcohol to the unmodified polyamide resin and introducing an alkoxymethyl group into the nitrogen atom constituting the amide bond. .. Specific examples thereof include modified polyamide resins obtained by alkoxymethylating 6-nylon, 66-nylon and the like. The introduction of the N-alkoxymethyl group contributes to a decrease in melting point, an increase in flexibility, and an improvement in solubility in a solvent, and the introduction rate is appropriately set according to the purpose.

The resin having a polyolefin structure is not particularly limited, and examples thereof include polyethylene, polypropylene, polybutene, and copolymers thereof. Further, the resin having a polyolefin structure may be a copolymer of an olefin and another ethylenically unsaturated compound, or may be a block copolymer of a polyolefin and a polycondensation resin. For example, the resin having a polyolefin structure includes a styrene-butadiene copolymer, a styrene-butadiene-styrene block copolymer, a styrene-ethylene / propylene-styrene block copolymer, a styrene-ethylene / butylene-styrene block copolymer, and the like. It may be a styrene resin such as a styrene-isoprene / butadiene-styrene block copolymer or a styrene-isoprene-styrene block copolymer.
Among them, the resin having an acid-modified polyolefin structure is preferably an acid-modified polyolefin resin.

The method for introducing a carboxy group or a carboxylic acid anhydride structure into the polyamide resin and the resin having a polyolefin structure is not particularly limited, but a method for copolymerizing an unsaturated carboxylic acid anhydride or a resin can be used. Examples thereof include a method of modifying with a carboxylic acid anhydride. Specifically, for example, a resin obtained by graft-polymerizing a polyolefin resin such as polypropylene with an unsaturated carboxylic acid anhydride such as maleic anhydride, itaconic anhydride, acrylic acid, or methacrylic acid, or dibasic acid with respect to diamine. A polyamide resin having an acid terminal obtained by excessively reacting the above, a resin obtained by reacting a polyamide resin with a carboxylic acid anhydride, and two or more carboxylic acid anhydrides such as pyromellitic anhydride as a raw material carboxylic acid component. Examples thereof include a polyamide resin using a compound having a structure.

The acid value of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is not particularly limited as long as it has at least a carboxy group or a carboxylic acid anhydride structure, but is not particularly limited, but is 0.1 mgKOH / g to 200 mgKOH / g. It is preferably 1 mgKOH / g to 100 mgKOH / g, more preferably 2 mgKOH / g to 50 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g.

The amine value of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is not particularly limited. Generally, when the amine value of the polyamide resin is high, the reaction between the amino group and the epoxy group is fast, and good curability can be obtained by heat treatment in a short time, but on the other hand, a carboxy group or a carboxylic acid anhydride structure can be obtained. Immediately after mixing the resin (C) and the epoxy resin (B) having the above, the reaction gradually proceeds, and the viscosity of the composition is significantly increased or gelled. Therefore, curability and stability can be achieved at the same time by selecting the amine value of the resin (C) having a carboxy group or a carboxylic acid anhydride structure. The preferred range of the amine value of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is 1 mgKOH / g to 6 mgKOH / g.

The melting point of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is not particularly limited, but is preferably 50 ° C. to 220 ° C. from the viewpoint of solubility in a solvent and heat resistance of the cured product. It is in the range, more preferably in the range of 70 ° C to 180 ° C.

Examples of the solvent for dissolving the resin (C) having a carboxy group or a carboxylic acid anhydride structure include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol and ethylene glycol monomethyl ether. , Alcohols such as propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone; aromatic charcoal such as toluene, xylene, ethylbenzene, mesitylene, etc. Hydrogens; Examples thereof include esters such as methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. These solvents may be used alone or in combination of two or more.

The resin composition of the present invention may contain one kind of resin (C) having a carboxy group or a carboxylic acid anhydride structure alone, or may contain two or more kinds.
The content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is the polyester polyurethane resin (A) and the epoxy resin (B) in the resin composition from the viewpoint of adhesiveness, conductivity, and heat resistance. And 5% by mass to 90% by mass with respect to the total amount of the resin (C) having a carboxy group or a carboxylic acid anhydride structure and the imidazole silane compound (D) which may be contained as an optional component. It is preferably 5% by mass to 70% by mass, more preferably 30% by mass to 50% by mass, and particularly preferably 30% by mass to 50% by mass.
Further, in the resin composition of the present invention, from the viewpoint of adhesiveness, conductivity and heat resistance, the polyester polyurethane resin (A), the epoxy resin (B) and the carboxy group or the carboxylic acid anhydride structure in the resin composition. The content of the polyester polyurethane resin (A) is 10% by mass to 90% by mass with respect to the total amount of the resin (C) having the above and the imidazole silane compound (D) which may be contained as an optional component. The content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is preferably 5% by mass to 70% by mass.

Further, in the resin composition of the present invention, the content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is the polyester polyurethane resin (A) 100 from the viewpoint of adhesiveness, conductivity and heat resistance. It is preferably 1 part by mass to 100 parts by mass, preferably 20 parts by mass to 100 parts by mass, further preferably 50 parts by mass to 95 parts by mass, and 70 parts by mass to 90 parts by mass. It is particularly preferable that it is by mass.
Further, the content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is preferably less than or equal to the content of the polyester polyurethane resin (A) from the viewpoint of adhesiveness, conductivity and heat resistance. , It is more preferable that the content is smaller than the content of the polyester polyurethane resin (A).

The content of the polyester polyurethane resin (A) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure in the resin composition is determined in the resin composition from the viewpoints of adhesiveness, conductivity, and heat resistance. With respect to the total amount of the polyester polyurethane resin (A), the epoxy resin (B) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure, and the imidazole silane compound (D) which may be contained as an optional component. , 50% by mass to 98% by mass, more preferably 70% by mass to 97% by mass, and particularly preferably 75% by mass to 95% by mass.

<Imidazole silane compound (D)>
The resin composition of the present invention preferably contains the imidazole silane compound (D) from the viewpoint of conductivity and adhesiveness.
The imidazole silane compound (D) is a compound having one or more imidazole ring structures and one or more silane structures, and is presumed to act as a curing agent for the epoxy resin (B).
The imidazole silane compound (D) is preferably a compound having one imidazole ring structure and one silyl group from the viewpoint of conductivity and adhesiveness.
Further, as the imidazole silane compound (D), a compound represented by the following formula (D) or an acid adduct thereof is preferably mentioned from the viewpoint of conductivity and adhesiveness.

In the formula (D), R ¹ and R ² independently represent a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group or an aryl group, and each of the above groups may have a substituent, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, at least one of R ³ is an alkyl group, the alkyl group may have a substituent, and n is an integer of 1 to 3. Represents an alkylene group, or a group in which a part of the alkylene group is substituted with at ^least one of the formulas (D2) to (D5).

In formula (D2), formula (D3) and formula (D5), R ⁶ represents a hydrogen atom or a hydroxy group, R ⁷ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁸ and R ⁹ are independent of each other. , Hydrogen atom, alkyl group or aryl group, each group may have a substituent, and the wavy line portion represents a bond position with another structure.

When the imidazole silane compound (D), particularly the compound represented by the above formula (D), is contained, the adhesiveness to a metal, particularly a gold-plated copper foil is improved. It is presumed that this is because the silane structure and the imidazole ring structure show high affinity with both the metal surface and the resin (C) having a carboxy group or a carboxylic acid anhydride structure, and the adhesion is improved by the interaction thereof. .. Further, since the imidazole ring structure can also react with the epoxy resin (B), it is presumed that this adhesiveness improving effect can be maintained even in the reflow step described later.

The imidazole silane compound (D) is preferably a compound having an imidazole ring structure as a first functional group and an alkoxysilyl group as a second functional group in one molecule.
The imidazole ring in the imidazole ring structure may have a substituent such as a saturated hydrocarbon group or an unsaturated hydrocarbon group.
In the formula (D), when R ¹ , R ² , R ³ and R ⁴ are alkyl groups, the preferred number of carbon atoms is 1 to 3.
Examples of the imidazole ring structure constituting the imidazole silane compound (D) include an imidazole ring structure, a 2-alkylimidazole ring structure, a 2,4-dialkylimidazole ring structure, and a 4-vinylimidazole ring structure.
In the imidazole silane compound (D), the alkoxysilyl group and the imidazole ring structure are alkylene groups or groups in which a part of the alkylene group is substituted with at least one of the formulas (D2) to (D5). It is preferable that they are bonded via.
The carbon number of the alkylene group in R5 of the formula ⁽ D) is preferably 1 to 10, and more preferably 3 to 7.
The imidazole silane compound (D) can be suitably synthesized by, for example, a reaction between the imidazole compound and a 3-glycidoxyalkylsilane compound or the like.
Further, the imidazole silane compound (D) may be a silanol compound produced by hydrolysis of an alkoxysilyl group, a polyorganosiloxane compound produced by a dehydration condensation reaction of the silanol compound, or a mixture thereof. good.
The acids added to the compound represented by the formula (D) include acetic acid, lactic acid, salicylic acid, benzoic acid, adipic acid, phthalic acid, citric acid, tartrate acid, maleic acid, trimellitic acid, phosphoric acid and isocyanuric acid. And so on. These can be used alone or in combination of two or more.

Further, the imidazole silane compound (D) is more preferably a compound represented by the following formula (D6) or formula (D7) or an acid adduct thereof from the viewpoint of conductivity and adhesiveness. ..

In the formula (D6) and the formula (D7), R ¹ and R ² independently represent a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group or an aryl group, and each of the above groups has a substituent. R ³ and R ⁴ may each independently represent a hydrogen atom or an alkyl group, at least one of R ³ is an alkyl group, and the alkyl group may have a substituent, where n is. An integer of 1 to 3 is represented, R ^5'represents an alkylene group, and R ⁶ represents a hydrogen atom or a hydroxy group.

The carbon number of the alkylene group in ^R5'of the formulas (D6) and (D7) is preferably 1 to 10, and more preferably 3 to 7.

Specific examples of the imidazole silane compound (D) include 1- (2-hydroxy-3-trimethoxysilylpropoxypropyl) imidazole, 1- (2-hydroxy-3-triethoxysilylpropoxypropyl) imidazole, 1- (2). -Hydroxy-3-tripropoxysilylpropoxypropyl) imidazole, 1- (2-hydroxy-3-tributoxysilylpropoxypropyl) imidazole, 1- (2-hydroxy-3-triethoxysilylpropoxypropyl) -2-methylimidazole , 1- (2-Hydroxy-3-triethoxysilylpropoxypropyl) -4-methylimidazole, 1- (3-oxo-4-trimethoxysilylpropoxypropyl) imidazole, 1- (3-trimethoxysilylpropylamino) Examples include imidazole.

Among them, the compound represented by the formula (D6) or the formula (D7) or an acid adduct thereof is preferable because it has good heat resistance and good solubility in a solvent. Acid adducts are more preferred.

The compound represented by the formula (D6) is an imidazole compound such as imidazole, 2-alkylimidazole, 2,4 dialkylimidazole, 4-vinylimidazole, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxy. It can be preferably obtained by reacting with a 3-glycidoxypropylsilane compound such as propyldialkoxyalkylsilane or 3-glycidoxypropylalkoxydialkylsilane. Of these, a reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane is particularly preferable.
The compound represented by the formula (D7) can be preferably obtained by reacting the imidazole compound with 3-methacryloyloxypropyltrimethoxysilane or the like.

The resin composition of the present invention may contain the imidazole silane compound (D) alone or in combination of two or more.
The content of the imidazole silane compound (D) has a polyester polyurethane resin (A), an epoxy resin (B), a carboxy group or a carboxylic acid anhydride structure in the resin composition from the viewpoint of conductivity and adhesiveness. It is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, based on the total amount of the resin (C) and the imidazole silane compound (D). It is particularly preferably from% by mass to 5% by mass.

<Inorganic filler (E)>
The resin composition of the present invention contains an inorganic filler (E) from the viewpoint of the extensibility of the obtained cured product, the initial stage of the obtained cured product, after soldering, after a long-term reliability test, and after a thermal cycle test. It is more preferable to contain an inorganic filler (E) and an organic filler (F) described later.
The inorganic filler (E) in the present specification is a filler made of a metal or an alloy thereof, that is, an inorganic filler other than the metal filler (G) described later.

The inorganic filler (E) is not particularly limited, and for example, non-conductive inorganic fillers such as calcium carbonate particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, talc particles, and silica particles, carbon black particles, and the like. Examples include conductive inorganic fillers.
Among them, at least one kind of particles selected from the group consisting of talc particles and silica particles is preferable from the viewpoint of conductivity after the initial stage of the obtained cured product, after soldering, after a long-term reliability test and after a thermal cycle test. , Talc particles are more preferred.

The average particle size of the inorganic filler (E) is not particularly limited, but the conductivity, coatability, and coating thickness adjustability of the obtained cured product at the initial stage, after soldering, after a long-term reliability test, and after a thermal cycle test are not particularly limited. From the viewpoint, it is preferably 0.001 μm to 50 μm, more preferably 0.005 μm to 30 μm, and particularly preferably 0.01 μm to 10 μm.
The average particle size of the filler in the present specification was obtained by measuring the filler with a tornado dry powder sample module using a laser diffraction / scattering method particle size distribution measuring device LS 13320 (manufactured by Beckman Coulter). The average particle size of the particle size, which is the D50 average particle size and the integrated value of the particles is 50%, was used.

The resin composition of the present invention may contain the inorganic filler (E) alone or in combination of two or more, but the obtained cured product has long-term reliability in the initial stage and after soldering. From the viewpoint of conductivity after the test and the thermal cycle test, it is preferable to contain two or more kinds, and it is more preferable to contain two kinds.
The content of the inorganic filler (E) is a polyester polyurethane resin (A), an epoxy resin (B) and a carboxy group or a carboxylic acid anhydride structure in the resin composition from the viewpoint of adhesiveness, conductivity and curability. It is preferably 0.1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the resin (C) having the above and the imidazole silane compound (D) which may be contained as an optional component. It is more preferably 5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 10 parts by mass.

<Organic filler (F)>
The resin composition of the present invention preferably contains an organic filler (F) from the viewpoint of the extensibility, conductivity, and moisture and heat resistance of the obtained cured product. The organic filler (F) usually contains a resin as a main component and is non-conductive.
Examples of the organic filler (F) include (meth) acrylic resin particles, polybutadiene particles, nylon fine particles, polyolefin particles, polyester particles, polycarbonate particles, polyvinyl alcohol particles, polyvinyl ether particles, polyvinyl butyral particles, silicone rubber particles, and polyurethane particles. , Phenolic resin particles, polytetrafluorinated ethylene particles and the like.
The organic filler has been found to have an effect of enhancing the compatibility of the polyester polyurethane resin (A), the epoxy resin (B) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure when dissolved. Further, from the viewpoint of further improving the compatibility and liquid stability of these resins, silicone particles, polybutadiene particles, (meth) acrylic resin particles, or polyurethane particles are particularly preferable.

The average particle size of the organic filler (F) is not particularly limited, but is preferably 0.5 μm to 50 μm, more preferably 1 μm to 30 μm, from the viewpoint of coatability and coat thickness adjustability.

The resin composition of the present invention may contain the organic filler (F) alone or in combination of two or more.
The content of the organic filler (F) is the polyester polyurethane resin (A), the epoxy resin (B) and the carboxy group or the carboxylic acid anhydride structure in the resin composition from the viewpoint of adhesiveness, conductivity and curability. It is preferably 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the resin (C) having the above and the imidazole silane compound (D) which may be contained as an optional component. It is more preferably 40 parts by mass, and particularly preferably 10 parts by mass to 20 parts by mass.

<Metal filler (G)>
The resin composition of the present invention preferably contains a metal filler (G) from the viewpoint of conductivity and heat resistance. The metal filler (G) is usually conductive.
The metal filler (G) preferably includes metal particles made of a conductive metal such as gold, platinum, silver, copper or nickel or an alloy thereof. Further, particles having a metal or resin as a nuclei instead of particles having a single composition and having a coating layer formed of a highly conductive material are also preferable from the viewpoint of cost reduction. The nucleus is preferably made of at least one material selected from the group consisting of nickel, silica, copper and resin, and more preferably made of a conductive metal or an alloy thereof. The coating layer is preferably a layer made of a material having excellent conductivity, and preferably a layer made of a conductive metal or a conductive polymer.
Examples of the conductive metal include gold, platinum, silver, tin, manganese, indium and the like, and alloys thereof. Examples of the conductive polymer include polyaniline and polyacetylene. Among these, silver is preferable from the viewpoint of conductivity.

From the viewpoint of cost and conductivity, the particles composed of the core and the coating layer preferably have a coating layer at a ratio of 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the core. It is more preferable to have a coating layer in a proportion of about 30 parts by mass.

The particles composed of the nucleolus and the coating layer are preferably particles in which the coating layer completely covers the nucleolus. However, in reality, a part of the nucleolus may be exposed. Even in such a case, if the conductive substance covers 70% or more of the surface area of the nucleus, it is easy to maintain the conductivity.

The shape of the metal filler (G) is not limited as long as the desired conductivity can be obtained. Specifically, for example, spherical shape, flake shape, leaf shape, dendritic shape, plate shape, needle shape, rod shape, or grape shape is preferable.

The average particle size of the metal filler (G) is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and particularly preferably 4 μm to 15 μm from the viewpoint of conductivity and storage stability. preferable.
In addition to the method described above, the average particle size of the metal filler (G) is obtained from an average value of about 20 particles randomly selected in an enlarged image (about 1,000 to 10,000 times) of an electron microscope. You can also do it. In this case, the average particle size is also preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm. When the metal filler (G) has a major axis direction and a minor axis direction (for example, rod-shaped particles), the average particle diameter is calculated from the length in the major axis direction.

The resin composition of the present invention may contain the metal filler (G) alone or in combination of two or more.
The content of the metal filler (G) is the polyester polyurethane resin (A), the epoxy resin (B) and the carboxy group or the carboxylic acid anhydride in the resin composition from the viewpoint of conductivity, heat resistance, and storage stability. It is preferably 1 part by mass to 500 parts by mass, more preferably 10 parts by mass to 350 parts by mass, and 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the total amount of the resin (C) having a structure. It is particularly preferable that it is a part.

The resin composition of the present invention may contain additives other than the above-mentioned components.
Other additives include thermoplastic resins other than those described above, tackifiers, flame retardants, curing agents, curing accelerators, coupling agents, heat aging inhibitors, leveling agents, defoaming agents, solvents and the like. , Can be contained to the extent that it does not affect the function of the resin composition.

Examples of the other thermoplastic resin include phenoxy resin, polyester resin, polycarbonate resin, polyphenylene oxide resin, polyurethane resin, polyacetal resin, polyethylene resin, polypropylene resin, polyvinyl resin and the like. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the tackifier include kumaron-inden resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum hydrocarbon resin, and the like. Examples thereof include hydrogenated hydrocarbon resins and terepine resins. These tackifiers may be used alone or in combination of two or more.

The flame retardant may be either an organic flame retardant or an inorganic flame retardant.
Examples of the organic flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate amide ammonium, polyphosphate amide ammonium, phosphate carbamate, and polyphosphate carbamate. , Aluminum Trisdiphenylphosphite, Aluminum Trismethylethylphosphinate, Aluminum Trisdiphenylphosphinate, Zinc bisdiethylphosphinate, Zinc bismethylethylphosphinate, Zinc bisdiphenylphosphite, Titanyl bisdiphenylphosphite, Titanium tetrakisdiethylphosphinate , Phosphate-based flame retardants such as titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate; triazine compounds such as melamine, melam, melamine cyanurate, and cyanuric acid compounds. , Isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea and other nitrogen-based flame retardant; silicone compound, silane compound and other silicon-based flame retardant.
Examples of the inorganic flame retardant include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, and zinc oxide. Metal oxides such as molybdenum oxide and nickel oxide; zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, hydrated glass and the like can be mentioned.
These flame retardants may be used alone or in combination of two or more.

The curing agent is a component for forming a crosslinked structure by reaction with the epoxy resin (B), and is, for example, an amine-based curing agent such as an aliphatic diamine, an aliphatic polyamine, a cyclic aliphatic diamine, and an aromatic diamine. Acid-based curing agents such as polyamide amine-based curing agents, aliphatic polyvalent carboxylic acids, alicyclic polyvalent carboxylic acids, aromatic polyvalent carboxylic acids and their acid anhydrides; basicity such as dicyandiamide and organic acid dihydrazide. Examples thereof include an active hydrogen-based curing agent; a polypeptide-based curing agent; a novolak resin-based curing agent; a urea resin-based curing agent; and a melamine resin-based curing agent.
These curing agents may be used alone or in combination of two or more.

Examples of the aliphatic diamine-based curing agent include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, polymethylenediamine, polyetherdiamine, 2,5-dimethylhexamethylenediamine, and trimethylhexamethylenediamine. And so on.

Examples of the aliphatic polyamine-based curing agent include diethylenetriamine, iminobis (hexamethylene) triamine, trihexatetramine, tetraethylenepentamine, aminoethylethanolamine, tri (methylamino) hexane, dimethylaminopropylamine, diethylaminopropylamine, and methylimino. Examples include bispropylamine.

Examples of the cyclic aliphatic diamine-based curing agent include mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-ethylaminopiperazin, 3, Examples thereof include 9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5.5] undecane and a hydrogenated product of methylylenediamine.

Examples of the aromatic diamine-based curing agent include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and metaxylylenediamine.

Examples of the aliphatic polyvalent carboxylic acid-based curing agent and the acid anhydride-based curing agent include succinic acid, adipic acid, dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysevacinic acid anhydride and the like.

Examples of the alicyclic polyvalent carboxylic acid-based curing agent and acid anhydride-based curing agent include methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylhymic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trialkyltetrahydrophthalic acid. , Methylcyclodicarboxylic acid and their acid anhydrides and the like.

Examples of the aromatic polyvalent carboxylic acid-based curing agent and the acid anhydride-based curing agent include phthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, ethylene glycol glycol bistrimellitic acid, glycerol tristrimeric acid and their substances. Acid anhydride and the like can be mentioned.

Examples of the polymercaptan-based curing agent include mercaptolated epoxy resin and mercaptopropionic acid ester.

Examples of the novolak-based curing agent include phenol novolac-based curing agents and cresol novolak-based curing agents.

When the resin composition of the present invention contains the curing agent, the content of the curing agent is such that the functional group equivalent is 1 molar equivalent of the epoxy group of the epoxy resin (B) from the viewpoint of adhesiveness and heat resistance. On the other hand, it is preferably set to be in the range of 0.2 molar equivalent to 2.5 molar equivalent, and more preferably in the range of 0.4 molar equivalent to 2.0 molar equivalent.

The curing accelerator is a component used for the purpose of accelerating the reaction of the epoxy resin (B), and includes a tertiary amine-based curing accelerator, a tertiary amine salt-based curing accelerator, an imidazole-based curing accelerator, and the like. Can be used.
These curing accelerators may be used alone or in combination of two or more.

Examples of the tertiary amine-based curing accelerator include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N'-. Examples thereof include dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo [5.4.0] undecene and the like.

As the tertiary amine salt-based curing accelerator, 1,8-diazabicyclo [5.4.0] undecene, formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenol Examples thereof include novolak resin salt and 1,5-diazabicyclo [4.3.0] nonen's formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt or phenolnovolak resin salt. Be done.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and 2-phenyl-. 4-Methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-Diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1') ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, Examples thereof include 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

When the resin composition of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 1 with respect to 100 parts by mass of the epoxy resin (B) from the viewpoint of adhesiveness and heat resistance. It is in the range of 10 parts by mass, particularly preferably 2 parts by mass to 5 parts by mass.

Examples of the coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, and N. -2- (Aminoethyl) -3-aminopropylmethyldimethoxylan, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isoxypropyltriethoxysilane , A silane-based coupling agent such as imidazole silane; a titanate-based coupling agent; an aluminate-based coupling agent; a zirconium-based coupling agent and the like. These may be used individually by 1 type, or may be used in combination of 2 or more type.

Examples of the heat antiaging agent include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propione. -To, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Phenol-based antioxidants such as methane; dilauryl-3,3'-thiodipropionate , Dimyristyl-3,3'-dithiopropionate and other sulfur-based antioxidants; trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite and other phosphorus-based antioxidants, etc. Be done. These may be used individually by 1 type, or may be used in combination of 2 or more type.

The resin composition of the present invention can be prepared by mixing a polyester polyurethane resin (A), an epoxy resin (B), and, if necessary, other components.
Since the resin composition of the present invention is preferably used in the state of a solution or a dispersion, it preferably contains a solvent.
Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, isophorone; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene; methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, Esters such as 3-methoxybutyl acetate; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane and the like can be mentioned. These solvents may be used alone or in combination of two or more. When the resin composition of the present invention is a solution containing a solvent or a dispersion liquid, coating on an adherend and formation of a resin composition layer can be smoothly performed, and a resin composition layer having a desired thickness can be obtained. It can be easily obtained.

When the resin composition of the present invention contains a solvent, the solvent has a solid content concentration of preferably 3% by mass to 80% by mass, more preferably 10% by mass or more, from the viewpoint of workability including coating film forming property. It is used so as to be in the range of 50% by mass.

A suitable adherend according to the resin composition of the present invention comprises a polymer material such as a polyimide resin, a polyether ether ketone resin, a polyphenylene sulfide resin, an aramid resin, and a liquid crystal polymer; and a metal material such as copper, aluminum, and stainless steel. It is an object. The shape of the adherend is not particularly limited. Then, two members made of the same material or different materials as an adherend can be adhered to each other by the resin composition of the present invention to produce an integrated composite. Further, it is possible to manufacture a product having an adhesive resin composition layer, such as the following coverlay film and bonding sheet.

(Laminate with resin composition layer and laminate)
The laminate with the resin composition layer of the present invention is a laminate using the resin composition of the present invention, and is formed by partially curing the resin composition layer made of the resin composition of the present invention and the resin composition. A base material in contact with at least one surface of the B-stage-shaped resin composition layer or the cured layer obtained by curing the resin composition and the resin composition layer, the B-stage-shaped resin composition layer or the cured layer. It is preferable to include a film.
In the present invention, the B-stage shape of the resin composition layer means a semi-cured state in which a part of the resin composition layer begins to cure, and a state in which the curing of the resin composition layer further progresses by heating or the like. Is.
Further, when the resin composition containing the solvent is used, the resin composition layer made of the resin composition of the present invention is preferably a layer in which at least a part of the solvent is removed from the resin composition of the present invention.

The laminate with the resin composition layer of the present invention and the laminate of the present invention preferably have a base material, and more preferably have a layer made of the resin composition of the present invention on the base material.
The base material is not particularly limited, and a known base material can be used.
Further, the base material is preferably a film-like base material (base material film).
The base film is preferably a resin film, more preferably a polyimide film or an aramid film, and particularly preferably a polyimide film.
The polyimide film or the aramid film is not particularly limited as long as it has an electrical insulating property, and may be a film made of only a polyimide resin or an aramid resin, a film containing the resin and an additive, or the like. A surface treatment may be applied to the side on which the resin composition layer is formed.
The thickness of the base material is not particularly limited, but is preferably 3 μm to 125 μm.
The thickness of the resin composition layer is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm.

As a method for producing a laminate with a resin composition layer of the present invention, for example, the resin composition of the present invention containing a solvent is applied to the surface of a base film such as a polyimide film to form a resin composition layer. Later, by removing at least a part of the solvent from the resin composition layer, a laminate having a B-stage resin composition layer can be produced.
The drying temperature at the time of removing the solvent is preferably 40 ° C to 250 ° C, more preferably 70 ° C to 170 ° C.
The drying is performed by passing the laminate coated with the resin composition through a furnace in which hot air drying, far infrared ray heating, high frequency induction heating and the like are performed.
The laminate with the resin composition layer of the present invention may further have a releasable film on the surface of the resin composition layer for storage or the like, if necessary.
As the releasable film, known films such as polyethylene terephthalate film, polyethylene film, polypropylene film, silicone releasable paper, polyolefin resin coated paper, polymethylpentene (TPX) film, and fluororesin film are used.

The thickness of the B-stage resin composition layer is preferably 5 μm to 100 μm, more preferably 5 μm to 70 μm, further preferably 5 μm to 50 μm, and particularly preferably 10 μm to 40 μm. preferable.
The thickness of the base film and the resin composition layer is selected depending on the application, but the base film tends to be thinner in order to improve the electrical characteristics. The preferred thickness of the base film is the same as the preferred thickness of the base film described above.
In the laminate with the resin composition layer of the present invention, the ratio (A / B) of the thickness (A) of the resin composition layer to the thickness (B) of the base film is 1 or more and 10 or less. It is preferable, and it is more preferable that it is 1 or more and 5 or less. Further, it is preferable that the thickness of the resin composition layer is thicker than the thickness of the base film.

The method for producing the laminate of the present invention is, for example, the same as in the case of the laminate with the resin composition layer of the present invention after the resin composition of the present invention containing a solvent is applied to the surface of the base film. Then, the surface of the formed resin composition layer and the adherend are brought into surface contact with each other, and laminating, for example, thermal laminating at 80 ° C. to 150 ° C. is performed. Next, a method of heat-pressing the laminate (base film / resin composition layer / adherend) and further curing the resin composition layer by after-cure to form a cured layer is preferable.
The conditions for heat crimping are not particularly limited as long as they can be crimped, but are preferably 150 ° C. to 200 ° C. and a pressure of 1 MPa to 3 MPa for 1 minute to 60 minutes. The conditions for aftercure are not particularly limited, but are preferably 100 ° C to 200 ° C and 30 minutes to 4 hours.
The thickness of the cured layer is preferably 5 μm to 100 μm, more preferably 5 μm to 70 μm, further preferably 5 μm to 50 μm, and particularly preferably 10 μm to 40 μm.
The adherend is not particularly limited, and examples thereof include those described above. Among them, a metal adherend is preferably mentioned, a copper foil or a plated copper foil is more preferably mentioned, and a gold-plated copper foil is particularly preferably mentioned.
Further, the shape and size of the adherend are not particularly limited, and known ones can be used.

Further, as one embodiment of the laminated body of the present invention, a flexible copper-clad laminate may be mentioned.
That is, the flexible copper-clad laminate of the present invention has a cured layer obtained by curing the resin composition made of the resin composition of the present invention, and the polyimide film or the aramid film and the resin composition of the present invention are cured. It is preferable that the cured layer made of the resin and the copper foil are laminated.
In the flexible copper-clad laminate of the present invention, the cured layer and the copper foil may be formed on both sides of a polyimide film or an aramid film. Since the resin composition of the present invention has excellent adhesiveness to articles containing copper, the flexible copper-clad laminate of the present invention has excellent stability as an integrated product.

The structure of the polyimide film or the aramid film is the same as that of the polyimide film or the aramid film in the coverlay film of the present invention described above.
The thickness of the cured layer is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm.
Further, the copper foil is not particularly limited, and electrolytic copper foil, rolled copper foil and the like can be used.
Further, the copper foil may be plated with a known metal or alloy such as gold or silver.

Examples of the embodiment of the laminate with the resin composition layer of the present invention include a bonding film, an electromagnetic wave shielding film, a coverlay film and the like, which will be described later.

-Bonding film-
The bonding film of the present invention uses the resin composition of the present invention, and is a B-stage resin composition layer obtained by partially curing the resin composition of the present invention and at least the resin composition layer. It is preferable to provide a release film in contact with one surface.
Further, the bonding film of the present invention is also an embodiment of the laminate with the resin composition layer of the present invention, which will be described later.
The bonding film of the present invention may have an embodiment in which a resin composition layer is provided between two releasable films.
As the releasable film, a known one as described above is used.
The thickness of the releasable film is preferably 20 μm to 100 μm.
The thickness of the resin composition layer is preferably 5 μm to 100 μm, more preferably 10 μm to 60 μm.

As a method for producing the bonding sheet of the present invention, for example, the resin composition of the present invention containing a solvent is applied to the surface of a releasable film, and then the above-mentioned laminate with the resin composition layer of the present invention is used. A method of drying in the same manner as in the case is preferably mentioned.

-Electromagnetic wave shield film-
The electromagnetic wave shielding film of the present invention uses the resin composition of the present invention, and is a resin composition layer made of the resin composition of the present invention and a B-stage resin obtained by partially curing the resin composition. It is preferable to have a composition layer or a cured layer obtained by curing the resin composition.
Further, the electromagnetic wave shielding film of the present invention preferably has the resin composition layer and the protective layer.
The protective layer is not particularly limited as long as it is a layer made of an insulating resin composition, and any known layer can be used. Further, the protective layer may use the resin component used in the resin composition of the present invention. Further, the protective layer may be formed of two or more layers having different compositions and hardness.
In addition, the protective layer includes a curing accelerator, a tackifier, an antioxidant, a pigment, a dye, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling agent, a filler, a flame retardant, and a viscosity control, if necessary. Agents, anti-blocking agents and the like may be included.

The thickness of the resin composition layer in the electromagnetic wave shielding film of the present invention is not particularly limited, but is preferably 3 μm to 30 μm from the viewpoint of conductivity and connectivity with the ground circuit.

Next, a specific embodiment of the method for manufacturing the electromagnetic wave shielding film of the present invention will be described.
For example, the resin composition for a protective layer is coated and dried on one surface of a peelable film to form a protective layer, and the resin composition of the present invention is coated and dried on the protective layer to form a resin composition layer. The method of forming the above can be mentioned.
By the manufacturing method as exemplified, it is possible to obtain an electromagnetic wave shielding film in a laminated state of a resin composition layer / protective layer / peelable film.

As a method for providing the resin composition layer and the protective layer, conventionally known coating methods such as gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade coating method, roll coating method and knife coating method are used. , Spray coat method, bar coat method, spin coat method, dip coat method and the like.

The electromagnetic wave shielding film of the present invention can be adhered onto a printed wiring board by, for example, a hot press. The resin composition layer becomes soft by heating and flows into a gland portion provided on the printed wiring board by pressurization. As a result, the ground circuit and the conductive adhesive are electrically connected, and the shielding effect can be enhanced.

Hereinafter, the present invention will be specifically described based on examples. The present invention is not limited to these examples. Further, in the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<< Raw materials used >>
1. 1. Polyester polyurethane resin (A)
As the polyester used for producing polyester polyurethane, commercially available products and synthetic products were used.

<Commercial product>
As commercial products, Aronmelt PES-360HVXM30 and Aronmelt PES-310S30 manufactured by Toagosei Co., Ltd. were used. The number average molecular weight of PES-360HVXM30 was 20,000, and the glass transition point was 65 ° C. The number average molecular weight of PES-310S30 was 20,000, and the glass transition point was 8 ° C.

<Synthesis of polyester resin (PES-1)>
In a flask equipped with a stirrer, a nitrogen introduction tube, a distillate tube, and a thermometer, 201 parts by mass of dimethyl terephthalate, 86 parts by mass of ethylene glycol, 140 parts by mass of neopentyl glycol, 0.9 parts by mass of trimethylolpropane, and as a catalyst. 0.22 parts by mass of zinc acetate was charged, the temperature was raised while introducing nitrogen, and after distilling methanol at 150 ° C to 180 ° C, 183 parts by mass of isophthalic acid, 0.6 parts by mass of trimethylolpropane and trioxide were added. After 0.12 parts by mass of Antimon was added and water was distilled off at 180 ° C. to 210 ° C., the reaction was continued for 6 hours at 230 ° C. under a reduced pressure of 200 Pa while gradually reducing the pressure. The obtained polyester resin PES-1 had a number average molecular weight of 7,000 and a glass transition point of 60 ° C. The monomer composition by nuclear magnetic resonance (NMR) analysis was terephthalic acid / isophthalic acid / ethylene glycol / neopentyl glycol = 48/52/43/56 in molar ratio. 180 parts by mass of the synthesized polyester resin was taken, and 378 parts by mass of toluene and 42 parts by mass of methyl isobutyl ketone were added to prepare a polyester solution.

<Synthesis of polyester polyurethane resin a1>
(1) Synthesis of polyester polyurethane resin a1 In a flask equipped with a stirrer, a reflux dehydrator and a distillation tube, 600 parts by mass of PES-360HVXM30, 100 parts by mass of toluene, 2-butyl-2-ethyl-1,3-propanediol 30 parts by mass was charged. After raising the temperature to 120 ° C. and distilling 100 parts by mass of the solvent containing water, the temperature was lowered to 105 ° C., and 0.4 parts by mass of 2,2-bis (hydroxymethyl) propionic acid was charged and dissolved. .. Then, 42 parts by mass of Cosmonate NBDI (NBDI) manufactured by Mitsui Chemicals, Inc. was added, and after 30 minutes, 0.2 parts by mass of dibutyltin dilaurate was added. After continuing the reaction until the predetermined molecular weight was reached, a solution of polyester urethane resin a1 was obtained by diluting with toluene / 2-propanol and adjusting the solid content concentration to 30%. The number average molecular weight at that time was 35,000, and the acid value was 2 mgKOH / g.

<Synthesis of polyester polyurethane resins a2 to a12>
Regarding the synthetic method of the polyester polyurethane resin a1, the synthesis was carried out in the same manner as the synthetic method of the polyester polyurethane resin a1 except that the polyester, diol and diisocyanate shown in Table 1 were changed to be the parts by mass in the table.

The abbreviations shown in Table 1 other than those described above will be described below.
Takenate 600: 1,3-bis (isocyanatomethyl) cyclohexane, manufactured by Mitsui Chemicals, Inc. HDMI: methylenebis (4-cyclohexyldiisocyanate), manufactured by Manka Chemicals Japan Co., Ltd., trade name WANNAME (registered trademark) HMDI
HDI: Hexamethylene diisocyanate, manufactured by Tosoh Corporation, trade name HDI
Dimer diol: A diol having 36 carbon atoms obtained by reducing dimer acid, manufactured by Croda Japan Co., Ltd., trade name PRIPOL 2033.

2. 2. Epoxy resin (B)
The following commercially available products were used.
(1) Epoxy resin b1
Bisphenol A novolak type epoxy resin "EPICLON N-865" manufactured by DIC Corporation (trade name)
(2) Epoxy resin b2
Bisphenol A type epoxy resin "jER 1055" manufactured by Mitsubishi Chemical Corporation (trade name)

3. 3. Resin (C) having a carboxy group or a carboxylic acid anhydride structure
(1) Synthesis of Polyamide Resin c1 Polyamide resin c1 was synthesized as follows.
A flask equipped with a stirrer, a reflux dehydrator and a distillation tube was charged with 65 parts by mass of azelaic acid, 190 parts by mass of dodecanedioic acid, 100 parts by mass of piperazine and 120 parts by mass of distilled water. After raising the temperature to 120 ° C. and distilling water, the temperature was raised to 240 ° C. at a rate of 20 ° C./hour, and the reaction was continued for 3 hours to obtain the polyamide resin c1. The amine value of this resin was 4.5 mgKOH / g, and the acid value was 10.5 mgKOH / g.

(2) Synthesis of Polyamide Resin c2 Polyamide resin c2 was synthesized as follows.
A flask equipped with a stirrer, a reflux dehydrator and a distillation tube was charged with 485 parts by mass of dimer acid, 100 parts by mass of hexamethylenediamine and 120 parts by mass of distilled water. After raising the temperature to 120 ° C. and distilling water, the temperature was raised to 240 ° C. at a rate of 20 ° C./hour, and the reaction was continued for 3 hours to obtain the polyamide resin c2. The amine value of this resin was 4.5 mgKOH / g, and the acid value was 10.5 mgKOH / g.

(3) Synthesis of Polyolefin Resin c3 100 parts by mass of a propylene-butene random copolymer composed of 80% by mass of a propylene unit and 20% by mass of a butene unit, 1 part by mass of maleic anhydride, and methacrylic acid produced by using a metallocene catalyst as a polymerization catalyst. 0.3 parts by mass of lauryl and 0.4 parts by mass of dit-butyl peroxide were kneaded and reacted using a twin-screw extruder in which the maximum temperature of the cylinder part was set to 170 ° C. Then, degassing under reduced pressure was performed in the extruder to remove the residual unreacted material to produce the polyolefin resin c1. The polyolefin resin c1 had a weight average molecular weight of 80,000 and an acid value of 10 mgKOH / g. The content ratio of the graft portion in the polyolefin resin c1 was 1.5% by mass.

(4) Synthesis of Polyolefin Resin c4 (Resin having no carboxy group and carboxylic acid anhydride structure) Using a metallocene catalyst as a polymerization catalyst, 80% by mass of a propylene unit and 20% by mass of a butene unit were reacted to obtain a polyolefin resin c4. .. The polyolefin resin c4 had a weight average molecular weight of 100,000.

4. Imidazole silane compound (D)
1- (2-Hydroxy-3-trimethoxysilylpropoxypropyl) imidazole

5. Inorganic filler (E)
(1) Inorganic filler e1
Talc "SG-95" manufactured by Nippon Talc Co., Ltd. (trade name; average particle size 2.5 μm)
(2) Inorganic filler e2
Aerosil "R972" (trade name; average particle size 16 nm, silica particles), obtained from Toshin Kasei Co., Ltd.

6. Organic filler (F)
(1) Organic filler f1
Urethane beads "TK-800T" manufactured by Negami Kogyo Co., Ltd. (trade name; average particle size 8 μm)
(2) Organic filler f2
Acrylic beads "J-4P" manufactured by Negami Kogyo Co., Ltd. (trade name; average particle size 2.2 μm)

7. Metal filler (G)
Copper powder "FCC-115A" manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. (trade name, particle size distribution, the amount of particles of 45 μm or less exceeds 90% by mass, the amount of particles of 45 μm to 63 μm is less than 10% by mass, 63 μm The amount of particles of ~ 75 μm is less than 3% by mass.)

8. Flame Retardant Clariant phosphinic acid metal salt "Exolit OP935" (trade name)

9. Curing Accelerator Shikoku Chemicals Corporation imidazole-based curing accelerator "Curesol C11-Z" (trade name)

10. Solvent A mixed solvent consisting of toluene, methyl isobutyl ketone and 2-propanol (mass ratio = 100: 20: 20)

(Examples 1 to 29 and Comparative Example 1)
The above raw materials are added to a flask equipped with a stirrer at the ratio shown in Table 2, and the mixture is stirred under heating at 60 ° C. for 6 hours to add the component (A), the component (B), the component (C), and the imidazole silane to the solvent. A liquid adhesive composition was produced by dissolving a compound and a curing accelerator and dispersing an inorganic filler, an organic filler, a metal filler, and a flame retardant. Then, a coverlay film, a bonding sheet, and adhesive test pieces A and B were prepared using all of these liquid adhesive compositions, and the following evaluations (i) to (ix) were performed. The evaluation results are shown in Table 2.

(1) Preparation of Coverlay Film A liquid adhesive composition is rolled onto the surface of a 25 μm-thick polyimide film so that the thickness after drying is 15 μm, dried at 120 ° C. for 2 minutes, and adhered. A coverlay film having an agent layer was obtained.

(2) Preparation of Adhesive Test Piece A A rolled copper foil with a thickness of 35 μm manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. was prepared. Then, the mirror surface was superposed so as to be in contact with the adhesive layer surface of the coverlay film, and laminating was performed under the conditions of 150 ° C., 0.3 MPa, and 1 m / min. The obtained laminate (polyimide film / adhesive layer / copper foil) is heated at 150 ° C. and 3 MPa for 5 minutes and pressure-bonded, and then after-cured at 160 ° C. for 2 hours in an oven. By doing so, an adhesion test piece A was obtained.

(3) Preparation of Bonding Sheet A releasable PET film with a thickness of 35 μm was prepared. Then, a mixture in which the liquid adhesive composition and the copper powder "FCC-115A" manufactured by Fukuda Metal Foil Powder Industry Co., Ltd. are blended on the surface so as to be 15% by mass of the total solid content resin is added to the thickness after drying. The roll was applied so as to have a diameter of 25 μm, and the mixture was dried at 140 ° C. for 2 minutes to obtain a bonding sheet having an adhesive layer.

(4) Preparation of Adhesion Test Piece B A copper circuit pattern is formed on the surfaces of a nickel-plated SUS304 plate with a thickness of 300 μm and a polyimide film with a thickness of 25 μm, and the circuit pattern has a diameter of 1 mm. A flexible printed wiring board on which a coverlay film having a thickness of 37.5 μm having a through hole was laminated was prepared. First, the nickel-plated surface of the SUS304 plate is laminated so as to be in contact with the adhesive layer surface of the bonding sheet, and laminating is performed under the conditions of 150 ° C., 0.3 MPa, and 1 m / min to form a laminate (SUS plate). / Adhesive layer / Releasable PET film) was obtained. After that, the releasable PET film was peeled off, and a flexible printed wiring board (a copper foil circuit was formed on a polyimide having a thickness of 25 μm on the surface of the exposed adhesive layer, and a diameter of 1 mm was formed on the copper foil circuit. A wiring board on which a coverlay film having a thickness of 37.5 μm having a through hole is laminated) is heat-pressed for 5 minutes at 150 ° C. and 3 MPa, and then after-cured at 160 ° C. for 2 hours in an oven. By doing so, an adhesion test piece B (SUS plate / adhesive layer / flexible printed wiring board) was produced.

(I) Peeling Adhesive Strength In order to evaluate the adhesiveness, each adhesive test is performed under the conditions of JIS C 6481 "Copper-clad laminate test method for printed wiring board", temperature 23 ° C. and tensile speed 50 mm / min. The 180 ° peeling adhesive strength (N / mm) when the copper foil of the piece A was peeled off from the polyimide film was measured. The width of the adhesion test piece at the time of measurement was 10 mm. As a result, the peel strength of 0.5 N / mm or more is "A", the peel strength of 0.35 N / mm or more and less than 0.5 N / mm is "B", and the peel strength of less than 0.35 N / mm is "C". Displayed as.

(Ii) Peeling adhesion strength after long-term moist heat test In order to evaluate the adhesiveness after storage at 85 ° C for 85% RH 1,000 hours, it complies with JIS C 6481 "Copper-clad laminate test method for printed wiring boards". The 180 ° peeling adhesion strength (N / mm) when the copper foil of each adhesion test piece A was peeled off from the polyimide film was measured under the conditions of a temperature of 23 ° C. and a tensile speed of 50 mm / min. The width of the adhesion test piece at the time of measurement was 10 mm. As a result, the peel strength reduction rate of less than 15% compared to the initial stage is "A", the peel strength reduction rate is 15% or more and less than 30% is "B", and the peel strength reduction rate is 30% or more and less than 50% is "C", 50%. The above is displayed as "D".

(Iii) Solder heat resistance (appearance at the time of soldering, peeling adhesive strength after soldering)
The test was conducted under the following conditions in accordance with JIS C 6481 (1996).
The adhesion test piece A was floated in a solder bath at 260 ° C. for 60 seconds with the side of the polyimide film facing up, and the presence or absence of appearance abnormalities such as swelling and peeling of the adhesive layer was visually evaluated. As a result, "A" was found to have no abnormal appearance such as microvoids, swelling and peeling, "B" was found to have slight microvoids, and abnormal appearance such as swelling and peeling was confirmed. Was displayed as "C".
Further, the test piece taken out from the solder bath was measured in accordance with JIS C 6481, and the 180 ° peeling adhesive strength (N / cm) when the polyimide film was peeled off from the gold-plated copper foil at 23 ° C. The width of the adhesion test piece at the time of measurement was 10 mm, and the tensile speed was 50 mm / min. The width of the adhesion test piece at the time of measurement was 10 mm. As a result, the peel strength reduction rate of less than 15% compared to the initial stage is "A", the peel strength reduction rate is 15% or more and less than 30% is "B", and the peel strength reduction rate is 30% or more and less than 50% is "C", 50%. The above is displayed as "D".

(Iv) Flame Retardant The coverlay film was heat-cured at 160 ° C. for 2 hours, and the flame retardancy was evaluated according to UL-94 defined by Undewriters Laboratories. Those that passed the test (VTM-0 class) were displayed as "A", and those that failed were displayed as "F".

(V) Conductivity (initial, connection resistance)
The connection resistance value between the SUS plate of the adhesion test piece B (SUS plate / adhesive layer / flexible printed wiring board) and the copper foil circuit of the flexible printed wiring board was measured with a resistance value measuring device. As a result, the connection resistance value of less than 0.3Ω is "A", the connection resistance value of 0.3Ω or more and less than 0.5Ω is "B", and the connection resistance value of 0.5Ω or more and 1Ω or less is "C". Those with 1Ω or more and 3Ω or less are displayed as “D”, and those with more than 3Ω are displayed as “E”.

(Vi) Conductivity after soldering (Conductivity after soldering, connection resistance)
The adhesion test piece B was floated in a solder bath at 260 ° C. for 60 seconds. Then, the connection resistance value between the SUS plate of the adhesion test piece B taken out from the solder bath and the copper foil circuit of the flexible printed wiring plate was measured with a resistance value measuring device. As a result, the connection resistance value of less than 0.3Ω is "A", the connection resistance value of 0.3Ω or more and less than 0.5Ω is "B", and the connection resistance value of 0.5Ω or more and 1Ω or less is "C". Those with 1Ω or more and 3Ω or less are displayed as “D”, and those with more than 3Ω are displayed as “E”.

(Vii) Conductivity after long-term reliability test (conductivity after storage at 85 ° C for 85% RH for 1,000 hours, connection resistance)
The adhesion test piece B was left in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 1,000 hours. Then, the connection resistance value between the SUS plate of the adhesion test piece B and the copper foil circuit of the flexible printed wiring plate was measured with a resistance value measuring device. As a result, the connection resistance value of less than 0.3Ω is "A", the connection resistance value of 0.3Ω or more and less than 0.5Ω is "B", and the connection resistance value of 0.5Ω or more and 1Ω or less is "C". Those with 1Ω or more and 3Ω or less are displayed as “D”, and those with more than 3Ω are displayed as “E”.

(Viii) Conductivity after thermal cycle test (connection resistance)
The adhesion test piece B is placed in a high-temperature (125 ° C) and low-temperature (-40 ° C) thermal shock tester, held at -40 ° C for 30 minutes, and then held at 125 ° C for 30 minutes. After 1,000 cycles, the connection resistance value between the SUS plate of the adhesive test piece B and the copper foil circuit of the flexible printed wiring plate was measured with a resistance value measuring device. As a result, the connection resistance value of less than 0.3Ω is "A", the connection resistance value of 0.3Ω or more and less than 0.5Ω is "B", and the connection resistance value of 0.5Ω or more and 1Ω or less is "C". Those with 1Ω or more and 3Ω or less are displayed as “D”, and those with more than 3Ω are displayed as “E”.

(Ix) Storage Stability of Resin Compositions The adhesive compositions (resin compositions) of Examples 1 to 29 and Comparative Example 1 having the compositions shown in Table 1 are placed in glass bottles, sealed, and prescribed at 5 ° C. It was stored for a long time and the crystallinity of the composition was observed. After storage for a predetermined time, the point where gelation or liquid separation of the adhesive composition was confirmed was regarded as poor storage stability and evaluated.
<Evaluation criteria>
A: No gelation or liquid separation was confirmed for 1 week or longer.
F: Gelation or liquid separation occurred in less than 1 week.

In addition, the unit of the numerical value of each component column in the resin composition composition shown in Table 2 is a mass part.

As is clear from the results shown in Table 2, in the resin compositions of Examples 1 to 29, the obtained cured product was stored for a long period of time and cooled in a high temperature and high humidity environment as compared with the resin composition of Comparative Example 1. It was a resin composition having excellent conductivity regardless of which test was performed after the cycle test.
Further, in the resin compositions of Examples 1 to 29, the obtained cured product has an initial peeling adhesive strength, a peeling adhesive strength after soldering, a peeling adhesive strength after a long-term reliability test, flame retardancy, and initial conductivity. It was also excellent in properties and conductivity after soldering.

The disclosure of Japanese Patent Application No. 2020-178234, filed October 23, 2020, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Is incorporated herein by reference.

Claims

Polyester polyurethane resin (A) and
Containing epoxy resin (B),
A resin composition in which the diisocyanate component constituting the polyester polyurethane resin (A) contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms.
The resin composition according to claim 1, further containing a resin (C) having a carboxy group or a carboxylic acid anhydride structure.
The resin composition according to claim 1 or 2, wherein the polyester polyurethane resin (A) has a molecular weight of 200 to 8,000 per urethane bond.
The polyester polyurethane resin (A), the epoxy resin (B) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure in the resin composition, and the imidazole silane compound (D) which may be contained as an optional component. The content of the polyester polyurethane resin (A) is 10% by mass to 90% by mass with respect to the total amount, and the content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is 5% by mass. The resin composition according to any one of claims 1 to 3, which is ~ 70% by mass.
The resin composition according to any one of claims 1 to 4, further containing an inorganic filler (E).
The resin composition according to any one of claims 1 to 5, further containing an organic filler (F).
The resin composition according to any one of claims 1 to 6, wherein the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms has an alicyclic structure.
The resin composition according to any one of claims 1 to 7, wherein the diol component constituting the polyester polyurethane resin (A) contains a diol compound having a hydrocarbon group having 5 to 32 carbon atoms.
The resin composition according to claim 8, wherein the diol compound having a hydrocarbon group having 5 to 32 carbon atoms contains an alicyclic structure or a diol compound having two or more side chains.
The resin composition according to any one of claims 1 to 9, wherein the polyester polyurethane resin (A) contains a polyester polyurethane resin having a polyester structure having a number average molecular weight of 8,000 to 30,000.
The resin composition according to any one of claims 1 to 10, wherein the polyester polyurethane resin (A) has a number average molecular weight of 10,000 to 80,000.
The resin composition according to any one of claims 1 to 11, wherein the polyester polyurethane resin (A) has an acid value of 0.1 mgKOH / g to 20 mgKOH / g.
The resin composition according to any one of claims 1 to 12, wherein the polyester polyurethane resin (A) has a glass transition temperature of 30 ° C to 150 ° C.
The resin composition according to any one of claims 1 to 13, wherein the content of the epoxy resin (B) is 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the polyester polyurethane resin (A).
The resin composition according to any one of claims 1 to 14, wherein the epoxy resin (B) contains a bisphenol A type epoxy resin and / or a novolak type epoxy resin.
Any of claims 1 to 15, wherein the content of the resin (C) having a carboxy group or a carboxylic acid anhydride structure is 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the polyester polyurethane resin (A). The resin composition according to item 1.
Any of claims 1 to 16, wherein the resin (C) having a carboxy group or a carboxylic acid anhydride structure contains at least one of a polyamide resin having an acid value and a resin having an acid-modified polyolefin structure. The resin composition according to item 1.
The resin composition according to any one of claims 1 to 17, further containing a metal filler (G).
The content of the metal filler (G) is contained in the polyester polyurethane resin (A), the epoxy resin (B) and the resin (C) having a carboxy group or a carboxylic acid anhydride structure in the resin composition, and as an optional component. The resin composition according to claim 18, which is 10 parts by mass to 350 parts by mass with respect to 100 parts by mass of the total amount of the imidazole silane compound (D) which may be used.
The resin composition according to claim 18 or 19, wherein the metal filler (G) is a conductive filler.
A release film in contact with a B-stage resin composition layer obtained by partially curing the resin composition according to any one of claims 1 to 20 and at least one surface of the resin composition layer. Bonding film with and.
A resin composition layer made of the resin composition according to any one of claims 1 to 20, a B-stage resin composition layer obtained by partially curing the resin composition, or the resin composition. A laminate with a resin composition layer comprising a cured layer obtained by curing an object and a base film in contact with at least one surface of the resin composition layer, the B-stage resin composition layer, or the cured layer.
A laminate provided with a cured layer obtained by curing the resin composition according to any one of claims 1 to 20.
A flexible copper-clad laminate comprising a copper foil, a cured layer obtained by curing the resin composition according to any one of claims 1 to 20, and a base material.
A flexible flat cable including a copper wiring, a cured layer obtained by curing the resin composition according to any one of claims 1 to 20, and a covering material.
A resin composition layer made of the resin composition according to any one of claims 1 to 20, a B-stage resin composition layer obtained by partially curing the resin composition, or the resin composition. An electromagnetic wave shielding film having a cured layer formed by curing an object.