KR20180090739A - Printed wiring board with protective sheet, thermosetting adhesive sheet with sheet-like substrate, manufacturing methods thereof and thermosetting adhesive sheet - Google Patents

Abstract

A printed circuit board having adhesive properties after curing, heat resistance (particularly after humidification) and flexibility, a thermosetting adhesive sheet provided with a sheet-like substrate, a process for producing them, and a thermosetting adhesive sheet.
The thermosetting adhesive sheet according to the present invention is formed of a thermosetting composition containing a specific resin (A), a specific curing agent (B), and a specific amount of an alkali metal compound (C) Contains 1 to 10000 ppm of the alkali metal compound (C) in terms of mass of the alkali metal element.

Description

TECHNICAL FIELD [0001] The present invention relates to a printed wiring board having a protective sheet, a thermosetting adhesive sheet provided with a sheet-like substrate, a method of producing the same, and a thermosetting adhesive sheet having a thermosetting adhesive sheet, a thermosetting adhesive sheet, THERMOSETTING ADHESIVE SHEET}

The present invention relates to a printed wiring board provided with a protective sheet, a thermosetting adhesive sheet provided with a sheet-like substrate, a process for producing the same, and a thermosetting adhesive sheet. The thermosetting adhesive sheet of the present invention is suitably used, for example, for protecting the circuit surface of a printed wiring board.

In recent years, the field of electronics has been remarkably developed, and in particular, electronic devices have become smaller, lighter, and higher in density, and electronic materials including printed wiring boards have become increasingly demanded for thinning, multilayering, and high precision. Examples of the adhesive or coating agent used in the vicinity of such electronic materials include the following (1) to (6).

(1) Interlayer adhesive: It is used to bond the circuit boards together. It is directly connected to a circuit made of copper or silver conductor. And is used in the form of a liquid or a sheet.

(2) Adhesive for coverlay film: used for bonding a coverlay film (a polyimide film or the like used for protecting the outermost surface of a circuit) to a base circuit board, and a polyimide film and an adhesive layer are integrated in advance There are many.

(3) Adhesive for copper clad film (CCL): It is used for sticking a copper foil to a polyimide film. And processing such as etching is performed at the time of forming the copper circuit.

(4) Coverage: Used to protect the outermost surface of a circuit, printed by printing ink on a circuit or attached with an adhesive sheet, and then cured. There are photosensitive or heat curable ones.

(5) Adhesive for Bonding Plate: It is used for fixing a part of the wiring board to a reinforcing plate such as metal, glass epoxy, polyimide or the like for the purpose of supplementing the mechanical strength of the wiring board.

(6) Adhesive for electromagnetic wave shielding: It is bonded to a flexible printed wiring board for the purpose of blocking electromagnetic noise generated in an electronic circuit.

These forms include a liquid phase (inked for printing) or a sheet (prefilmized), and a suitable form is selected depending on the application.

Various studies have been conducted in order to meet the high demand for such members around electronic materials. For example, the following patent documents 1 and 2 disclose a curable composition containing a cyanate ester resin and a monovalent phenol compound.

Patent Document 3 discloses a curable composition comprising a phenol resin obtained by reacting a phenol, a compound having a triazine ring (ring), and a hydroxyl group-substituted aromatic aldehyde, and an epoxy resin.

Patent Document 4 discloses a curable composition for radical polymerization of a polyether ester amide.

Patent Document 5 discloses an example of using a liquid crystal polymer as a method of forming a laminate circuit using a thermoplastic resin having no crosslinked structure.

Patent Document 6 discloses a tape provided with an adhesive for TAB having a flexible organic insulating film, an adhesive layer and a protective film, wherein the adhesive layer is a TAB adhesive containing a polyamide resin, an organic metal compound and an epoxy resin A tape provided is disclosed. More specifically, when a copper foil and a polyimide film are adhered to each other with an adhesive sheet containing a polyamide resin, an organic metal compound and a bifunctional epoxy resin, the peel strength (adhesion strength) after plating is excellent, And is excellent in insulating properties.

Patent Document 7 discloses a heat-polymerizable and radiation-polymerizable adhesive sheet comprising a polyimide resin (A), an epoxy resin (B), and an epoxy resin curing agent (C).

Patent Document 8 discloses a resin composition comprising a structural unit derived from a monomer having at least two (A) (a-1) ethylenic polymerizable unsaturated groups having an alkali metal ion content of 50 ppm or less and (a-2) a structural unit derived from a monomer having an alcoholic hydroxyl group (A-3) an adhesive composition containing a copolymer containing a structural unit derived from at least one selected from the group consisting of styrene, styrene derivatives, (meth) acrylic acid, and (meth) acrylic acid derivatives has been disclosed (Refer to claim 1).

Japanese Patent Application Laid-Open No. 2001-214053 Japanese Patent Application Laid-Open No. 2002-138199 Japanese Patent Application Laid-Open No. 2006-249178 Japanese Laid-Open Patent Publication No. 2013-45755 Japanese Patent Application Laid-Open No. 2005-105165 Japanese Patent Application Laid-Open No. 9-64111 Japanese Patent Application Laid-Open No. 2003-41202 Japanese Patent Application Laid-Open No. 2008-81678

However, it is difficult to satisfy a plurality of characteristics at the same time for a high demand as a member around the electronic material, and the required characteristics can not be sufficiently satisfied.

The curable compositions disclosed in Patent Documents 1 and 2 exhibit good adhesiveness and heat resistance derived from high Tg, but there is a problem that the molded article is weak.

The curable composition disclosed in Patent Document 3 exhibits high heat resistance and flame retardancy derived from a high aromatic content, but has a problem of low flexibility due to high intermolecular interaction.

The curable composition disclosed in Patent Document 4 exhibits high adhesiveness and insulating property derived from an amide or an ether, but has a problem of poor heat resistance after humidification since it is a structure that is easy to absorb moisture.

The laminate circuit forming method disclosed in Patent Document 5 is capable of exhibiting high adhesiveness by dissolving a resin at a high temperature. However, since the melting temperature is as high as 280 ° C or higher, it has an adverse effect on a member having low heat resistance, There was a problem of necessity of introducing one facility.

In the tape provided with the adhesive disclosed in Patent Document 6, since the epoxy resin used is bifunctional, the heat resistance after curing is insufficient.

Patent Document 7 has a problem that the flexibility is insufficient because the crosslinking density becomes excessively high although the polyimide resin and the epoxy resin can impart resistance to reflow resistance due to high thermal decomposition resistance.

In Patent Document 8, after all the butadiene (a-1), 2-hydroxybutyl methacrylate (a-2) and styrene (a-3) are mixed, polymerization is carried out using a general peroxide, (Example 1) obtained by mixing the copolymer (A) obtained from the copolymer (see Synthesis Example 1), the epoxy resin (thermosetting resin (B)) and diaminodiphenyl methane (curing agent ) Is excellent in adhesive force, heat resistance and electrical characteristics. However, the adhesive composition obtained by combining the nonblocking copolymer (A) and the epoxy resin (thermosetting resin (B)) described in the document has a problem in flexibility.

Thus, heat-curable adhesive sheets that require heat resistance and flexibility as well as adhesiveness, and satisfy other requirements, are desperately required.

The first object of the present invention is to provide a printed wiring board having a protective sheet excellent in adhesiveness, heat resistance (particularly after humidification), flexibility and resistance to plating solution resistance and electrical insulation after curing, , A thermosetting adhesive sheet provided with a sheet-like substrate, a process for producing the same, and a thermosetting adhesive sheet. A second object of the present invention is to provide a printed wiring board having a protective sheet excellent in adhesiveness, heat resistance (particularly after humidification) and flexibility, excellent in reworkability and adhesion after humidification, A heat-curable adhesive sheet provided with the thermosetting adhesive sheet, a method for producing the same, and a thermosetting adhesive sheet.

As a result of intensive investigations, the inventors of the present invention have found that, in order to solve the above-mentioned problems, the inventors of the present invention have found that by using the thermosetting composition containing the resin (A), the curing agent (B), and the specific amount of the alkali metal compound And the present invention has been accomplished.

[1] A thermosetting adhesive sheet formed from a thermosetting composition satisfying all of the following conditions (1) to (5):

(1) a resin (A), a curing agent (B), and an alkali metal compound (C).

(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-

(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).

(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.

(5) The alkali metal compound (C) is contained in an amount of 1 to 110 ppm in terms of mass of the alkali metal element in the solid content of the thermosetting composition.

[2] A thermosetting adhesive sheet formed from a thermosetting composition satisfying all of the following (1) to (4) and (6):

(1) a resin (A), a curing agent (B), and an alkali metal compound (C).

(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-

(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).

(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.

(6) The alkali metal compound (C) is contained in an amount of more than 110 ppm and not more than 10,000 ppm in the solid content of the thermosetting composition in terms of mass of the alkali metal element.

[3] The thermosetting adhesive sheet according to [1] or [2], wherein the reactive functional group is at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group and an acid anhydride group.

[4] The thermosetting adhesive sheet according to any one of [1] to [3], wherein the total amount of the reactive functional groups of 1 g of the resin (A) is 1 to 80 mg in terms of potassium hydroxide.

[5]: [1] to [4], wherein the total amount of epoxy group, isocyanate group, aziridinyl group and oxetanyl group in the curing agent (B) is 0.1 to 12 mol per 1 mol of the reactive functional group of the resin (A) The heat curable adhesive sheet according to any one of claims 1 to 3,

[6] A thermosetting adhesive sheet comprising a thermosetting adhesive sheet according to any one of [1] to [5] and two sheet-like substrates covering both surfaces of the thermosetting adhesive sheet.

[7] A heat-curable adhesive sheet comprising a sheet-like base material according to [6], wherein at least one of the two sheet-like base materials is a releasable sheet-like base material.

[8] A method for producing a thermosetting adhesive sheet, comprising: applying a thermosetting composition satisfying all of the following conditions (1) to (5) on at least one surface of a sheet-like substrate and drying the same to form a thermosetting adhesive sheet; Wherein the sheet-like base material is provided on one side of the sheet-like base material and the other sheet-like base material is superimposed on the side of the sheet-like base material.

(1) a resin (A), a curing agent (B), and an alkali metal compound (C).

(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-

(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).

(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.

(5) The alkali metal compound (C) is contained in an amount of 1 to 110 ppm in terms of mass of the alkali metal element in the solid content of the thermosetting composition.

[9] A method for producing a thermosetting adhesive sheet, comprising: applying a thermosetting composition satisfying all of the following conditions (1) to (4) and (6) on at least one surface of a sheet- A method for producing a thermosetting adhesive sheet provided with a sheet-like base material, wherein another sheet-like base material is superimposed on the other side of the sheet.

(1) a resin (A), a curing agent (B), and an alkali metal compound (C).

(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-

(3) The resin (A) has a reactive functional group capable of reacting with the curing agent (B) without having an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group.

(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.

(6) The alkali metal compound (C) is contained in an amount of more than 110 ppm and not more than 10000 ppm of the solid content of the thermosetting composition in terms of mass of the alkali metal element.

[10] A heat-curable adhesive sheet as described in any one of [1] to [5], wherein the circuit surface of the printed wiring board having a conductive circuit is protected by a sheet- And a protective sheet.

[11] A heat-curable adhesive sheet according to any one of [1] to [5], wherein the heat-curable adhesive sheet is sandwiched between the circuit surface of the printed wiring board having a conductive circuit and the sheet- Wherein the protective sheet is thermally cured.

According to the invention relating to the above-mentioned [1] and [8], it is possible to provide a printed wiring board provided with a protective sheet having both adhesive strength, heat resistance after bending and flexibility and excellent in resistance to plating solution and electric insulation after curing, A thermosetting adhesive sheet, a method for producing the same, and a thermosetting adhesive sheet. According to the invention related to the above-mentioned [2] and [9], a printed wiring board having a protective sheet having adhesiveness, heat resistance (particularly after humidification) and flexibility and excellent adhesion after reworkability and humidification, A thermosetting adhesive sheet provided with a shape substrate, a method for producing the same, and a thermosetting adhesive sheet.

[First Embodiment]

[Thermosetting adhesive sheet]

The thermosetting adhesive sheet of the first embodiment comprises a resin (A), a curing agent (B), and a specific amount of an alkali metal compound (C).

<< Resin (A) >>

The resin (A) in the first embodiment may be at least one selected from the group consisting of an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, a polyphenylene ether resin, , Fluororesin, and styrene maleic anhydride resin. These are suitably selected and used singly or in combination. Particularly, styrene elastomer and polyphenylene ether resin are preferable from the viewpoints of high insulation derived from the height of hydrophobic property and high heat resistance derived from less thermal decomposition point.

The resin (A) in the first embodiment does not have an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).

Examples of the reactive functional group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, an acid anhydride group, an amino group, an isocyanato group, a cyanate group, an isocyanato group, an imidazole group, A methacryloyl group, an aldehyde group, a hydrazide group, a hydrazone group, and a phosphoric acid group. Of these, at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group and an acid anhydride group is preferable.

The reactive functional group is preferably capable of reacting with the curing agent (B) at 20 to 200 占 폚, and more preferably at 140 to 200 占 폚.

The total amount of the reactive functional group of 1 g of the resin (A) is preferably 1 to 80 mg, more preferably 1 to 50 mg, and still more preferably 4 to 30 mg in terms of potassium hydroxide.

Since the reactive functional group contributes to the formation of crosslinking, the reactive functional group is preferably 1 mg or more in terms of potassium hydroxide in terms of heat resistance and insulation of the cured product. In view of adhesiveness and flexibility of the cured product, the reactive functional group is preferably 80 mg or less in terms of potassium hydroxide.

<< Hardener (B) >>

The curing agent (B) is at least one member selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound, and an oxetanyl group-containing compound. Two or more species may be used in combination.

<Epoxy group-containing compound>

The epoxy group-containing compound as one of the curing agents (B) is not particularly limited as long as it is a compound having an epoxy group in the molecule, and those having an average of at least two epoxy groups in one molecule can be preferably used. As the epoxy group-containing compound, for example, a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, or an epoxy resin of a cyclic aliphatic (alicyclic) epoxy resin can be used.

Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, cresol novolak type epoxy resin, phenol novolak type epoxy resin ,? -naphthol novolak type epoxy resin, bisphenol A type novolak type epoxy resin, dicyclopentadiene type epoxy resin, tetrabrombisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, tris (glycidyloxyphenyl ) Methane, or tetrakis (glycidyloxyphenyl) ethane.

Examples of the glycidylamine-type epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidylparaaminophenol, triglycidylmethaminophenol, tetraglycidylmethoxyldiaminol, and the like.

Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, and the like.

As the cyclic aliphatic (alicyclic) epoxy resin, for example, epoxycyclohexylmethyl-epoxycyclohexanecarboxylate or bis (epoxycyclohexyl) adipate may be mentioned.

The epoxy group-containing compound may be used singly or in combination of two or more kinds.

Examples of the epoxy group-containing compound include bisphenol A type epoxy resin, cresol novolak type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyl Oxyphenyl) ethane is preferably used.

<Isocyanate group-containing compound>

The isocyanate group-containing compound as one of the curing agents (B) may be any compound having an isocyanate group in the molecule, and is not particularly limited.

Specific examples of the isocyanate group-containing compound having one isocyanate group in one molecule include n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth) acryloyloxyethyl isocyanate, 1,1- ) Acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, aryl isocyanate, (meth) acryloyl isocyanate, isopropenyl- alpha, alpha -dimethyl benzyl isocyanate and the like.

Further, it is also possible to use 1,6-diisocyanatohexane, diisocyanate isophorone, diisocyanate 4,4'-diphenylmethane, polymethyldiphenylmethane diisocyanate, xylene diisocyanate, 2,4- , Diisocyanate toluene, 2,4-diisocyanate toluene, diisocyanate hexamethylene, diisocyanate 4-methyl-m-phenylene, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylene diisocyanate, Cyclohexyldiisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m (cyclohexylmethane diisocyanate), cyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, cyclohexyl diisocyanate, - diisocyanate ester compounds such as tetramethylxylene diisocyanate, P-tetramethylxylene diisocyanate and dimeric acid diisocyanate, and Compounds obtained by reacting a hydroxyl group, a carboxyl group or an amide group-containing vinyl monomer with an equivalent (such as moles) may also be used as isocyanate compounds.

Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, Methane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, Aromatic diisocyanates such as nishidine diisocyanate, 4,4'-diphenyl ether diisocyanate and 4,4 ', 4 "-triphenylmethane triisocyanate;

Butylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, dodecamethylene diisocyanate, Aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate,

ω'-diisocyanate-1,3-dimethylbenzene, ω'-diisocyanate-1,4-dimethylbenzene, ω'-diisocyanate-1,4-diethylbenzene, 1,4- Aromatic aliphatic diisocyanates such as tetramethyl xylylene diisocyanate and 1,3-tetramethyl xylylene diisocyanate,

3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate [aka: isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanate methyl) cyclohexane , And 1,4-bis (isocyanatomethyl) cyclohexane.

Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanate and lysine triisocyanate, aromatic aliphatic polyisocyanates and alicyclic polyisocyanates. A trimethylolpropane adduct of diisocyanate, a bidentate which is reacted with water, and a trimer having an isocyanurate ring.

As the isocyanate group-containing compound, a blocked isocyanate group-containing compound in which isocyanate groups in various isocyanate group-containing compounds exemplified above are protected with? -Caprolactam, MEK oxime or the like can also be used.

Specifically, the isocyanate group-containing compound is blocked with ε-caprolactam, methyl ethyl ketone (hereinafter referred to as MEK) oxime, cyclohexanone oxime, pyrazole, phenol, and the like. Particularly, the hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is very preferable because it is excellent in adhesion strength to polyimide and copper and heat resistance when used in the first embodiment.

<Aziridinyl group-containing compound>

The aziridinyl group-containing compound as one of the curing agents (B) may be any compound having an aziridinyl group in the molecule, and is not particularly limited.

Examples of the aziridinyl group-containing compound include N, N'-diphenylmethane-4,4'-bis (aziridine carboxide), N, N'- -Bis (1-aziridine carboxamide), bisisophthaloyl-1- (2-methyl aziridine), tri-1-aziridinylphosphine oxide, N, Bis (1-aziridine carboxamide), trimethylolpropane-tri-? -Aziridinylpropionate, tetramethylolmethane-tri-? -Aziridinylpropionate, tris- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane tris [3- (1-aziridinyl) propionate], trimethylolpropane tris [3- Butyrate], trimethylolpropane tris [3- (1- (2-methyl) aziridinyl) propionate], trimethylolpropane tris [3- (1-aziridinyl) -2-methylpropionate] , 2,2'-bis hydroxymethyl butanol tris [3- (1-aziridinyl) propionate], Pentaerythritol tetra [3- (1-aziridinyl) propionate], diphenylmethane-4,4-bis-N, N'- ethylene urea, 1,6-hexamethylene bis- Urea, 2,4,6- (triethyleneimino) -sym-triazine, and bis [1- (2-ethyl) aziridinyl] benzene-1,3-carboxylate amide.

Particularly, when used in the first embodiment, 2,2'-bis hydroxymethyl butanol tris [3- (1-aziridinyl) propionate] can suppress the protrusion during thermal pressing, The heat resistance can be improved while maintaining the flexibility of the coating film, which is suitably used in the first embodiment.

<Oxetanyl group-containing compound>

Examples of the oxetanyl group-containing compound as one of the curing agent (B) include 1,4-bis {[(3-ethyloxetan-3- yl) methoxy] methyl} benzene, 3- [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4'-bis [ (2-ethyl-2-oxetanyl) ethanol and terephthalic acid, (2-ethyl-2-oxetanyl) ethanol and phenol An esterified product of (2-ethyl-2-oxetanyl) ethanol with a polyvalent carboxylic acid compound, and the like.

The curing agent (B) used in the first embodiment is preferably an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group (hereinafter may be referred to as &quot; epoxy group &quot;) with respect to 1 mol of the reactive functional group in the resin (A) Is preferably in the range of 0.1 to 12 mol, more preferably 0.3 to 10 mol, and still more preferably 0.5 to 5 mol. With respect to the reactive functional group of the resin (A), by setting the epoxy group or the like in the curing agent (B) to 0.1 mol or more, the crosslinking density can be increased to improve the heat resistance, insulation and adhesiveness. By controlling the epoxy group or the like to 20 mol or less, the flexibility and electrical insulation can be improved.

<< Alkali metal compound (C) >>

The heat curable adhesive sheet (solid content of the thermosetting composition forming the sheet) of the first embodiment contains 1 to 110 ppm of the alkali metal compound (C) in terms of mass of the alkali metal element in view of resistance to the plating solution after curing. The plating solution resistance can be imparted when the content of the alkali metal compound (C) in terms of mass of the alkali metal element is 1 ppm or more. The reason is not clear, but it is considered that the alkali metal having a high ionization tendency promotes ionization during the immersion of the plating liquid, and the reactive functional group of the resin (A) forms a hard metal bridge.

In addition, since the content of the alkali metal compound (C) in terms of mass of the alkali metal element is 110 ppm or less, the insulating property can be secured. If it contains 110 ppm or more, the electrical insulation may deteriorate. The content of the alkali metal compound (C) in terms of mass of the alkali metal element is preferably 10 to 90 ppm, more preferably 30 to 70 ppm.

The alkali metal compound (C) contained in the thermosetting adhesive sheet of the first embodiment may be contained in the resin (A), the curing agent (B), other curing agents described below and various additives, Or may be blended separately from the curing agent (B) and the like. In the case of the resin (A) or the curing agent (B) containing a large amount of the alkali metal compound (C), the amount of the alkali metal compound (C) may be reduced by washing.

When the alkali metal compound (C) is contained in the resin (A), the curing agent (B), other curing agents to be described later, and various additives, the alkali metal compound (C) , Or may be mixed in the process

The element-converted content X (ppm) of the alkali metal compound (C) contained in 1 g of the solid component (thermosetting adhesive sheet) of the thermosetting composition can be obtained as follows.

Content of alkali metal compound (C): Y (g),

Molecular weight of the alkali metal compound (C): A,

And the amount of the alkali metal element in the alkali metal compound (C): B,

X = [Y x (B / A)] x 10 ⁶

For example, in the case of lithium carbonate (Li ₂ CO ₃ )

Molecular weight A of 73.89,

The amount B of the alkali metal contained is 6.94 x 2,

When 0.0001 g of lithium carbonate is contained in 1 g of the solid (thermosetting adhesive sheet) of the thermosetting composition,

X = [0.0001 x (6.94 x 2) /73.89)] x 10 ⁶ = 18.8.

The kind and amount of the alkali metal compound (C) contained in each of the raw materials contained in the solid component (thermosetting adhesive sheet) of the thermosetting composition are respectively obtained and the content of the alkali metal compound (C): Y g) can be obtained to obtain the element-converted content X (ppm), but the element-converted content X (ppm) can also be obtained as follows.

That is, the solid component (thermosetting adhesive sheet) of an arbitrary mass of the thermosetting composition is decomposed by the following method, and the resulting solution is subjected to ICP emission spectroscopy (hereinafter referred to as ICP analysis) (C) can be obtained.

When both of the homogeneous alkali metal compounds are contained, for example, when lithium carbonate and lithium acetate are included, the ICP analysis method can determine the content in terms of the lithium element.

Specifically, a sample to be weighed can be thermally decomposed with nitric acid, diluted to a constant volume, and then measured with an ICP analyzer, and quantified by a calibration curve made of a standard solution of the target element.

Specific examples of the alkali metal compound (C) include, but are not limited to, hydroxides of alkali metals, carbonates of alkali metals, hydrogencarbonates of alkali metals, carboxylates of alkali metals, and alkali metal salts.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like.

Examples of the alkali metal carbonate include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate and the like, and hydrates thereof.

Examples of the alkali metal hydrogencarbonate include sodium hydrogencarbonate, potassium hydrogencarbonate, etc., and hydrates thereof.

As the carboxylic acid salt of an alkali metal, a carboxylic acid salt having 1 to 10 carbon atoms is preferable, and a carboxylic acid salt having 1 to 13 carbon atoms is more preferable.

Specific examples of the carboxylic acid include straight chain saturated fatty acids such as acetic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enantic acid, capric acid, and pelargonic acid; Aliphatic dicarboxylic acids such as oxalic acid, fumaric acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid; Hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxybutyric acid, tartaric acid, malic acid and mevalonic acid; Aromatic carboxylic acids such as benzoic acid, terephthalic acid, isophthalic acid and orthophthalic acid, and hydrates thereof.

Among them, a hydroxide of an alkali metal, a nitrate of an alkali metal, and a carbonate of an alkali metal are preferable, and a hydroxide of an alkali metal is more preferable because an alkali metal tends to be ionized.

Examples of the alkylaluminum metal include methyllithium, i-propyllithium, sec-butyllithium, n-butyllithium, t-butyllithium and n-dodecyllithium.

Other examples include phenyl lithium,? - and? -Naphthyl lithium, styryl lithium, benzyl lithium and the like.

The alkali metal is an element belonging to Group 1 in the periodic table, and specific examples thereof include sodium, potassium, lithium, rubidium, and cesium.

<< Other additives >>

The thermosetting composition (thermosetting adhesive sheet) of the first embodiment may contain other curing agents in addition to the resin (A), the curing agent (B) and the alkali metal compound (C) within the range not impairing the physical properties.

Specific examples of other curing agents include, but are not limited to, carbodiimide group-containing compounds, benzoxadine compounds,? -Hydroxyalkylamide group-containing compounds, and sulfur-containing compounds.

<Carbodiimide group-containing compound>

As the carbodiimide group-containing compound, one of the other curing agents, Carbodite series of Nissei Bowseki Co., Ltd. is mentioned. Of these, carboditlite V-01, 03, 05, 07, and 09 are preferred because of their excellent compatibility with organic solvents. When used in the first embodiment, an improvement in adhesion is expected, so that it is suitably used.

<Benzoxazine Compound>

Pa, "P-alP", "P-ala", "B-ala", Macromolecules, 34, 7257 (described in Macromolecules, 36, 6010 (2003)) as the benzooxazine compound P-appe "," B-appe "," Ba type benzoxadine "," Fa type benzoxazine ", and" Bm type benzoxazine "manufactured by Shikoku Kasei Co., Ltd. are listed.

<? -hydroxyalkylamide group-containing compound>

N, N, N ', N'-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Maskemis Co., Ltd.) is used as the compound having one- And various kinds of compounds.

&Lt; Sulfur-containing compound &

As one of the other curing agents, sulfur-containing compounds, thiol compounds, sulfide compounds, and polysulfide compounds are mentioned. When used in the first embodiment, adhesion and heat resistance can be expected to be improved and used accordingly.

<Thiol compound>

The thiol compound contains at least, for example, a thiol group and a hydrocarbon group of a linear, branched, or cyclic type (cyclic). Two or more thiol groups may be contained. The hydrocarbon group is saturated and unsaturated. A part of the hydrogen atoms of the hydrocarbon group may be substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, an alkoxysilyl group or the like. More specifically, examples of the colorless thiol include 1-propanethiol, 3-mercaptopropionic acid, (3-mercaptopropyl) trimethoxysilane, 1-butanethiol, 1-hexanethiol hydrochloride, 1-heptanethiol, 7-carboxy-1-hexanethiol, 1-hexanethiol, 1-hexanethiol, 1-hexanethiol, 1-hexanethiol, mercapto, isoamyl mercaptan, cyclopentanethiol, 1-heptanethiol, 1-heptanethiol, 1-octanethiol, tert-octanethiol, 8-hydroxy-1-octanethiol, 1-decanethiol, 1-naphthalenethiol, 2-naphthalenethiol, 1-undecenethiol, 2-naphthalenethiol, 1-undecane thiol, 1-undecane thiol, 1-hexadecane thiol, 16-hydroxy-1-undecane thiol, Hexadecanethiol, 16-amino-1-hexadecanethiol hydrochloride, 1-octadecanethiol , 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,2-benzenedithiol, 1,9-nonanedithiol, , 3,5-benzenetriethiol, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. These thiols may be used alone or in combination of two or more.

<Sulfide compound>

The sulfide compound contains at least, for example, a sulfide group and a hydrocarbon group of linear, branched, or ring type. Two or more sulfide groups may be contained. A part of the hydrogen atoms of the hydrocarbon group may be substituted with a hydroxyl group, an amino group, a carboxyl group, a halogen atom, an alkoxysilyl group and the like.

More specifically, examples of sulfide compounds include propyl sulfide, furfuryl sulfide, hexyl sulfide, phenyl sulfide, phenyltrifluoromethyl sulfide, bis (4-hydroxyphenyl) sulfide, But are not limited to, heptylsulfide, octylsulfide, nonylsulfide, desilsulfide, dodecylsulfide, dodecylsulfide, tetradecylsulfide, hexadecylsulfide, octadecylsulfide, bis (triethoxysilylpropyl) tetra And sulphide. These sulfides may be used alone or in combination of two or more.

&Lt; Polysulfide compound >

Examples of the polysulfide compound include 2-hydroxyethyl disulfide, propyl disulfide, isopropyl disulfide, 3-carboxypropyl disulfide, aryl disulfide, isobutyl disulfide, tert-butyl disulfide, But are not limited to, disulfide, isoamyl disulfide, 5-carboxypentyl disulfide, furfuryl disulfide, hexyl disulfide, cyclohexyl disulfide, phenyl disulfide, 4-aminophenyl disulfide, heptyl disulfide, , Benzyl disulfide, tert-octyl disulfide, decyl disulfide, 10-carboxydecyl sulfide, hexadecyl disulfide, and the like can be used.

In the first embodiment, the amount of the other curing agent to be used is not particularly limited, but it is preferably 0.01 to 20 mol, more preferably 0.5 to 10 mol, per 1 mol of the reactive functional group of the resin (A) And more preferably 0.1 to 5 mol.

It is more preferable that it contains 0.01 to 20 mol, more preferably 0.5 to 10 mol, and even more preferably 0.1 to 5 mol, relative to 1 mol of the epoxy group or the like in the curing agent (B).

<Filler>

Next, the fillers usable in the first embodiment will be described in detail.

The thermosetting adhesive sheet of the first embodiment may contain a filler for the purpose of imparting flame retardancy, controlling the flowability of the adhesive, and improving the modulus of elasticity of the cured product.

The filler is not particularly limited, and examples of the shape include a spherical shape, a powder shape, a fibrous shape, a needle shape, and a scaly shape.

As the filler, for example, a multi-layered product using silicon, acrylic, styrene butadiene rubber, butadiene rubber, etc. in addition to polytetrafluoroethylene powder, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, A polymer filler such as a core cell of a structure;

(Poly) phosphate compounds such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate amide, ammonium polyphosphate, ammonium carbamate, and polyphosphoric acid carbamate; Compounds such as phosphazene compounds, phosphonic acid compounds, phosphonic acid compounds, aluminum diethylphosphinic acid, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, aluminum polyethylene terephthalate, Phosphorus flame retardant fillers such as phosphine oxide compounds, phosphorane compounds, and phosphoramide compounds;

Nitrogen-based flame retardant fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole-based compounds, tetrazole compounds, diazo compounds and urea;

Silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, xonotlite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogenphosphate, calcium phosphate, glass flake, hydrated glass, calcium titanate, Magnesium oxide, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, Inorganic fillers such as magnesium carbonate, calcium carbonate, barium carbonate, zinc borate and aluminum borate.

Among them, it is preferable to use a non-halogen flame retardant such as a phosphorus-based flame retardant filler or a nitrogen-based flame retardant filler in consideration of the influence of the environment which has recently been discussed. Among them, the filler is preferably added to the thermosetting composition of the first embodiment A phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, and melamine cyanurate, which are effective by the flame retardancy, are preferably used. In addition, it is preferable to use polytetrafluoroethylene powder for further lowering the dielectric constant and dielectric tangent, and it is possible to obtain a cured product having excellent balance between adhesiveness, flexibility, electrical insulation and heat resistance as well as dielectric properties . In the first embodiment, these fillers can be used singly or in combination.

The average particle diameter (D50) of these fillers is preferably 0.1 m to 25 m. When a filler having an average particle diameter of close to 0.1 m is used, the improvement effect by the filler is easily obtained and the stability of the dispersion and the dispersion are liable to be improved. Further, when a filler having an average particle diameter close to 25 m is used, the mechanical properties of the cured film are likely to be improved.

The amount of the filler to be added is preferably 0.01 to 500 parts by mass with respect to 100 parts by mass of the resin (A). If the amount of the filler added is less than this range, it is difficult to obtain an improvement effect by the filler, and if the filler content is more than this range, the mechanical properties of the cured film may be seriously impaired.

The method of adding the filler is not particularly limited and any conventionally known method may be used. Specifically, a method of adding the filler to the polymerization solution before or during polymerization, a method of kneading the filler using three rolls or the like, And a method of mixing and dispersing them. In order to disperse the filler well and to stabilize the dispersed state, a dispersant, a thickening agent or the like may be used in a range not affecting the physical properties of the adhesive sheet.

In addition, the heat-curable adhesive sheet of the first embodiment may contain optional components such as a dye, a pigment, an antioxidant, a polymerization inhibitor, a defoaming agent, a leveling agent, an ion scavenger, a moisturizer, A preservative, an antibacterial agent, an antistatic agent, an anti-blocking agent, an ultraviolet absorber, an infrared absorber, and an electromagnetic shielding agent.

Japanese Patent Laid-Open Publication No. 2011-105916 discloses an epoxy resin composition containing as a main component a urethane-modified epoxy resin and an epoxy resin curing agent. This epoxy resin composition exhibits adhesiveness derived from urethane and a good circuit embedding property, but has a problem that it contains a lot of high-polarity urethane bonds and lowers electrical insulation. Further, Japanese Patent Application Laid-Open No. 2007-077330 discloses a curable composition comprising an oxetane structure and a thermal cation curing catalyst as a main component. This curable composition exhibits low dielectric constant due to inhibition of the formation of hydroxyl groups and processing stability resulting from low cure shrinkage which is an advantage of cationic polymerization. However, there is a concern about metal corrosion due to acid generation, There is a problem in terms of stability. Further, Japanese Patent Laid-Open Publication No. 2011-37927 discloses an adhesive for optical use which further contains an acrylic polymer, an isocyanate curing agent, and an epoxy or metal chelating curing agent. However, this adhesive sheet is used after adhering, that is, after curing the sheet attached to a glass plate, and does not disclose that the adhesive sheet before curing is sandwiched between adherends to thermally cure.

In addition, Japanese Patent Application Laid-Open Nos. 2008-195943 and 2008-121005 disclose an adhesive film containing an epoxy resin, a curing agent, and a macromolecule compound which is incompatible with an epoxy resin. However, in these documents, a fine phase separation structure is formed of two components for non-use, resulting in an excellent heat stress absorbing property and an adhesive film having a high resistance to cracking. However, since a minute interface is increased There is a problem that the plating solution resistance is insufficient.

On the other hand, the thermosetting adhesive sheet according to the first embodiment exerts the effect of having adhesiveness, heat resistance after moistening, and flexibility, and excellent resistance to plating solution and electric insulation after curing.

[Thermosetting adhesive sheet provided with sheet-shaped substrate]

The heat-curable adhesive sheet provided with the sheet-like base material of the first embodiment can be obtained, for example, as follows.

The thermosetting adhesive composition as a solution or a dispersion liquid is applied to at least one surface of a sheet-like substrate and then dried at a temperature of usually 40 to 150 ° C so that the sheet-like substrate is adhered to the so-called B- Can be obtained. Next, the other surface of the thermosetting adhesive sheet is covered with another sheet-like substrate to obtain a thermosetting adhesive sheet provided with the sheet-like substrate of the first embodiment.

It is preferable that at least one of the sheet-like substrates used is a peelable sheet-like substrate. That is, the heat-curable composition in the form of solution or dispersion may be applied to a releasable sheet-like substrate to form a heat-curable adhesive sheet, and then the other surface of the heat-curable adhesive sheet may be covered with another releasable sheet- , And may be covered with a sheet-like base material which does not have a peelability which becomes an adherend. Alternatively, a thermosetting composition in the form of a solution or a dispersion is applied to a sheet-like base material that does not have releasability as an adherend and dried to form a thermosetting adhesive sheet, and then the other surface of the heat- It may be covered with a substrate.

The dried film thickness of the thermosetting adhesive sheet is preferably 5 to 500 占 퐉, more preferably 10 to 100 占 퐉, from the viewpoint of exhibiting sufficient adhesiveness and solder heat resistance and easy handling.

Examples of application methods include comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating and spin coating.

Examples of the sheet-like base material that does not have peelability include various plastic films such as a polyimide film, a polyester film, a polyphenylene ether film, a polyphenylene sulfide film, a polystyrene film, a polycarbonate Film, and polyether ether ketone film.

Among the sheet-like substrates used, those having peelability include those obtained by peeling off various plastic films and those peeled off from paper. Examples of various plastic films to be subjected to the peeling treatment include polyester films and polyolefin films.

[Sheet-shaped cured product], [Printed wiring board provided with a protective sheet]

The sheet-like cured product of the first embodiment is obtained by curing the thermosetting adhesive sheet of the first embodiment by heat curing, for example, at a temperature of about 40 to 200 ° C.

In the case of using a thermosetting adhesive sheet provided with a sheet-like base material in which one surface of a thermosetting adhesive sheet is covered with a peelable sheet-like base material and the other surface is covered with an adherend (for example, a polyimide film or a polyester film) Will be described.

The releasable sheet-like base material is removed from the heat-curable adhesive sheet provided with the sheet-like base material. (For example, the circuit surface side of the printed wiring board having a conductive circuit) on the exposed thermosetting adhesive sheet. Subsequently, the thermosetting adhesive sheet put between the two covers is thermally cured by heating and pressing to obtain a sheet-like cured product.

This makes it possible to obtain a printed wiring board provided with a protective sheet obtained by protecting the circuit surface of a printed wiring board having a conductive circuit with a sheet-shaped substrate through a sheet-shaped cured product.

Next, a case of using a thermosetting adhesive sheet provided with a sheet-like base material on which both releasable sheet-like base materials are covered on both sides of the thermosetting adhesive sheet will be described.

One separable sheet-like base material is removed from the thermosetting adhesive sheet provided with the sheet-like base material. An adherend (for example, a polyimide film or a polyester film) is overlaid on the exposed thermosetting adhesive sheet. The other releasable sheet-like base material covering the other surface of the thermosetting adhesive sheet is removed. (For example, the circuit surface side of the printed wiring board having a conductive circuit) on the exposed thermosetting adhesive sheet. Then, the thermosetting adhesive sheet put between the two covers is heat-cured by heating and pressing. The circuit surface side of the printed circuit board having the conductive circuit may be overlapped on the side on which the peelable sheet-like base material is first removed and the other side of the heat-curable adhesive sheet may be overlapped with the polyimide film or the polyester film.

As a printed wiring board having a conductive circuit, a flexible printed wiring board in which a conductive circuit is formed on a flexible or insulating plastic film such as polyester or polyimide is mentioned.

As a method of providing the conductive circuit, for example, there is a method in which a photosensitive etching resist layer is formed on a copper foil of a flexible copper foil obtained by providing a copper foil on a base film with or without an adhesive layer, There may be exemplified a method of forming a conductive circuit with a copper foil by curing only the exposed portion by exposure and then removing the copper foil of the unexposed portion by etching and peeling off the remaining resist layer.

Alternatively, a method may be employed in which only necessary circuits are provided on the base film by means such as sputtering or plating. Alternatively, a conductive circuit is formed on the base film by a printing technique using a conductive ink containing silver or copper particles.

The thermosetting adhesive sheet of the first embodiment can be used as follows in addition to being suitably used for the production of a printed wiring board provided with a protective sheet.

&Lt; Multiple layers of flexible printed wiring &

A multilayer flexible printed wiring board can be obtained by heating and pressing the thermosetting adhesive sheet of the first embodiment between a plurality of flexible printed wiring lines to cure the thermosetting adhesive sheet.

<Bonding of base film and copper foil for flexible printed wiring board>

For example, the thermosetting adhesive sheet may be cured by heating and pressing the thermosetting adhesive sheet of the first embodiment between the polyimide film and the copper foil.

[Second Embodiment]

[Thermosetting adhesive sheet]

The thermosetting adhesive sheet of the second embodiment includes a resin (A), a curing agent (B), and a specific amount of an alkali metal compound (C). Hereinafter, the same portions as those in the first embodiment will be appropriately omitted.

<< Resin (A) >>

The resin (A) in the second embodiment can be preferably used in the same manner as in the first embodiment except that the resin (A) in the second embodiment is an acrylic resin, a polyester resin, a polyurethane resin, a polyurethane polyurea resin, a polyamide resin, a polyimide resin, a polycarbonate resin, A styrene-based elastomer, a fluororesin, and a styrene-maleic anhydride-based resin. These are used singly or in combination. Particularly, styrene elastomer and polyphenylene ether resin are preferable from the viewpoints of high insulation derived from the height of hydrophobic property and high heat resistance resulting from less thermal decomposition point. Here, the styrene-based elastomer refers to a block copolymer in which a portion composed of styrene and a portion composed of butadiene, isoprene, ethylene, or the like form a &quot; block &quot;.

The resin (A) in the second embodiment has a reactive functional group capable of reacting with the curing agent (B) without an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group. Specific examples of the reactive functional groups are described in the first embodiment. Among these, at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group and an acid anhydride group is preferable.

The reactive functional group is preferably capable of reacting with the curing agent (B) at 20 to 200 占 폚, and more preferably at 140 to 200 占 폚.

The total amount of the reactive functional groups of 1 g of the resin (A) is preferably 1 to 80 mg, more preferably 1 to 50 mg, still more preferably 4 to 30 mg in terms of potassium hydroxide.

Since the reactive functional group contributes to the formation of crosslinking, it is preferable that the reactive functional group is 1 mg or more in terms of potassium hydroxide in view of the heat resistance and the insulating property of the cured product. In view of adhesiveness and bending property of the cured product, the reactive functional group is preferably 80 mg or less in terms of potassium hydroxide.

<< Hardener (B) >>

The curing agent (B) is at least one member selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound, and an oxetanyl group-containing compound. Two or more species may be used in combination.

Specific compounds and preferred examples of the epoxy group-containing compound, the isocyanate group-containing compound, the aziridinyl group-containing compound and the oxetanyl group-containing compound are as described in the first embodiment.

The curing agent (B) used in the second embodiment is preferably a combination of an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group (hereinafter also referred to as &quot; epoxy group &quot;) with respect to 1 mol of the reactive functional group in the resin (A) Is preferably in the range of 0.1 to 12 mol, more preferably 0.3 to 10 mol, and still more preferably 0.5 to 5 mol. With respect to the reactive functional group of the resin (A), by setting the epoxy group or the like in the curing agent (B) to 0.1 mol or more, the crosslinking density can be increased to improve the heat resistance, insulation and adhesiveness. By setting the epoxy group or the like to 20 mol or less, the flexibility and electrical insulation can be improved.

<< Alkali metal compound (C) >>

The heat-curable adhesive sheet (solid content of the thermosetting composition forming the sheet) of the second embodiment has an alkali metal compound (C) in a mass conversion of more than 110 ppm and not more than 10000 ppm Or less. Since the content of the alkali metal compound (C) in terms of mass of the alkali metal element is more than 110 ppm, re-peelable reworkability is imparted when the uncured adhesive sheet is stuck at room temperature. The reason is not clear, but it is considered that the alkali metal having a high polarity shifts to the substrate surface side in the adhesive sheet and hinders the tackiness upon uncured.

In addition, since the content of the alkali metal compound (C) in terms of mass of the alkali metal element is 10,000 ppm or less, adhesion after humidification can be ensured. The content of the alkali metal compound (C) in terms of mass of the alkali metal element is preferably more than 110 ppm, more preferably 9000 ppm or less, and more preferably 300 to 3000 ppm.

The alkali metal compound (C) contained in the thermosetting adhesive sheet of the second embodiment may be contained in the resin (A), the curing agent (B), other curing agents described below and various additives, , The curing agent (B), and the like. In the case of the resin (A) or the curing agent (B) containing a large amount of the alkali metal compound (C), the amount of the alkali metal compound (C) may be reduced by washing.

When the alkali metal compound (C) is contained in the resin (A), the curing agent (B), other curing agents to be described later, and various additives, the alkali metal compound (C) It may be a decomposition product or a process mixture.

The element-converted content X (ppm) of the alkali metal compound (C) contained in 1 g of the solid component (thermosetting adhesive sheet) of the thermosetting composition can be obtained in the same manner as in the first embodiment.

Specific examples of the alkali metal compound (C) are the same as those described in the first embodiment in the second embodiment.

<< Other additives >>

The thermosetting composition (thermosetting adhesive sheet) of the second embodiment may contain other curing agents in addition to the resin (A), the curing agent (B) and the alkali metal compound (C) have.

Specific examples of other curing agents include, but are not limited to, carbodiimide group-containing compounds, benzoxadine compounds,? -Hydroxyalkylamide group-containing compounds, and sulfur-containing compounds.

Examples of suitable examples of the carbodiimide group-containing compound, the benzoxazine compound, the? -Hydroxyalkylamide group-containing compound, and the sulfur-containing compound are the same as those of the first embodiment. The thiol compound, the sulfide compound, and the polysulfide compound, which are suitable examples of the sulfur-containing compound, are also the same as in the first embodiment.

In the second embodiment, the amount of other curing agent to be used is not particularly limited, but a suitable amount for 1 mol of the reactive functional group of the resin (A) and a suitable amount for 1 mol of the epoxy group or the like in the curing agent (B) As shown in Fig.

<Filler>

The thermosetting adhesive sheet of the second embodiment may contain a filler for the purpose of imparting flame retardancy, controlling the flowability of the adhesive, and improving the modulus of elasticity of the cured product.

The filler is not particularly limited, but an appropriate shape and specific examples are the same as those described in the first embodiment. It is preferable to use a non-halogen flame retardant such as a phosphorus-based flame retardant filler or a nitrogen-based flame retardant filler in consideration of the influence on the environment which is being recently discussed. Among them, , Phosphine compounds, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate and the like are preferably used. Further, polytetrafluoroethylene powder is preferably used in view of lowering the dielectric constant and dielectric tangent, and has an effect of improving dielectric properties and electrical insulation in addition to adhesiveness, flexibility and heat resistance. In the second embodiment, these fillers may be used singly or in combination.

The preferable range of the average particle diameter (D50) of these fillers is also the same as in the first embodiment. The preferable range of the filler addition amount and the technical significance are also the same as those of the first embodiment. In addition, the method of adding the filler is not particularly limited, and any conventionally known method may be used. As a specific example, the first embodiment can be mentioned.

In addition, the heat-curable adhesive sheet of the second embodiment can further contain the additives described in the first embodiment as optional components within the scope of not impairing the object.

However, when there is a problem in position or the like when the adhesive sheet is adhered to an object to be adhered, it is required to peel off the adhesive sheet or the like and to rework it without leaving an adhesive on the object to be adhered. In addition, it is also required to be able to exhibit high adhesion even after being placed under a high humidity environment after bonding. As a known adhesive sheet, International Publication No. 2013/002001 discloses a thermosetting adhesive sheet having a thermosetting adhesive layer having a glass transition point of -50 ° C or more and 10 ° C or less and 20 ° C or more and 100 ° C or less, . According to this thermosetting adhesive sheet, an acrylic polymer having a glass transition point of -50 DEG C or more and 10 DEG C or less is contained, thereby exhibiting adhesive force and heat resistance after humidification. However, there is a problem that reworkability is insufficient by including a low molecular weight component.

In addition, International Publication WO02074135 discloses a resin composition for an adhesive containing a thermoplastic resin, an inorganic filler, a solvent, and an epoxy resin. According to the resin composition for an adhesive, an adhesive force can be developed after high humidification by increasing the acid value of the thermoplastic resin, but there is a problem that the flexibility is insufficient due to high crosslinking density.

On the other hand, Japanese Patent Laid-Open Publication No. 2017-31383 discloses a resin composition containing a butylene resin, a resin having at least one kind of group selected from an epoxy group and an oxetanyl group, and a photopolymerization initiator, The resin composition exhibits reworkability by including a relatively rigid epoxy or oxetane resin, but has a problem that the heat resistance is insufficient due to the butylene resin. In addition, International Publication No. 2013/073364 discloses a resin composition containing an acryl oligomer, an acrylic monomer, a thiol compound, and a photoinitiator, which exhibits good bending properties but has a problem of insufficient adhesion after humidification.

On the other hand, the thermosetting adhesive sheet according to the second embodiment exhibits the adhesive property, the heat resistance after the humidification and the bending property, and also exhibits the excellent adhesiveness after reworkability and humidification.

[Thermosetting adhesive sheet provided with sheet-shaped substrate]

The method of producing the thermosetting adhesive sheet provided with the sheet-like substrate of the second embodiment is not particularly limited, but the same method as that of the first embodiment can be exemplified.

[Sheet-shaped cured product], [Printed wiring board provided with a protective sheet]

The sheet-like cured product of the second embodiment is obtained by curing the heat-curable adhesive sheet of the second embodiment by heat-curing, for example, at a temperature of about 40 to 200 ° C.

In the case of using a thermosetting sheet provided with a sheet-like base material on one side of which is covered with a peelable sheet-like base material and the other side is covered with an adherend (for example, a polyimide film or a polyester film) Can also be obtained in the same manner as in the first embodiment.

&Lt; Conductive adhesive sheet &

In the thermosetting adhesive sheet of the second embodiment, a conductive filler such as copper or silver, or a conductive filler such as carbon is mixed and dispersed in addition to the resin (A), the curing agent (B) and the specific amount of the alkali metal compound Can be used as a conductive thermosetting adhesive sheet in sheet form.

&Lt; Electromagnetic wave shielding sheet &

Furthermore, the thermosetting adhesive sheet of the second embodiment can be also used as an electromagnetic wave shielding sheet by making a multi-layer structure with the insulating layer using the conductive thermosetting adhesive sheet produced above. Further, not only the conductive layer portion but also the heat-curable adhesive sheet of the second embodiment can be used as an insulating layer.

<Heat-conductive adhesive sheet>

In addition, the thermosetting adhesive sheet of the second embodiment is a thermosetting adhesive sheet obtained by mixing and dispersing thermally conductive inorganic filler, metal filler and the like in addition to the resin (A), the curing agent (B) and the specific amount of the alkali metal compound The thermosetting composition can be used as a thermally conductive thermosetting adhesive sheet made into a sheet shape.

[Example]

Hereinafter, the present invention will be more specifically described by way of examples, but the following examples do not limit the scope of rights of the present invention. In the examples, "part" and "%" are "mass part" and "mass%", respectively, and Mw means mass average molecular weight.

<Method for measuring phenolic hydroxyl group value and alcoholic hydroxyl group value>

The phenolic and alcoholic hydroxyl groups are those in which the amount of hydroxyl groups contained in 1 g of resin solids (hereinafter also referred to as &quot; samples &quot;) is adjusted to the amount of potassium hydroxide necessary to neutralize the acetic acid bound to the hydroxyl groups when the hydroxyl group is acetylated ).

The hydroxyl value is measured in accordance with JIS K0070 and calculated in consideration of the acid value as shown in the following formula.

About 1 g of sample (resin solid content) is precisely weighed in an Erlenmeyer flask and 100 mL of cyclohexanone solvent is added to dissolve. Then exactly 5 mL of an acetylating agent (25 g of anhydrous acetic acid dissolved in pyridine to make a volume of 100 mL) was added and mixed for about 1 hour. Here, the phenolphthalein solution is added as an indicator and is maintained for 30 seconds. Then, the solution is titrated with 0.5N alcoholic potassium hydroxide solution until it becomes pale red.

The hydroxyl value was determined by the following formula (unit: mgKOH / g).

(MgKOH / g) = [{(b-a) x F x 28.05} / S] + D,

but,

S: Weight of sample (g)

a: consumption of 0.5N alcoholic potassium hydroxide solution (mL)

b: Consumed amount of 0.5N alcoholic potassium hydroxide solution (mL)

F: Potency of 0.5N Alcoholic Potassium Hydroxide Solution

D: acid value (mgKOH / g)

&Lt; Measurement of acid value &

About 1 g of sample (resin solid content) is precisely weighed in a revolving Erlenmeyer flask and 100 mL of cyclohexanone solvent is added to dissolve. Here, phenolphthalein solution is added as an indicator and kept for 30 seconds. The solution is then titrated with 0.1N alcoholic potassium hydroxide solution until the solution becomes pale red. The acid value was determined by the following formula (unit: mgKOH / g).

Acid value (mgKOH / g) = (5.611 x a x F) / S

but,

S: Weight of sample (g)

a: consumption of 0.1N alcoholic potassium hydroxide solution (mL)

F: Potency of 0.1N Alcoholic Potassium Hydroxide Solution

&Lt; Measurement method of acid anhydride value >

Approximately 1 g of the sample (resin solid content) was precisely weighed in a revolving Erlenmeyer flask, and 100 mL of 1,4-dioxane solvent was added to dissolve. 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mass ratio of 1.49 / 800/80) was added thereto, followed by stirring for 15 minutes to complete the reaction.

Thereafter, excess octylamine was titrated with a mixed solution of 0.02M perchloric acid and 1,4-dioxane. Further, 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mixing ratio of mass: 1.49 / 800/80) without addition of a sample was measured as a blank. The acid anhydride content is determined by the following formula (unit: mgKOH / g).

Acid anhydride value (mgKOH / g) = 0.02 x (B-S) x F x 56.11 / W

B: Appropriate amount of blank (mL)

S: Amount of the mixed solution (mL)

W: solid content (g)

F: 0.02 mol / L Potency of perchloric acid

&Lt; Measurement method of mass average molecular weight (Mw)

The Mw was measured by GPC (gel permeation chromatography) &quot; HPC-8020 &quot; manufactured by TOSOH CORPORATION. GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size. In the measurement in the first embodiment, two columns of "LF-604" (product of Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) were connected in series and used at a flow rate of 0.6 mL / min, And the column temperature was 40 DEG C to determine the mass average molecular weight (Mw) in terms of polystyrene.

[Synthesis Example 1]

<Synthesis Example of Acrylic Resin>

300 g of methyl ethyl ketone (hereinafter referred to as MEK) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer, and heated to 80 DEG C while introducing nitrogen gas into the container. 30 g of butyl methacrylate, 28 g of methyl methyl acrylate, 3 g of a 1: 1 (by mass ratio) mixture of lauryl methacrylate and tridecyl methacrylate, 12 g of methacrylic acid, 2,2'-azobisisobutyronitrile 0.8 g was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was reacted at 80 ° C for 3 hours. Then, 1.2 g of 2,2'-azobisisobutyronitrile dissolved in 50 g of MEK was added and reacted at 80 ° C. for 1 hour to obtain an acrylic resin solution. The mass average molecular weight was 52,000, and the acid value was 78.2 mgKOH / g.

[Synthesis Examples 2 to 3]

Synthesis was carried out according to the composition shown in Table 1 in the same manner as in Synthesis Example 1 to obtain an acrylic resin.

[Synthesis Example 4]

<Synthesis Example of Polyester Resin>

A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer was charged with 57.6 g of sebacic acid, 3.2 g of trimesic acid, 27.5 g of cyclohexanedimethanol, 9.7 g of 1,6- 0.012 g of butyl titanate was added thereto, and the mixture was stirred until the exothermic temperature became constant. When the temperature stabilized, the temperature was elevated to 110 ° C. After confirming that the temperature was stable, the temperature was elevated to 120 ° C after 30 minutes, and the dehydration reaction was continued while the temperature was elevated by 10 ° C every 30 minutes. When the temperature reached 230 deg. C, the reaction was continued at the same temperature for 3 hours, and maintained at a vacuum of about 2 kPa for 1 hour. Thereafter, the temperature was lowered to obtain a polyester resin. The mass average molecular weight was 3.2 million, and the acid value was 39.8 mgKOH / g.

[Synthesis Examples 5 to 10]

Synthesized according to the composition shown in Table 2 in a similar manner to Synthesis Example 4 to obtain a polyester-based resin.

[Synthesis Example 11]

&Lt; Synthesis Example of Polyurethane-based Resin &

Necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer was charged with 10.6 g of 1,6-hexanediol and 113.3 g of C36 dimer diol (PRIPOL2033: Kroda Japan Co., OH = 207 mgKOH / g) 44.3 g of tolylene diisocyanate, and 240 g of toluene as a solvent were charged, and the mixture was heated to 60 DEG C with stirring in a nitrogen stream and uniformly dissolved. Then, 0.016 g of dibutyltin dilaurate was added as a catalyst to the flask, and the mixture was stirred at 100 ° C for 3 hours to carry out urethanization reaction. Then, 40 g of toluene and 17.6 g of anhydrous trimellitic acid were added, stirred at 90 ° C for 1 hour, then heated to 135 ° C and reacted for 4 hours. And then cooled to room temperature to obtain a polyurethane resin. The mass average molecular weight was 1.1 million, and the acid value was 55.3 mgKOH / g.

[Synthesis Example 12]

Synthesis was carried out according to the composition shown in Table 3 in the same manner as in Synthesis Example 11 to obtain a polyurethane-based resin.

[Synthesis Example 13]

<Synthesis Example of Polyurethane-urea Resin>

28.4 g of 1,6-hexanediol, 8.9 g of dimethylolbutanoic acid, 55.6 g of tolylene diisocyanate and 122 g of toluene as a solvent were placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, The mixture was heated to 60 DEG C with stirring under a nitrogen gas stream to be uniformly dissolved. Then, 0.008 g of dibutyltin dilaurate was added as a catalyst to the flask, and the mixture was stirred at 100 ° C for 3 hours to carry out urethanization reaction. Subsequently, the temperature was lowered to 80 占 폚 and 1.9 g of hexylamine dissolved in 20 g of toluene was dropped over 30 minutes, and then stirred at 100 占 폚 for 6 hours. And then cooled to room temperature to obtain a polyurethaneurea resin. The mass average molecular weight was 14,000, and the acid value was 34.8 mgKOH / g.

[Synthesis Example 14]

<Synthesis Example of Polyurethane-urea Resin>

Synthesis was carried out according to the composition shown in Table 4 in the same manner as in Synthesis Example 13 to obtain a polyurethaneurea resin.

[Synthesis Example 15]

<Synthesis Example of Polyamide-Based Resin>

A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer was charged with 54.5 g of sebacic acid, 6.4 g of trimethic acid, and 13 g of free amine 1074: C36 dimer diamine : 210 mgKOH / g), and 100 g of ion-exchanged water were charged, and the mixture was stirred until the exothermic temperature became constant. When the temperature stabilized, the temperature was elevated to 110 ° C. After confirming the outflow of water, the temperature was elevated to 120 ° C after 30 minutes, and the dehydration reaction was continued while being heated at 10 ° C every 30 minutes. When the temperature reached 230 deg. C, the reaction was continued at the same temperature for 3 hours and maintained under a vacuum of about 2 kPa for 1 hour. Thereafter, the temperature was lowered to obtain a polyamide resin. The mass average molecular weight was 2.8 million, and the acid value was 20.0 mgKOH / g.

[Synthesis Examples 16 to 17]

Synthesis was carried out according to the composition shown in Table 5 in a similar manner to Synthesis Example 15 to obtain a polyamide-based resin.

[Synthesis Example 18]

<Synthesis Example of Polyimide Resin>

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer, 88.8 g of 4,4 '- (hexafluoroisopropyridine) diphthalic acid anhydride 6FDA, 50 g of dimer diisocyanate (product of BASF Japan Co., , NCO% = 13.8%) and 6.06 g of an IPDI nylate (napped product of isophorone diisocyanate) were put in a flask and stirred until the exothermic temperature became constant. When the temperature was stabilized, the temperature was elevated to 110 ° C and the water was allowed to flow out. After 30 minutes, the temperature was raised to 120 ° C, and then the dehydration reaction was continued while the temperature was raised by 10 ° C every 30 minutes. When the temperature reached 230 占 폚, the reaction was continued at the same temperature for 3 hours, and maintained at a vacuum of about 2 kPa for 3 hours. Thereafter, the temperature was lowered to obtain a polyimide resin. The mass average molecular weight was 3.4 million, and the acid anhydride value was 7.5 mgKOH / g.

[Synthesis Examples 19 to 23]

Synthesis was carried out according to the composition of Table 6 in the same manner as in Synthesis Example 18 to obtain a polyimide group resin.

[Synthesis Example 24]

<Synthesis Example of Polycarbonate Resin>

A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer was charged with 25.2 g of ethylene carbonate, 38.9 g of 1,4-cyclohexanedimethanol, 4.0 g of trimethylolpropane, 0.003 g of tetrabutyl titanate And the ester exchange reaction was carried out for 8 hours while distilling off a mixture of cyclohexanedimethanol and ethylene carbonate under normal pressure and with stirring. Meanwhile, the reaction temperature was gradually raised to 190 ° C by raising the temperature by 10 ° C every 30 minutes, and the composition of the effluent was adjusted to be in the vicinity of the azeotropic composition of the mixture of cyclohexanedimethanol and ethylene carbonate. The reaction was continued at the same temperature for 3 hours, and the reaction was further maintained under a vacuum of about 2 kPa for 3 hours. Thereafter, the temperature was lowered to obtain a polycarbonate resin. The mass average molecular weight was 14,000, and the hydroxyl value was 48.2 mgKOH / g.

[Synthesis Example 25]

<Synthesis Example of Polycarbonate Resin>

25.2 g of ethylene carbonate, 35.5 g of 1,6-hexanediol and 0.003 g of tetrabutyl titanate were put into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer, , Ester exchange reaction was carried out for 8 hours while distilling off a mixture of 1,6-hexanediol and ethylene carbonate. Meanwhile, the reaction temperature was gradually raised to 190 deg. C while the temperature was elevated by 10 deg. C every 30 minutes, and the composition of the effluent was adjusted to be close to the azeotropic composition of the mixture of 1,6-hexanediol and ethylene carbonate. The reaction was continued at the same temperature for 3 hours and maintained at a vacuum of about 2 kPa for another 3 hours. Thereafter, the temperature was lowered, 2.2 g of trimellitic anhydride and 30 g of toluene were added, and the mixture was reacted at 110 DEG C for 3 hours, and then the temperature was lowered to obtain a polycarbonate resin. The mass average molecular weight was 13,000, the acid value was 20.4 mgKOH / g, and the hydroxyl value was 15.3 mgKOH / g.

[Synthesis Example 26]

<Synthesis Example of Polyphenylene Ether Resin>

A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube and a thermometer was placed in a constant temperature water bath at 30 ° C. 9.9 g of copper (I) chloride was added to 2.0 g of pyridine, and 5.0 g of toluene was added while stirring the solution while blowing oxygen to obtain a copper (II) pyridine complex solution to be a catalyst solution. Further, 98.0 g of 2,6-dimethylphenol and 30.0 g of 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane were dissolved in 3.0 g of toluene to obtain a phenol solution. Thereafter, the catalyst solution and the phenol solution were added dropwise into the reaction vessel maintained at 30 占 폚 and replaced with oxygen, and the mixture was agitated. The polymerization was stopped by changing the oxygen to nitrogen after 66 minutes from the start of monomer addition. The reaction solution was added dropwise to 110 g of methanol containing 0.3 g of concentrated hydrochloric acid. The precipitated polymer was filtered, washed with 25.0 g of methanol containing 1.0 g of concentrated hydrochloric acid, and finally with 25.0 g of methanol. After drying at 120 ° C for 3 hours, the mixture was diluted with 50.0 g of toluene and 50.0 g of 2-propanol to obtain a polyphenylene ether resin. The mass average molecular weight was 15,000, and the phenolic hydroxyl group was 15.4 mgKOH / g.

[Synthesis Example 27] < Synthesis Example of Styrene-Based Elastomer &

To 100 g of the styrene elastomer having a styrene / butadiene ratio of 15: 85 (mass%) and a mass average molecular weight of 60000 in the block ratio of the polymer, 0.49 g of maleic anhydride, 0.1 g of benzoyl peroxide, (Antioxidant, product of BASF Japan Co., Ltd.) was dry blended and further blended using a 32 mm twin-screw extruder equipped with a vent and melt-kneaded to obtain a pellet-shaped sample. The temperature of the twin-screw extruder at the time of mixing and melt-kneading was 40 ° C. under the hopper, 80 ° C. in the mixing zone, 170 ° C. in the reaction zone and 180 ° C. in the reaction zone.

85 parts by mass of acetone and 85 parts by mass of heptane were added to 100 parts by mass of the obtained pellet-shaped sample, and the mixture was heated and stirred in a pressure reactor at 85 占 폚 for 2 hours. After completion of the operation, the pellets were recovered from the wire net and dried in vacuum at 140 DEG C and 0.1 Torr for 20 hours to obtain a styrene-butadiene block copolymer having an acid anhydride group. The molecular weight distribution was narrow, the mass average molecular weight was 60000, and the acid anhydride value was 2.8 mg CH ₃ ONa / g.

[Synthesis Example 28]

Was prepared in the same manner as in Synthesis Example 1, except that the styrene-based elastomer used was changed to styrene: isoprene = 15: 85 (mass%). As a result, a styrene-isoprene block copolymer having a mass average molecular weight and an acid anhydride group .

[Synthesis Example 29]

The same procedure as in Synthesis Example 1 was carried out except that the styrene type elastomer used was styrene: [ethylene / butylene] = 15: 85 (mass%). -Ethylene / butylene-styrene block copolymer.

[Synthesis Examples 30 to 33]

A styrene-ethylene / butylene-styrene block copolymer having a mass average molecular weight and an acid anhydride group shown in Table 9 was obtained in the same manner as in Synthesis Example 29 except that the amount of maleic anhydride to be used was changed and the amount of modification was changed.

[Synthesis Example 34]

&Lt; Synthesis Example of Fluorine Resin >

A stainless steel autoclave having a volume of 1000 mL was charged with 35.2 g of hexafluoropropylene, 46.5 g of vinyl pivalate, 4.93 g of hydroxybutyl vinyl ether, 12.7 g of ethyl vinyl ether, 0.7 g of crotonic acid and 0.8 g of diisopropyl peroxydicarbonate After cooling to 0 ° C, it was degassed under reduced pressure. Thereafter, the mixture was heated to 40 DEG C under stirring and allowed to react for 24 hours. When the internal pressure of the reactor dropped to 2 kg / cm2 at 5 kg / cm2, the reaction was stopped to obtain a fluorine resin. The mass average molecular weight was 4.8 million, and the acid value was 4.6 mgKOH / g.

[Synthesis Example 35]

&Lt; Synthesis Example of Fluorine Resin >

A fluorinated resin was obtained by synthesizing according to the composition shown in Table 10 in a similar manner to Synthesis Example 34.

[Synthesis Example 36]

&Lt; Synthesis Example of Styrene Maleic Anhydride Resin &

In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 300 g of MEK was placed and heated to 80 DEG C while introducing nitrogen gas into the flask. 516.1 g of styrene, 48.4 g of maleic anhydride, Was dropped over 1 hour and polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 DEG C for 3 hours, and then 0.2 g of benzoyl peroxide dissolved in 50 g of MEK was added and reacted at 80 DEG C for 1 hour to obtain a maleic anhydride styrene resin solution. The mass average molecular weight was 6.2 million, and the acid anhydride value was 49.0 mgKOH / g.

[Synthesis Examples 37 to 38]

&Lt; Synthesis Example of Styrene Maleic Anhydride Resin &

Synthesis was carried out according to the composition shown in Table 11 in the same manner as in Synthesis Example 36 to obtain a styrene-maleic anhydride-based resin.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

Hereinafter, in Tables 1 to 11,

BMA: n-butyl methacrylate

MMA: methyl methacrylate

LMA: Lauryl methacrylate

TDMA: tridecyl methacrylate

LMA / TDMA = 1/1 mixed product

tBA: ter-butyl acrylate

MAA: methacrylic acid

HEMA: 2-hydroxyethyl methacrylate

AIBN: azobisisobutyronitrile

Freepol 2033: manufactured by Kuroda Japan Co., Ltd., C36 dimer diol (OH value: 207 mg KOH / g)

Freepol 1009: a product of Croda Japan Co., Ltd., C36 dimer acid (acid value: 195.0 mgKOH / g)

TDI: tolylene diisocyanate

TMA: Anhydrous trimellitic acid

Free amine 1074: C36 dimer diamine (amine value: 210 mgKOH / g) manufactured by Kuroda Japan Co., Ltd.,

NBDA: norbornanediamine

Bisaniline M: manufactured by Mitsui Chemicals, Inc., 1,3-bis [2- (4-aminophenyl) -2-propyl]

IPDI Nutrate: Nutrate of isophorone diisocyanate

Wandamin HM: manufactured by Shin-Nippon Rika Co., Ltd., 4,4'-diaminodicyclohexyl methane

KF-8010: amino-modified silicone oil of both ends (amine value: 430 mgKOH / g) manufactured by Shin-Etsu Silicone Co.,

HAB: 4,4'-diamino 3,3'-dihydroxybiphenyl

1,6-HD: 1,6-hexanediol

2,6-DMP: 2,6-dimethylphenol

BXF: 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane

&Lt; First Embodiment &gt;

[Example 1]

1.1 mol of the epoxy group in the jER 103S (tetrafunctional tetrakisphenol type epoxy compound manufactured by Mitsubishi Chemical Corporation) as the curing agent (B) was added to 1 mol of the reactive functional group in the styrene-based elastomer obtained in Synthesis Example 30 of Resin (A) , Lithium carbonate was added as the alkali metal compound (C), and the mixture was dissolved in a cyclohexane solvent so as to have a solid concentration of 25% to prepare a thermosetting composition.

The thermosetting composition was uniformly coated on the exfoliated polyester film so as to have a film thickness after drying of 30 占 퐉 and dried to prepare a thermosetting adhesive sheet (hereinafter also referred to as an &quot; adhesive sheet &quot;). Subsequently, another peeled polyester film was laminated on the adhesive sheet to obtain an adhesive sheet provided with a double-side protective film.

The amount of lithium in the solid content of the thermosetting composition was determined by ICP emission spectrometry in the following order, and found to be 50 ppm.

After removing the double-sided protective film from the adhesive sheet prepared above, about 0.25 g was precisely weighed in a Teflon container of a Microwave Sample Disassembler (TOPwave, ANALYTICAL SCREWS), 7 mL of nitric acid was added and allowed to stand for 1 hour, It was put in the outer container and installed in the device. The apparatus was subjected to heat treatment at a final temperature of 200 占 폚 for 10 minutes. Thereafter, the solution was cooled to room temperature, and the treated solution was placed in a 50 mL volumetric flask. The treated Teflon container was washed with ultrapure water and placed in a measuring flask. When insoluble matter was present, the filtrate was filtered with an NNo.6 filter paper manufactured by Advantech Co., To prepare a measurement sample. Thereafter, the treatment solution was measured by an ICP analyzer (product of SPECTRO Co., AECOS), and the amount of alkali metal element in the adhesive sheet was quantitatively determined by a calibration curve prepared with the standard solution of the target element.

[Examples 2 to 8]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 1 except that the alkali metal compound (C) shown in Table 12 was added in place of the lithium carbonate used in Example 1.

[Comparative Example 1]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 1 except that lithium carbonate was not added.

[Comparative Examples 2 to 4]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 1 except that alkaline earth metal compounds shown in Table 1-A were added in place of lithium carbonate used in Example 1.

[Examples 9 to 16], [Comparative Examples 5 to 8]

As shown in Table 1-B, in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used in place of the styrene-based elastomer obtained in Synthesis Example 30, To prepare an adhesive sheet provided with a film.

[Examples 17 to 24], [Comparative Examples 9 to 12]

As shown in Table 1-C, an adhesive sheet provided with a double-side protective film was produced in the same manner as in Example 1 except that the styrene-based elastomer obtained in Synthesis Example 30 was used to change the amounts of alkali metal compounds and alkaline earth metal compounds I wrote.

[Examples 25 to 32], [Comparative Examples 13 to 16]

As shown in Table 1-D, the polyphenylene ether resin obtained in Synthesis Example 26 was used to change the amounts of alkali metal compounds and alkaline earth metal compounds, An adhesive sheet was prepared.

[Examples 33 to 40]

As shown in Table 1-E, an adhesive sheet having a double-side protective film was prepared in the same manner as in Example 1, except that the styrene-based elastomer obtained in Synthesis Example 30 was used in combination with two alkali metal compounds.

[Examples 41 to 48]

As shown in Table 1-F, an adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 9 except that the polyphenylene ether resin obtained in Synthesis Example 26 was used in combination with two alkali metal compounds.

[Examples 49 to 51, 126], [Comparative Example 17]

As shown in Table 1-G, in the same manner as in Example 1 except that the styrene-based elastomer obtained in Synthesis Example 30 was used as an epoxy group-containing compound (B) and another epoxy group-containing compound described later was used instead of jER1031S, To prepare an adhesive sheet.

Example 1 is also shown in Table 1-G.

[Examples 52 to 58], [Comparative Example 18]

As shown in Table 1-H, in the same manner as in Example 9 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used as an epoxy group-containing compound (B) and another epoxy group- An adhesive sheet having a double-sided protective film was prepared.

In addition, Example 9 is also shown in Table 1-H.

[Examples 59 to 68]

As shown in Table 1-I, an adhesive sheet having a double-side protective film was prepared in the same manner as in Example 1, except that the kind and amount of the curing agent (B) were changed using the styrene-based elastomer obtained in Synthesis Example 30.

[Examples 69 to 83]

As shown in Table 1-J, the polyphenylene ether resin obtained in Synthesis Example 26 was used to change the type and amount of the curing agent (B), and an adhesive sheet provided with a double- I wrote.

[Examples 84 to 108], [Examples 115 to 119]

As shown in Tables 1-K to 1-Q and 1-S to 1-T, instead of the styrene type elastomer obtained in Synthesis Example 30, each resin (A) obtained in Synthesis Examples 1 to 25 and 34 to 38 Except that an isocyanate in which a polyfunctional type of isophorone diisocyanate (hereinafter also referred to as IPDI) was blocked with methyl ethyl ketone oxime was used as a curing agent (B), BL4265SN manufactured by Sumika Bayer Urethane Co., Ltd. An adhesive sheet having a double-side protective film was prepared in the same manner as in Example 1. [

[Examples 109 to 114]

As shown in Table 1-R, an adhesive sheet having a double-side protective film was prepared in the same manner as in Example 1, except that the styrene-based elastomer obtained in Synthesis Examples 29 to 33 was used instead of the styrene-based elastomer obtained in Synthesis Example 30 .

[Examples 120 to 125]

As shown in Table 1-U, the resin obtained in Synthetic Examples 29, 26, 15, 20, 34, 11, and 1 was used as the resin (A) instead of the styrene- An adhesive sheet provided with a double-side protective film was prepared.

Example 52 is also shown in Table 1-U.

Common in Table 1-A to 1-U below.

jER1031S: manufactured by Mitsubishi Chemical Corporation, tetrafunctional tetrakisphenol type epoxy compound

TETRAD-X: manufactured by Mitsubishi Chemical Co., Ltd., tetrafunctional glycidyl amine compound

BL4265SN: Isocyanate blocked with methyl ethyl ketone oxime by a polyfunctional type of isophorone diisocyanate (hereinafter also referred to as IPDI) manufactured by Sumika Bayer Urethane Co., Ltd.

BL3175: Isocyanate blocked with methyl ethyl ketone oxime, trimer (nuate) of hexamethylene diisocyanate (hereinafter referred to as HDI), product of Sumika Bayer Urethane Co., Ltd.

BL1100: manufactured by Sumika Bayer Urethane Co., Ltd., and tolylene diisocyanate (hereinafter, also referred to as TDI) as a prepolymer type was evaluated as? -Caprolactam blocked isocyanate

OXTP: manufactured by Ube Chemical Co., Ltd., bifunctional oxetane compound

OXT-121: manufactured by TOAGOSE CO., LTD., Bifunctional oxetane compound

Chemitite PZ: Nippon Shokubai Co., Ltd., polyfunctional aziridine compound

With respect to the adhesive sheets obtained in Examples and Comparative Examples, the plating solution resistance, adhesiveness, heat resistance, bendability and electrical insulation were evaluated by the following methods. The results are shown in Tables 1-A to 1-U.

<Evaluation>

(1) Resistance to plating solution

A 65 mm x 65 mm adhesive sheet having a protective film on one side removed was laminated on a copper surface of a two-layer CCL (Espanex MC18-25-00FRM) made by Sinetettsu Sumikin Kagaku Co., Ltd. at 80 DEG C, followed by laminating at 160 DEG C , And 1.0 MPa for 30 minutes. Further, the test piece was thermally cured at 160 DEG C for 2 hours, and finally the protective film was peeled off to prepare a test piece for evaluation. This test piece was subjected to electroless nickel plating treatment in accordance with the procedures and conditions shown in the following items a to g.

a. Acid degreasing process: Immersed in ICP Clean S-135K (manufactured by Okuno Seiyaku Kogyo Co., Ltd.) at 40 ° C for 4 minutes

↓

b. Soft etching process: 1 minute immersion in sodium peroxodisulfate at 30 ° C

↓

c. Desmat process: immersing in sulfuric acid at 25 캜 for 1 minute

↓

d. Pre-dip process: immersing in hydrochloric acid at 25 ° C for 30 seconds

↓

e. Activation process: Immersing for 1 minute in an ICP liquid crystal (manufactured by Okuno Seiyaku Kogyo Co., Ltd.) at 30 ° C

↓

f. Post dip process: immersing in sulfuric acid at 25 캜 for 1 minute

↓

g. Electroless nickel plating process: Immersed in ICP Nikolon FPF (Okuno Seiyaku Kogyo Co., Ltd.) at 85 ° C for 20 minutes.

The appearance of the test piece after immersing in the electroless nickel plating solution was visually observed, and after the curing, the presence or absence of abnormality such as expansion and peeling of the adhesive layer was checked and the steps a to g were repeated without any abnormality.

This test is to evaluate the resistance of the adhesive layer after curing to the plating solution by appearance, and the resistance was evaluated by repeating the number of times a to g.

A ... No bad appearance even after 4th immersion.

B ... There is no bad appearance in third immersion, but it occurs after fourth immersion.

C ... There is no bad appearance in the secondary immersion, but it occurs after the third immersion.

D ... There is no bad appearance in the first immersion, but it occurs after the second immersion.

E ... Appearance failure due to primary immersion.

(2) Adhesiveness

A 65 mm x 65 mm size adhesive sheet from which the protective film had been removed was sandwiched between polyimide films having a thickness of 75 占 퐉 ("CATPTON 300H" manufactured by Du Pont, DuPont) and laminated at 80 DEG C, MPa for 30 minutes. Further, this test piece was thermally cured at 160 DEG C for 2 hours to prepare a test piece for evaluation. The test piece was cut to a width of 10 mm and a length of 65 mm, and subjected to a T peel test at a tensile rate of 300 mm / min in an atmosphere at 23 캜 and 50% relative humidity, and the adhesive strength (N / cm) was measured. This test was carried out to evaluate the adhesive strength of the adhesive layer at room temperature, and the results were judged based on the following criteria.

A ... &quot; 12 (N / cm) &lt; Adhesive strength &

B ... 8 (N / cm) < Adhesive strength? 12 (N / cm)

C ... 5 (N / cm) < Adhesion strength? 8 (N / cm)

D ... &quot; 3 (N / cm) &lt; adhesion strength &amp;le; 5 (N / cm)

E ... &quot; Adhesive strength? 3 (N / cm) &quot;

(3) Heat resistance

A test piece cut into a width of 10 mm and a length of 65 mm was stored in an atmosphere having a relative humidity of 50% at 23 캜 for at least 24 hours and then the surface of the polyimide film was contacted with molten solder at various temperatures for one minute It was. Thereafter, the appearance of the test piece was visually observed, and the presence or absence of adhesion such as foaming, peeling, peeling of the cured adhesive layer was evaluated. This test evaluates the thermal stability of the cured adhesive layer at the time of solder contact in terms of appearance. A good heat resistance does not change the appearance, while a poor heat resistance results in foaming or peeling after soldering. The results of these evaluations were judged based on the following criteria.

A ... "No change in appearance even at 300 ℃"

B ... "No change in appearance at 280 ℃. At 300 ° C, foaming was confirmed. "

C ... "No change in appearance even at 260 ℃. At 280 ° C, foaming was confirmed. "

D ... "No change in appearance even at 240 ℃. The foaming was confirmed at 260 ° C. "

E ... "Foaming was observed at 240 ° C"

(4) Flexibility

A 65 mm x 65 mm adhesive sheet from which the protective film had been removed was laminated on a polyimide film (CAPTON 100H, manufactured by Toray DuPont Co., Ltd.) having a thickness of 25 μm and a comb pattern (Conductor pattern width / space width = 50 mu m / 50 mu m) formed thereon, and laminated at 80 DEG C, followed by compression bonding at 160 DEG C and 1.0 MPa for 30 minutes. Further, this test piece was thermally cured at 160 DEG C for 2 hours to prepare a test piece for evaluation. The test specimen for evaluation was bent 180 degrees with a load of 500 g placed on the outside of the cured coating film surface, and the number of times until the crack occurred was evaluated by the following criteria.

A ... "Crack (crack) is not seen even when bent 20 times"

B ... "I can not see the crack when I bend 14 times. Cracking up to 20 times "

C ... "I can not see a crack even when I bend eight times. Cracking up to 14 times "

D ... "I can not see the crack when I bend three times. Cracking up to 8 times "

E ... "Cracking to bend three times"

(5) Electrical insulation

A 65 mm x 65 mm adhesive sheet having a protective film removed was laminated on a polyimide film ("CAPTON 100H", product of DuPont-DuPont) having a thickness of 25 μm and a comb-like pattern Width / space width = 50 占 퐉 / 50) was laminated at 80 占 폚 under the condition of 160 占 폚 and 1.0 MPa for 30 minutes. Further, this test piece was thermally cured at 160 DEG C for 2 hours to prepare a test piece for evaluation. A direct current voltage of 50 V was continuously applied to the conductor circuit of this test piece in an atmosphere at a temperature of 130 캜 and a relative humidity of 85% for 100 hours, and the insulation resistance value between the conductors after 100 hours was measured. The evaluation criteria are as follows.

A ... Insulation resistance value 10 ⁹ Ω or more

B ... Insulation resistance 10 ⁸ Ω or more 10 ⁹ Ω or less

C ... Insulation resistance 10 ⁷ Ω or more 10 ⁸ Ω or less

D ... Insulation resistance value 10 ⁶ Ω or more 10 ⁷ Ω or less

E ... Insulation resistance value Less than 10 ⁶ Ω

[Table 1-A]

[Table 1-B]

[Table 1-C]

[Table 1-D]

[Table 1-E]

[Table 1-F]

[Table 1-G]

[Table 1-H]

[Table 1-I]

[Table 1-J]

[Table 1-K]

[Table 1-L]

[Table 1-M]

[Table 1-N]

[Table 1-O]

[Table 1-P]

[Table 1-Q]

[Table 1-R]

[Table 1-S]

[Table 1-T]

[Table 1-U]

As can be seen from the Examples and Comparative Examples shown in Tables 1-A to 1-U, in Comparative Examples 1 and 5, the resistance of the plating solution deteriorated without using the alkali metal compound (C). Further, in Comparative Examples 2 to 4 and 6 to 8, resistance to the plating solution deteriorated because another metal compound was added instead of the alkali metal compound (C). Furthermore, even in the case of containing the alkali metal compound (C), as shown in Comparative Examples 9, 11, 13 and 15, when the content of the alkali metal compound (C) was less than 1 ppm, the resistance of the plating solution deteriorated. Further, as in Comparative Examples 10, 12, 14, and 16, if the alkali metal compound (C) was contained in excess of 110 ppm, the electrical insulating properties deteriorated.

In addition, as can be seen from Comparative Example 17 and Comparative Example 18, when the curing agent (B) was not contained, the heat resistance and the insulation deteriorated markedly.

On the other hand, in the case of containing 1 to 110 ppm of the alkali metal compound (C) in terms of the mass of the alkali metal element including the resin (A), the curing agent (B) and the alkali metal compound . In the comparative example, both the plating solution resistance and the electric insulation property were found to be satisfactory in adhesive strength, heat resistance, and flexibility. This is because the resin (A) and the curing agent (B) give adhesion, heat resistance, and bendability and further contain the alkali metal compound (C), so that a stronger film can be formed by forming a metal bridge at the time of immersing the plating solution do.

&Lt; Second Embodiment &gt;

[Example 201]

1.1 mole of epoxy group in jER1031S (tetrafunctional tetrakisphenol type epoxy compound manufactured by Mitsubishi Chemical Corporation) was used as the curing agent (B) relative to 1 mole of the reactive functional group in the styrene-based elastomer obtained in Synthesis Example 30 in which the resin (A) , Lithium carbonate was added as the alkali metal compound (C), and the solid content was adjusted to 25% by using a cyclohexanone solvent to prepare a thermosetting composition.

The thermosetting composition was uniformly coated on the exfoliated polyester film so as to have a thickness of 30 mu m after drying and dried to provide a thermosetting adhesive sheet (hereinafter also referred to as an &quot; adhesive sheet &quot;). Subsequently, another peeled polyester film was laminated on the adhesive sheet to obtain an adhesive sheet provided with a double-side protective film.

Further, the amount of lithium in the solid content of the thermosetting composition was determined by ICP emission spectrometry in the following order, and it was 1000 ppm.

The double-sided protective film was removed from the adhesive sheet prepared above. About 0.25 g of the adhesive sheet was precisely weighed into a Teflon container of a microwave sample decomposing apparatus (TOPwave, ANALYTICAL SCREEN) and 7 mL of nitric acid was added thereto. I put it in the lid of exclusive use, the outer container, and installed in the device. The apparatus was subjected to heat treatment at a final temperature of 200 占 폚 for 10 minutes. Then, the solution was cooled to room temperature, and the treated solution was placed in a 50 mL volumetric flask. The treated Teflon container was washed with ultra pure water and placed in a volumetric flask. When insoluble matter was present, it was filtered through No. 6 filter paper, And a measurement sample was prepared. Thereafter, the treatment liquid was measured with an ICP analyzer (product of SPECTRO Co., Ltd., AECOS), and the amount of alkali metal element in the adhesive sheet was quantitatively determined by a calibration curve made of the standard solution of the target element.

[Examples 202 to 208]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 201 except that the alkali metal compound (C) shown in Table 2-A was added in place of the lithium carbonate used in Example 201.

[Comparative Example 2-1]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 201 except that lithium carbonate was not added.

[Comparative Examples 202 to 204]

An adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 201 except that alkaline earth metal compounds shown in Table 2-A were added in place of lithium carbonate used in Example 201.

[Examples 209 to 216], [Comparative Examples 205 to 208]

As shown in Table 2-B, in the same manner as in Examples 201 to 208 and Comparative Examples 1 to 4 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used in place of the styrene-based elastomer obtained in Synthesis Example 30, To prepare an adhesive sheet provided with a film.

[Examples 217 to 224], [Comparative Examples 209 to 212]

As shown in Table 2-C, an adhesive sheet provided with a double-side protective film was produced in the same manner as in Example 201 except that the styrene-based elastomer obtained in Synthesis Example 30 was used to change the amounts of alkali metal compounds and alkaline earth metal compounds I wrote.

[Examples 225 to 232], [Comparative Examples 213 to 216]

As shown in Table 2-D, the polyphenylene ether resin obtained in Synthesis Example 26 was used to change the amount of the alkali metal compound or alkaline earth metal compound, An adhesive sheet was prepared.

[Examples 233 to 240]

As shown in Table 2-E, an adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 201 except that two kinds of alkali metal compounds were used in combination with the styrene-based elastomer obtained in Synthesis Example 30.

[Examples 241 to 248]

As shown in Table 2-F, an adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 209 except that the polyphenylene ether resin obtained in Synthesis Example 26 was used in combination with two alkali metal compounds .

[Examples 249 to 251, 326], [Comparative Example 217]

As shown in Table 2-G, in the same manner as in Example 201 except that the styrene-based elastomer obtained in Synthesis Example 30 was used and another epoxy group-containing compound described below was used in place of jER 1031S as the epoxy group-containing compound (B) To prepare an adhesive sheet.

In addition, Example 201 is also shown in Table 2-G.

[Examples 252 to 258], [Comparative Example 218]

As shown in Table 2-H, in the same manner as in Example 209 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used and other epoxy group-containing compound described later was used instead of jER 1031S as the epoxy group-containing compound (B) An adhesive sheet having a double-sided protective film was prepared.

In addition, Example 209 is also shown in Table 2-H.

[Examples 259 to 268]

As shown in Table 2-I, the styrene-based elastomer obtained in Synthesis Example 30 was used to prepare an adhesive sheet provided with a double-side protective film in the same manner as in Example 201 except that the type and amount of the curing agent (B) were changed.

[Examples 269 to 283]

As shown in Table 2-J, an adhesive sheet provided with a double-side protective film was produced in the same manner as in Example 209 except that the type and amount of the curing agent (B) were changed using the polyphenylene ether resin obtained in Synthesis Example 26 I wrote.

[Examples 284 to 308], [Examples 315 to 319]

As shown in Tables 2-K to 2-P and 2-S to 2-T, instead of the styrene type elastomer obtained in Synthesis Example 30, each resin (A) obtained in Synthesis Examples 1 to 25 and 34 to 38 Except for using an isocyanate in which a polyfunctional type of BL4265SN manufactured by Sumika Bayer Urethane Co., Ltd. and isophorone diisocyanate (hereinafter also referred to as IPDI) was blocked with methyl ethyl ketone oxime as a curing agent (B) in place of jER1031S, 201, an adhesive sheet having a double-side protective film was prepared.

[Examples 309 to 314]

As shown in Table 2-Q, an adhesive sheet provided with a double-side protective film was prepared in the same manner as in Example 201 except that the styrene-based elastomer obtained in Synthesis Examples 29 to 33 was used instead of the styrene-based elastomer obtained in Synthesis Example 30 .

[Examples 320 to 325]

As shown in Table 2-U, in the same manner as in Example 249 except that each resin obtained in Synthesis Examples 29, 26, 15, 20, 34, 11, and 1 was used as the resin (A) instead of the styrene type elastomer obtained in Synthesis Example 30 An adhesive sheet provided with a double-side protective film was prepared.

Example 252 is also shown in Table 2-U.

The adhesive sheets obtained in Examples and Comparative Examples were evaluated for reworkability, adhesiveness, heat resistance, flexibility, and adhesiveness after humidification by the following methods. The results are shown in Tables 2-A to 2-U.

<Evaluation>

(1) Re-workability

A 65 mm x 65 mm adhesive sheet having a protective film on one side removed was laminated on a copper surface of a 50 mm x 50 mm two-layer CCL (Espanex MC18-25-00FRM, Shin Nitetsu Sumikin Kagaku Co., Ltd.) at room temperature A test piece for evaluation was prepared. The adhesive layer was peeled off for each protective film to evaluate reworkability (re-peelability).

A ... After peeling off the adhesive sheet, the remaining area of the adhesive is 1 mm 2 or less

C ... After peeling off the adhesive sheet, the remaining area of the adhesive is larger than 1 mm &lt; 2 &gt; but smaller than 40 mm &

E ... After peeling off the adhesive sheet, the remaining area of the adhesive is 40 mm2 or more

(2) adhesive property, (3) heat resistance, and (4) bendability.

(5) Adhesion after humidification

The specimens cut in a width of 10 mm and a length of 65 mm prepared in the above (2) were tested under the conditions of 85 ° C and 85% RH (hereinafter referred to as high peak), 40 ° C and 90% RH 7 days and 3 days, and then subjected to a T peel test at a tensile rate of 300 mm / min in an atmosphere at 23 ° C and a relative humidity of 50% as in the case of the above (2), and then the adhesive strength (N / cm) And evaluated according to the following criteria.

A ... High humidity, adhesion strength after 7 days is 3N or higher

B: High humidity, 7 days after the bonding strength is less than 3N, high humidity, 3 days after the bonding strength of 3N or more

C: high humidity, 3 days after 3 days, but the adhesive strength after low humidity and 7 days is not less than 3N

D ... Low-humidity, 7 days after the adhesive strength is less than 3N, low humidity, 3 days after the adhesive strength of 3N or more

E ... low humidity, adhesive strength after 3 days is less than 3N

[Table 2-A]

[Table 2-B]

[Table 2-C]

[Table 2-D]

[Table 2-E]

[Table 2-F]

[Table 2-G]

[Table 2-H]

[Table 2-I]

[Table 2-J]

[Table 2-K]

[Table 2-L]

[Table 2-M]

[Table 2-N]

[Table 2-O]

[Table 2-P]

[Table 2-Q]

[Table 2-R]

[Table 2-S]

[Table 2-T]

[Table 2-U]

As can be seen from the examples and comparative examples shown in Tables 2-A to 2-U, in Comparative Examples 201, 205, 209, 211, 213 and 215, since the content of the alkali metal compound (C) Workability deteriorated. Further, in Comparative Examples 202 to 204 and 206 to 208, the reworkability was deteriorated because another metal compound was added instead of the alkali metal compound (C). Further, when the alkali metal compound (C) was contained in excess of 10000 ppm as in Comparative Examples 210, 212, 214 and 216, the adhesion after wetting deteriorated. Further, as can be seen from Comparative Example 217 and Comparative Example 218, in the case of not containing the curing agent (B), the heat resistance and adhesion after humidification were markedly deteriorated.

On the other hand, when the alkali metal compound (C) is contained in an amount of more than 110 ppm and less than 10000 ppm in terms of mass of the alkali metal element including the resin (A), the curing agent (B) and the alkali metal compound , The adhesive properties, heat resistance, and flexibility were satisfied in addition to the reworkability in the comparative example and the adhesion after the humidification in the comparative example. This is because the resin (A) and the curing agent (B) impart adhesiveness, heat resistance, and bendability and further contain an appropriate amount of the alkali metal compound (C), so that reworkability and adhesiveness after humidification are both compatible.

The thermosetting composition used in the formation of the thermosetting adhesive sheet of the first embodiment gives a cured product excellent in plating solution resistance, adhesion, heat resistance after humidification, heat resistance, flexibility and electrical insulation, , A circuit-coating solder resist, a coverlay film, an electromagnetic shielding adhesive, a plating resist, an interlayer electric insulating material for a printed wiring board, an optical waveguide, and the like. In addition, the thermosetting composition used in the formation of the thermosetting adhesive sheet of the second embodiment gives a cured product excellent in reworkability, heat resistance after humidification, heat resistance, flexibility, and adhesiveness after humidification, Coating materials for electronic materials, solder resists for circuit coating, coverlay films, adhesives for shielding electromagnetic waves, optical waveguides, and the like.

Claims (11)

A thermosetting adhesive sheet formed from a thermosetting composition that satisfies all of the following conditions (1) to (5):
(1) a resin (A), a curing agent (B), and an alkali metal compound (C).
(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-
(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).
(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.
(5) The alkali metal compound (C) is contained in an amount of 1 to 110 ppm in terms of mass of the alkali metal element in the solid content of the thermosetting composition.
A thermosetting adhesive sheet formed from a thermosetting composition that satisfies all of the following conditions (1) to (4) and (6):
(1) a resin (A), a curing agent (B), and an alkali metal compound (C).
(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-
(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group, and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).
(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.
(6) The alkali metal compound (C) is contained in an amount of not less than 110 ppm and not more than 10,000 ppm in terms of mass of the alkali metal element in the solid content of the thermosetting composition.
The method according to claim 1,
Wherein the reactive functional group is at least one selected from the group consisting of a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group and an acid anhydride group.
The method according to claim 1,
The total amount of 1 g of the reactive functional group of the resin (A) is 1 to 80 mg in terms of potassium hydroxide.
The method according to claim 1,
Wherein the total amount of the epoxy group, isocyanate group, aziridinyl group and oxetanyl group in the curing agent (B) is 0.1 to 12 mol based on 1 mol of the reactive functional group of the resin (A).
A thermosetting adhesive sheet comprising the thermosetting adhesive sheet according to claim 1 and two sheet-like substrates covering both surfaces of the thermosetting adhesive sheet.
The method according to claim 6,
A heat-curable adhesive sheet comprising a sheet-like base material, wherein at least one of the two sheet-like base materials is a peelable sheet-like base material.
(1) to (5) are applied to at least one surface of a sheet-like base material and dried to form a thermosetting adhesive sheet, and a thermosetting adhesive sheet is formed on the other surface of the thermosetting adhesive sheet, A method of producing a thermosetting adhesive sheet provided with a sheet-shaped substrate,
(1) a resin (A), a curing agent (B), and an alkali metal compound (C).
(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-
(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).
(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, A resin, and a styrene maleic anhydride-based resin.
(5) The alkali metal compound (C) is contained in an amount of 1 to 110 ppm in terms of mass of the alkali metal element in the solid content of the thermosetting composition.
(1) to (4) and (6) are applied to at least one surface of a sheet-like substrate and dried to form a thermosetting adhesive sheet, and the other side of the thermosetting adhesive sheet A method for producing a thermosetting adhesive sheet provided with a sheet-shaped substrate,
(1) a resin (A), a curing agent (B), and an alkali metal compound (C).
(2) The curing agent (B) is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, an aziridinyl group-containing compound and an oxetanyl group-
(3) The resin (A) does not have an epoxy group, an isocyanate group, an aziridinyl group and an oxetanyl group, and has a reactive functional group capable of reacting with the curing agent (B).
(4) The resin composition according to the above item (1), wherein the resin (A) is at least one resin selected from the group consisting of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, Resin and styrene maleic anhydride-based resin.
(6) The alkali metal compound (C) is contained in an amount of more than 110 ppm and not more than 10000 ppm of the solid content of the thermosetting composition in terms of mass of the alkali metal element.
A method for manufacturing a circuit board, comprising the steps of: curing a thermosetting adhesive sheet according to any one of claims 1 to 5; A printed wiring board having a sheet.
A heat-curable adhesive sheet according to any one of claims 1 to 5, which is sandwiched between the circuit surface and the sheet-like substrate of a printed wiring board having a conductive circuit to thermally cure the thermosetting adhesive sheet Wherein the method comprises the steps of: