JP6943270B2 - Thermosetting adhesive sheet and its use - Google Patents

Description

The present invention relates to a thermosetting adhesive sheet. The thermosetting adhesive sheet of the present invention is suitably used 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 such as printed wiring boards are increasingly required to be thinner, multi-layered, and higher in definition. It is supposed to be done. Specific examples of the adhesive or coating agent used around such an electronic material include the following (1) to (6).

(1) Interlayer adhesive: Used to bond circuit boards together, and is in direct contact with copper or silver circuits. It is used between layers of a multilayer substrate and may be liquid or sheet-like.

(2) Adhesive for coverlay film: A polyimide film used to bond a coverlay film (such as a polyimide film used for the purpose of protecting the outermost surface of a circuit) and an underlying circuit board, and a polyimide film in advance. In many cases, the adhesive layer is integrated.

(3) Adhesive for copper-clad film (CCL): Used for laminating a polyimide film and a copper foil. Processing such as etching is performed when the copper circuit is formed.

(4) Coverlay: It is used for the purpose of protecting the outermost surface of the circuit, and is formed by printing printing ink on the circuit, adhering an adhesive sheet, and then curing the circuit. Some are photosensitive and thermosetting.

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

(6) Electromagnetic wave shielding adhesive: Attached to a flexible printed wiring board for the purpose of shielding electromagnetic noise generated from an electronic circuit.

Examples of these forms include a liquid form (inked for printing) and a sheet form (preliminarily formed into a film), and the form is appropriately selected according to the application.

Various studies have been conducted in order to meet the high demand for such electronic material peripheral members, but none have been obtained that sufficiently satisfy all the characteristics.

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 containing a phenol, a compound having a triazine ring, a phenol resin obtained by reacting a hydroxyl group-substituted aromatic aldehyde, and an epoxy resin.

Patent Document 4 discloses a curable composition for radically polymerizing a polyether ester amide.

Patent Document 5 discloses an example in which a liquid crystal polymer is used as a method for forming a laminate circuit using a thermoplastic resin having no crosslinked structure.

Patent Document 6 describes a tape with an adhesive for TAB having a flexible organic insulating film, an adhesive layer, and a protective film, wherein the adhesive layer is a polyamide resin, an organic metal compound, and an epoxy resin. A tape with an adhesive for TAB, which is contained, is disclosed. Specifically, when the copper foil and the polyimide film are bonded together with an adhesive sheet containing a polyamide resin, an organic metal compound, and a bifunctional epoxy resin, the peel strength (adhesive strength) after the plating treatment is increased. It is described that it is excellent and has excellent insulation properties in an environment of 150 ° C.

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

Patent Document 8 discloses a thermosetting adhesive sheet characterized by having a thermosetting adhesive layer having a glass transition point at −50 ° C. or higher and 10 ° C. or lower and 20 ° C. or higher and 100 ° C. or lower, respectively. There is.

Patent Document 9 discloses a resin composition for an adhesive containing a thermoplastic resin, an inorganic filler, a solvent, and an epoxy resin.

Patent Document 10 discloses a resin composition containing a butylene resin, a resin having at least one group selected from an epoxy group and an oxetanyl group, and a photopolymerization initiator.

Patent Document 11 discloses a resin composition containing an acrylic oligomer, an acrylic monomer, a thiol compound, and a photoinitiator.

Japanese Unexamined Patent Publication No. 2001-214053 JP-A-2002-138199 Japanese Unexamined Patent Publication No. 2006-249178 Japanese Unexamined Patent Publication No. 2013-45755 Japanese Unexamined Patent Publication No. 2005-105165 Japanese Unexamined Patent Publication No. 9-64111 Japanese Unexamined Patent Publication No. 2003-41202 International Publication No. 2013/002001 International Publication No. 2010/074135 Japanese Unexamined Patent Publication No. 2017-31383 International Publication No. 2013/0733364

The curable compositions disclosed in Patent Documents 1 and 2 show good adhesiveness and heat resistance derived from high Tg, but have problems that the molded product is brittle.
Although the curable composition disclosed in Patent Document 3 exhibits high heat resistance and flame retardancy due to its high aromatic content, it has a problem of being inferior in flexibility due to high molecular interaction.
Although the curable composition disclosed in Patent Document 4 exhibits high adhesiveness and insulating properties derived from amides and ethers, it has a problem that it is inferior in heat resistance after humidification because it has a structure that easily absorbs moisture.
The laminate circuit forming method disclosed in Patent Document 5 can exhibit high adhesiveness by melting the resin at a high temperature, but since the melting temperature is as high as 280 ° C. or higher, it has an adverse effect on other members having poor heat resistance. There were also problems such as the need to introduce equipment that can handle high-temperature melting.

The adhesive tape disclosed in Patent Document 6 has insufficient heat resistance after curing because the epoxy resin used is bifunctional.
Patent Document 7 has a problem that the flexibility is insufficient because the crosslink density becomes too high, although the reflow resistance due to the high thermostable decomposition property derived from the polyimide resin and the epoxy resin can be imparted.

By the way, when the adhesive sheet or the like is attached to the object to be adhered, if there is a problem in the position or the like, the adhesive sheet or the like can be peeled off without leaving the adhesive on the object to be adhered, that is, reworkability is required. ..
Furthermore, it is also required that high adhesive strength can be exhibited even when placed in a high humidity environment after adhesion.

The thermosetting adhesive sheet disclosed in Patent Document 8 can exhibit adhesive strength and heat resistance after humidification by containing an acrylic polymer having a glass transition point at −50 ° C. or higher and 10 ° C. or lower, but is a low molecular weight component. There was a problem that the reworkability was insufficient due to the inclusion of.
The adhesive resin composition disclosed in Patent Document 9 can exhibit a high adhesive force after humidification by increasing the acid value of the thermoplastic resin, but has a problem that the flexibility becomes insufficient due to the high crosslink density. there were.
On the other hand, the resin composition disclosed in Patent Document 10 can exhibit reworkability by containing a relatively rigid epoxy or oxetane resin, but has a problem that it is derived from a butylene resin and has insufficient heat resistance.
Although the resin composition disclosed in Patent Document 11 exhibits good bendability, there is a problem that the adhesive force after humidification is insufficient.

An object of the present invention is to provide a thermosetting adhesive sheet having excellent reworkability, adhesiveness, heat resistance (particularly after humidification), flexibility, and adhesiveness after humidification.

In order to solve the above-mentioned problems, the present inventors have made diligent studies and, as a result of diligent studies, by using a thermosetting composition containing a resin (A), a curing agent (B), and a specific amount of an alkali metal compound (C). The present invention has been completed.
That is, the present invention relates to a thermosetting adhesive sheet formed from a thermosetting composition that satisfies all of the following conditions (1) to (5).
(1) Contains 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-containing compound.
(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 (A) is made of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, styrene elastomer, fluororesin and styrene maleic anhydride resin. It is at least one selected from the group of plastics.
(5) The alkali metal compound (C) is contained in the solid content of the thermosetting composition in an amount of more than 110 ppm and 10,000 ppm or less in terms of mass of the alkali metal element.

The reactive functional group is preferably 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 total reactive functional group value of 1 g of the resin (A) is preferably 1 to 80 mg in terms of potassium hydroxide.

The total amount of the epoxy group, isocyanate group, aziridinyl group, and oxetanyl group in the curing agent (B) is preferably 0.1 to 12 mol with respect to 1 mol of the reactive functional group of the resin (A).

The present invention also relates to a thermosetting adhesive sheet with a sheet-like substrate, which has the thermosetting adhesive sheet and two sheet-like substrates covering both sides of the thermosetting adhesive sheet.

Further, in the present invention, a thermosetting composition satisfying all of the following conditions (1) to (5) is applied and dried on at least one surface of a sheet-like base material to form a thermosetting adhesive sheet, and the heat is described. The present invention relates to a method for producing a thermosetting adhesive sheet with a sheet-like base material, in which another sheet-like base material is superposed on the other surface of the curable adhesive sheet.
(1) Contains 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-containing compound.
(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 (A) is made of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, styrene elastomer, fluororesin and styrene maleic anhydride resin. It is at least one selected from the group of plastics.
(5) The alkali metal compound (D) is contained in the solid content of the thermosetting composition in an amount of more than 110 ppm and 10,000 ppm or less in terms of mass of the alkali metal element.

Further, the present invention relates to a printed wiring board with a protective sheet, wherein the circuit surface of the printed wiring board having a conductive circuit is protected by a sheet-like base material via the sheet-shaped cured product.

Further, the present invention protects the thermosetting adhesive sheet by sandwiching the thermosetting adhesive sheet between the circuit surface of a printed wiring board having a conductive circuit and a sheet-like base material, and thermosetting the thermosetting adhesive sheet. The present invention relates to a method of manufacturing a printed wiring board with a sheet.

The thermosetting adhesive sheet of the present invention is excellent in reworkability, adhesiveness, heat resistance after humidification, flexibility, and adhesiveness after humidification.

As described above, the thermosetting adhesive sheet of the present invention contains the resin (A), the curing agent (B), and a specific amount of the alkali metal compound (C).
Hereinafter, the resin (A) will be described in detail.

The resin (A) in the present invention comprises 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, a styrene-based elastomer, a fluororesin, and a styrene maleic anhydride-based resin. Selected from the group. These can be appropriately selected and a plurality of them can be used. Of these, styrene-based elastomers and polyphenylene ether resins are preferable from the viewpoints of high insulating properties due to high hydrophobicity and high heat resistance due to the small number of pyrolysis points. The styrene-based elastomer referred to here refers to a block copolymer in which a portion composed of styrene and a portion composed of butadiene, isoprene, ethylene, etc. form a "block".

The resin (A) in the present invention has no epoxy group, isocyanate group, aziridinyl group, and 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 and an amino group, a cyanate group, an isocyano group, a cyanato group, an isocyanato group, an imidazole group, a pyrrol group, an acetal group and an acryloyl group. , Methacloyl group, aldehyde group, hydrazide group, hydrazone group, phosphoric acid group and the like, and it is preferable that it 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 reactive functional group is preferably capable of reacting with the curing agent (B) at 20 to 200 ° C, more preferably 140 ° C to 200 ° C.

The total reactive functional group value of 1 g of the resin (A) is preferably 1 to 80 mg in terms of potassium hydroxide, more preferably 1 to 50 mg, still more preferably 4 to 30 mg.
Since the reactive functional group contributes to the formation of crosslinks, the reactive functional group value is preferably 1 mg or more in terms of potassium hydroxide from the viewpoint of heat resistance and insulating property of the cured product. Further, from the viewpoint of adhesiveness and flexibility of the cured product, the reactive functional group value is preferably 80 mg or less in terms of potassium hydroxide.

The curing agent (B) will be described.
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-containing compound. Two or more types can be used together.

<Epoxy group-containing compound>
The epoxy group-containing compound, which is one of the curing agents (B), may be a compound having an epoxy group in the molecule, and is not particularly limited, but an average of two or more epoxy groups may be contained in one molecule. Those having can be preferably used. As the epoxy group-containing compound, for example, an epoxy resin such as a glycisyl ether type epoxy resin, a glycisyl amine type epoxy resin, a glycidyl ester type epoxy resin, or 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 novolac type epoxy resin, phenol novolac type epoxy resin, and α-naphthol novolac. Type epoxy resin, bisphenol A type novolac type epoxy resin, dicyclopentadiene type epoxy resin, tetrabrom bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyloxyphenyl) Etan and the like can be mentioned.

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

Examples of the glycidyl ester type epoxy resin include diglycidyl phthalate, diglycidyl hexahydrophthalate, and diglycidyl tetrahydrophthalate.
Examples of the cyclic aliphatic (alicyclic) epoxy resin include epoxycyclohexylmethyl-epoxycyclohexanecarboxylate and bis (epoxycyclohexyl) adipate.
As the epoxy group-containing compound, one of the above compounds may be used alone, or two or more of them may be used in combination.
Epoxy group-containing compounds include bisphenol A type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, tris (glycidyloxyphenyl) methane, or tetrakis (glycidyloxyphenyl) from the viewpoint of high adhesiveness and heat resistance. It is preferable to use ethane

<Isocyanate group-containing compound>
The isocyanate group-containing compound, which is 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-butylisocyanate, isopropylisocyanate, phenylisocyanate, benzylisocyanate, (meth) acryloyloxyethyl isocyanate, and 1,1-bis [ (Meta) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like can be mentioned.
In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate, xylylene diisocyanate, trilene 2,4-diisocyanate, toluene diisosocyanate, 2,4-diisocyanate Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylenediocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, trizine diisocyanate, 2,2 , 4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethylxylylene diisocyanate, P-tetramethylxylylene diisocyanate, diisocyanate compounds such as dimerate diisocyanate, hydroxyl group, carboxyl group, A compound obtained by reacting an amide group-containing vinyl monomer with an equimolar reaction can also be used as an isocyanate compound.

Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, and 4,4'-diphenylmethane. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, Aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate,
Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene Aliphatic diisocyanate such as diisocyanate,
ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate , 1,3-Tetramethylxylylene diisocyanate and other aromatic aliphatic diisocyanates,
3-Isocyanate Methyl-3,5,5-trimethylcyclohexylisocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, methyl-2,4-cyclohexane Diisocyanates, methyl-2,6-cyclohexanediisocyanates, 4,4'-methylenebis (cyclohexylisocyanate), 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane and other alicyclic diisocyanates Can be mentioned.

Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include the trimethylol propane adduct compound of diisocyanate described above, a burette compound that has reacted with water, and a trimeric compound having an isocyanurate ring.

As the isocyanate group-containing compound, a blocked isocyanate group-containing compound in which the isocyanate group in the various isocyanate group-containing compounds exemplified above is protected by ε-caprolactam, MEK oxime, or the like can also be used.
Specific examples thereof include those in which the isocyanate group of 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. In particular, a hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is highly preferable because it has excellent adhesive strength and heat resistance to polyimide and copper when used in the present invention.

<Aziridinyl group-containing compound>
The aziridine group-containing compound, which is one of the curing agents (B), may be any compound containing an aziridine group in the molecule, and is not particularly limited.
Examples of the aziridine group-containing compound include N, N'-diphenylmethane-4,4'-bis (1-aziridine carboxite), N, N'-toluene-2,4-bis (1-aziridine carboxite), and the like. Bisisophthaloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridinecarbokisite), trimethylpropan-tri -Β-aziridinyl propionate, tetramethylolmethane-tri-β-aziridinyl propionate, tris-2,4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane Tris [3- (1-aziridinyl) propionate], trimethylpropanthris [3- (1-aziridinyl) butyrate], trimethylpropanthris [3- (1- (2-methyl) aziridine) propionate], trimethylpropanate Tris [3- (1-aziridinyl) -2-methylpropionate], 2,2'-bishydroxymethylbutanol Tris [3- (1-aziridinyl) propionate], pentaerythritol tetra [3- (1-aziridinyl) Propionate], diphenylmethane-4,4-bis-N, N'-ethyleneurea, 1,6-hexamethylenebis-N, N'-ethyleneurea, 2,4,6- (triethyleneimino) -Syn-triazine , Bis [1- (2-ethyl) aziridineyl] benzene-1,3-carboxylic acid amide and the like.

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

<Oxetanyl group-containing compound>]
Examples of the oxetanyl group-containing compound, which is one of the curing agents (B), include 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene and 3-ethyl-3-{[((3-ethyloxetane-3-yl) methoxy] methyl} benzene. 3-Ethyloxetane-3-yl) methoxy] methyl} oxetane, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4'-bis [(3-ethyl-3-oxetanyl) ) Ethylmethyl] biphenyl, esterified with (2-ethyl-2-oxetanyl) ethanol and terephthalic acid, etherified with (2-ethyl-2-oxetanyl) ethanol and phenol novolac resin, (2-ethyl-2- Examples thereof include an esterified product of (oxetanyl) ethanol and a polyvalent carboxylic acid compound.

The curing agent (B) used in the present invention has a total of 0.1 to 12 mol of epoxy group, isocyanate group, aziridinyl group, and oxetanyl group with respect to 1 mol of the reactive functional group in the resin (A). It is preferably contained in the above range, more preferably 0.3 to 10 mol, and further preferably 0.5 to 5 mol mol. By setting the epoxy group or the like in the curing agent (B) to 0.1 mol or more with respect to the reactive functional group of the resin (A), the crosslink density can be increased and the heat resistance, insulating property, and adhesiveness can be improved. Flexibility and electrical insulation can be improved by setting the epoxy group or the like to 20 mol or less.

<Alkali metal compound (C)>
The thermosetting adhesive sheet of the present invention contains the alkali metal compound (C) in an amount of more than 110 ppm and 10,000 ppm or less in terms of mass conversion of the alkali metal element from the viewpoint of reworkability and adhesiveness after humidification. Since the content of the alkali metal compound (C) in terms of mass of the alkali metal element is more than 110 ppm, reworkability that can be re-peelable when the uncured adhesive sheet is attached at room temperature can be imparted. The reason for this is not clear, but it is considered that the highly polar alkali metal migrates to the surface side of the base material in the adhesive sheet and inhibits the adhesiveness when uncured.
Further, when the content of the alkali metal compound (C) in terms of mass of the alkali metal element is 10,000 ppm or less, the adhesiveness after humidification can be ensured. The content of the alkali metal compound (C) in terms of mass of the alkali metal element is more than 110, 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 present invention may be contained in the resin (A), the curing agent (B), other curing agents described later, and various additives. , Resin (A), curing agent (B) and the like may be blended separately. Further, 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) can be reduced by washing before use.
When the alkali metal compound (C) is contained in the resin (A), the curing agent (B), other curing agents described later, and various additives, the alkali metal compound (C) is added in each manufacturing process. It may be the catalyst used, a decomposition product thereof, or one mixed in the process.

The element-equivalent content X (ppm) of the alkali metal compound (C) contained in 1 g of the thermosetting composition (thermosetting adhesive sheet) can be determined as follows.
Content of alkali metal compound (C): Y (g),
Molecular weight of alkali metal compound (C): A,
Amount of alkali metal element in alkali metal compound (C): If B, then X = [Y × (B / A)] × 10 ⁶
For example, in the case of _{lithium carbonate (Li 2} CO ₃₎
Molecular weight A is 73.89,
The amount B of the alkali metal contained is (6.94 × 2), and
When 0.0001 g of lithium carbonate is contained in 1 g of the thermosetting composition (thermosetting adhesive sheet),
X = [0.0001 × ((6.94 × 2) /73.89)] × 10 ⁶
= 18.8.

The type and amount of the alkali metal compound (C) contained in each raw material contained in the thermosetting composition (thermocurable adhesive sheet) are determined, and the total content of the alkali metal compound (C) is calculated. : Y (g) can be obtained to obtain the element conversion content X (ppm), but the element conversion content X (ppm) can also be obtained as follows.
That is, a thermocurable composition (thermocurable adhesive sheet) having an arbitrary mass is decomposed by the following method, and the obtained decomposition liquid is contained by ICP emission spectroscopic analysis (hereinafter referred to as ICP analysis). The elemental equivalent content X of the alkali metal compound (C) can be determined.
When both compounds of the same alkali metal are contained, for example, when lithium carbonate and lithium acetoacetate are contained, the lithium element equivalent content is determined according to the ICP analysis method.

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

Specific examples of the alkali metal compound (C) include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal carboxylates, alkyl alkali metals and the like. It is not limited.

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 carbonate, lithium carbonate and the like, and hydrates thereof.

Examples of the alkali metal bicarbonate include sodium hydrogen carbonate, calcium hydrogen carbonate and the like, and hydrates thereof.

As the alkali metal carboxylic acid salt, a carboxylic acid salt having 1 to 10 carbon atoms is preferable, and a carboxylic acid salt having 1 to 3 carbon atoms is more preferable.
Specific examples of carboxylic acids include linear saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid and pelargonic acid; oxalic acid, fumaric acid, maleic acid and succinic acid. Alipid dicarboxylic acids such as acids, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid; hydroxy such as glycolic acid, lactic acid, hydroxybutyric acid, tartaric acid, malic acid, mevalonic acid; benzoic acid, terephthalic acid, isophthalic acid , Aromatic carboxylic acids such as orthophthalic acid, and hydrates thereof.
Among these, alkali metal hydroxides, alkali metal acetates, and alkali metal carbonates are preferable, and alkali metal hydroxides are particularly likely to ionize alkali metals.

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

In addition, phenyllithium, α- and β-naphthyllithium, styryllithium, benzyllithium and the like can be mentioned.

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.

The thermosetting composition (thermosetting adhesive sheet) of the present invention is, in addition to the resin (A), the curing agent (B), and the alkali metal compound (C), other curing agents as long as the physical properties are not impaired. Can be included.
Specific examples of other curing agents include, but are not limited to, carbodiimide group-containing compounds, benzoxazine compounds, β-hydroxyalkylamide group-containing compounds, sulfur-containing compounds, and the like.

[Carbodiimide group-containing compound]
Examples of the carbodiimide group-containing compound, which is one of the other curing agents, include the carbodilite series of Nisshinbo Holdings Co., Ltd. Among them, Carbodilite V-01, 03, 05, 07, 09 is preferable because it has excellent compatibility with an organic solvent. When used in the present invention, it is preferably used because it can be expected to improve the adhesiveness.

[Benzooxazine compound]
As one of the other curing agents, the benzoxazine compound, "P-a", "P-alP", "P-ala", "B-ala", Macromolecules, described in Macromolecules, 36,6010 (2003), "P-appe", "B-appe" described in 34,7257 (2001), "BA-type benzoxazine", "FA-type benzoxazine", "B-m-type benzoxazine" manufactured by Shikoku Kasei Co., Ltd. "And so on.

[Β-Hydroxyalkylamide group-containing compound]
Examples of the β-hydroxyalkylamide group-containing compound, which is one of the other curing agents, include N, N, N', N'-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Ems-Chemie). Various compounds can be mentioned.

[Sulfur-containing compounds]
Examples of the sulfur-containing compound, which is one of the other curing agents, include a thiol compound, a sulfide compound, and a polysulfide compound. When used in the present invention, it is preferably used because it can be expected to improve adhesiveness and heat resistance.

[Thiol compound]
The thiol compound contains, for example, a thiol group and at least a linear, branched or cyclic hydrocarbon group. It may contain two or more thiol groups. The hydrocarbon group may be saturated or unsaturated. A part of the hydrogen atom 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, colorless thiols include, for example, 1-propanethiol, 3-mercaptopropionic acid, (3-mercaptopropyl) trimethoxysilane, 1-butanethiol, 2-butanethiol, isobutyl mercaptan, isoamyl. Mercaptan, cyclopentane thiol, 1-hexane thiol, cyclohexane thiol, 6-hydroxy-1-hexane thiol, 6-amino-1-hexane thiol hydrochloride, 1-heptane thiol, 7-carboxy-1-heptan thiol, 7- Amid-1-heptane thiol, 1-octane thiol, tert-octane thiol, 8-hydroxy-1-octane thiol, 8-amino-1-octane thiol hydrochloride, 1H, 1H, 2H, 2H-perfluoro octane thiol, 1-Nonan thiol, 1-decane thiol, 10-carboxy-1-decane thiol, 10-amide-1-decane thiol, 1-naphthalene thiol, 2-naphthalene thiol, 1-undecane thiol, 11-amino-1-undecane Thiol hydrochloride, 11-hydroxy-1-undecane thiol, 1-dodecane thiol, 1-tetradecane thiol, 1-hexadecane thiol, 16-hydroxy-1-hexadecane thiol, 16-amino-1-hexadecane thiol hydrochloride, 1- Octadecanethiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol, 1,2-benzenedithiol, 1,9-nonandithiol, 1,10-decandithiol, 1,3,5 -Benzenetrithiol, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned. These thiols can be used alone or in combination of two or more.

[Sulfide compound]
The sulfide compound contains, for example, a sulfide group and at least a linear, branched or cyclic hydrocarbon group. It may contain two or more sulfide groups. A part of the hydrogen atom 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, as sulfide compounds, for example, propyl sulfide, furfuryl sulfide, hexyl sulfide, phenyl sulfide, phenyltrifluoromethyl sulfide, bis (4-hydroxyphenyl) sulfide, heptyl sulfide, octyl sulfide, nonyl sulfide, decyl. Examples thereof include sulfide, dodecyl methyl sulfide, dodecyl sulfide, tetradecyl sulfide, hexadecyl sulfide, octadecyl sulfide, and bis (triethoxysilylpropyl) tetrasulfide. These sulfides can be used alone or in combination of two or more.

[Polysulfide compound]
Examples of the polysulfide compound include 2-hydroxyethyl disulfide, propyl disulfide, isopropyl disulfide, 3-carboxypropyl disulfide, allyl disulfide, isobutyl disulfide, tert-butyl disulfide, amyl disulfide, isoamyl disulfide, 5-carboxypentyl disulfide and furfuryl. Disulfide, hexyl disulfide, cyclohexyl disulfide, phenyl disulfide, 4-aminophenyl disulfide, heptyl disulfide, 7-carboxyheptyl disulfide, benzyl disulfide, tert-octyl disulfide, decyl disulfide, 10-carboxydecyl disulfide, hexadecyl disulfide, thiuram disulfide, etc. Can be used.

In the present invention, the amount of the other curing agent used is not particularly limited, but is preferably 0.01 to 20 mol with respect to 1 mol of the reactive functional group of the resin (A). It is more preferably contained in an amount of 5 to 10 mol, and further preferably contained in an amount of 0.1 to 5 mol.
Alternatively, it is preferably contained in an amount of 0.01 to 20 mol, more preferably 0.5 to 10 mol, and further preferably 0.1 to 5 mol with respect to 1 mol of the epoxy group or the like in the curing agent (B). preferable.

<Filler>
Next, the filler that can be used in the present invention will be described in detail.
The thermosetting adhesive sheet of the present invention can contain a filler for the purpose of imparting flame retardancy, controlling the fluidity of the adhesive, improving the elastic modulus of the cured product, and the like.

The filler is not particularly limited, and examples of the shape include spherical, powdery, fibrous, needle-like, and scaly-like.
Examples of the filler include polytetrafluoroethylene powder, polyethylene powder, polyacrylic acid ester powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as silicone, acrylic, styrene butadiene rubber, butadiene rubber, etc. Polyurethane filler such as multi-layered core shell used;
(Poly) phosphate systems such as melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, etc. Phosphates such as compounds, organic phosphoric acid ester compounds, phosphazenic compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphite, aluminum methylbutylphosphinate, aluminum polyethylenephosphinate, etc. Phosphoric flame-retardant fillers such as acid compounds, phosphine oxide compounds, phosphoran compounds, and phosphoramide compounds;
Nitrogen-based flame-retardant fillers such as benzoguanamine, melamine, melam, melem, melon, melamine cyanurate, cyanuric acid compound, isocyanuric acid compound, triazole compound, tetrazole compound, diazo compound, urea, etc.;
Silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, zonotolite, silicon nitride, boron nitride, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, sulfuric acid. Magnesium, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, carbon dioxide Examples thereof include inorganic fillers such as zinc, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and aluminum borate.

Among them, as the filler, it is desirable 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 environmental impact, which has been widely discussed in recent years. Among them, the adhesive of the present invention. It is preferable to use a phosphazene compound, a phosphine compound, a melamine polyphosphate, an ammonium polyphosphate, a melamine cyanurate, or the like, which are more effective in flame retardancy when used in combination with the composition. Further, in terms of further reducing the dielectric constant and the dielectric loss tangent, it is preferable to use polytetrafluoroethylene powder, which cures in an excellent balance not only with dielectric properties but also with adhesiveness, flexibility, electrical insulation and heat resistance. You will be able to get things. In the present invention, these fillers can be used alone or in combination of two or more.

The average particle size D50 of these fillers is preferably 0.1 μm to 25 μm. When a filler having an average particle size close to 0.1 μm is used, the modification effect of the filler can be easily obtained, and the dispersibility and the stability of the dispersion liquid can be easily improved. Further, when a filler having an average particle size close to 25 μm is used, the mechanical properties of the cured film are likely to be improved.

The amount of the filler 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 the modifying effect of the filler, and if it exceeds this range, the mechanical properties of the cured film may be significantly 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 reaction solution before or during the polymerization, a three-roll or the like is used. Examples include a method of kneading the filler, a method of preparing a dispersion liquid containing the filler and mixing the dispersion. Further, in order to disperse the filler well and stabilize the dispersed state, a dispersant, a thickener or the like can be used within a range that does not affect the physical characteristics of the adhesive sheet.

<Other additives>
In addition, the thermosetting adhesive sheet of the present invention has dyes, pigments, antioxidants, polymerization inhibitors, defoamers, leveling agents, ion collectors, and moisturizers as optional components as long as the purpose is not impaired. Agents, viscosity modifiers, preservatives, antibacterial agents, antistatic agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic wave shielding agents and the like can be added.

[Thermosetting adhesive sheet with sheet-like base material]
The thermosetting adhesive sheet with a sheet-like substrate of the present invention can be obtained, for example, as follows.
A solution or dispersion of a thermosetting adhesive is applied to at least one side of a sheet-like substrate, and then dried at 40 to 150 ° C. to form a so-called B-stage thermosetting adhesive sheet. You can get the one with the material. Then, by covering the other surface of the thermosetting adhesive sheet with another sheet-like base material, the thermosetting adhesive sheet with the sheet-like base material of the present invention can be obtained.
At least one of the sheet-like base materials used is preferably a peelable sheet-like base material. That is, a thermosetting adhesive in a solution or dispersion state is applied and dried on a peelable sheet-like base material to form a thermosetting adhesive sheet, and then the other surface of the thermosetting adhesive sheet is applied to another surface. It can be covered with a peelable sheet-like base material, or it can be covered with a non-peelable sheet-like base material to be an adherend. Alternatively, a thermosetting adhesive in a solution or dispersion state is applied and dried on a non-peelable sheet-like base material to be an adherend to form a thermosetting adhesive sheet, and then a thermosetting adhesive sheet is formed. The other surface can also be covered with another peelable sheet-like substrate.

The dry film thickness of the thermosetting adhesive sheet is preferably 5 to 500 μm, more preferably 10 to 100 μm in order to exhibit sufficient adhesiveness and solder heat resistance and from the viewpoint of ease of handling.
Examples of the coating method include comma coating, knife coating, die coating, lip coating, roll coating, curtain coating, bar coating, gravure printing, flexographic printing, dip coating, spray coating, spin coating and the like.

Among the sheet-like substrates used, various plastic films are mentioned, and examples thereof include polyimide films, polyester films, polyphenylene ether films, polyphenylene sulfide films, polystyrene films, polycarbonate films, and polyether ether ketone films. Can be mentioned.
Among the sheet-like substrates used, those having peelability include those obtained by peeling various plastic films and those obtained by peeling paper. Examples of various plastic films to be peeled off include polyester films and polyolefin films.

[Sheet-like cured product], [Printed wiring board with protective sheet]
The sheet-like cured product of the present invention is obtained by thermosetting the thermosetting adhesive sheet of the present invention, for example, by curing at a temperature of about 40 to 200 ° C.

A thermosetting adhesive sheet with a sheet-like base material is used, in which one side of the thermosetting adhesive sheet 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). The case will be described.
Peel off the peelable sheet-like base material from the thermosetting adhesive sheet with the sheet-like base material. Another adherend (for example, the circuit surface side of the printed wiring board having a conductive circuit) is superposed on the exposed thermosetting adhesive sheet. Then, by heating and pressurizing, the thermosetting adhesive sheet sandwiched between both adherends is thermally cured.
In this way, it is possible to obtain a printed wiring board with a protective sheet in which the circuit surface of the printed wiring board having a conductive circuit is protected by a sheet-like base material via the sheet-shaped cured product.

Next, a case of using a thermosetting adhesive sheet with a sheet-like base material in which both sides of the thermosetting adhesive sheet are covered with two peelable sheet-like base materials will be described.
One of the peelable sheet-like base materials is peeled off from the thermosetting adhesive sheet with the sheet-like base material. An adherend (for example, a polyimide film or a polyester film) is superposed on the exposed thermosetting adhesive sheet. Peel off the other peelable sheet-like substrate covering the other surface of the thermosetting adhesive sheet. Another adherend (for example, the circuit surface side of the printed wiring board having a conductive circuit) is superposed on the exposed thermosetting adhesive sheet. Then, by heating and pressurizing, the thermosetting adhesive sheet sandwiched between both adherends is thermally cured. It is also possible to superimpose the circuit surface side of the printed wiring board having a conductive circuit on the surface on which the peelable sheet-like base material is first peeled off, and to superimpose a polyimide film or a polyester film on the other surface on the thermosetting adhesive sheet. ..

Examples of the printed wiring board having a conductive circuit include a flexible printed wiring board in which a conductive circuit is formed on a flexible and insulating plastic film such as polyester or polyimide.
As a method of providing a conductive circuit, for example, a photosensitive etching resist layer is formed on a copper foil of a flexible copper-clad plate in which a copper foil is provided on a base film with or without an adhesive layer, and a circuit is provided. The conductive circuit is formed from the copper foil by exposing it through a mask film having a pattern, curing only the exposed portion, then removing the copper foil in the unexposed portion by etching, and then peeling off the remaining resist layer. Can be formed.
Alternatively, a method of providing only the circuits necessary by means such as sputtering or plating on the base film can be mentioned.
Alternatively, a method of forming a conductive circuit on a base film by a printing technique using a conductive ink containing silver or copper particles can be mentioned.

The thermosetting adhesive sheet of the present invention is suitably used for manufacturing a printed wiring board with a protective sheet, and can also be used as follows.
<Multi-layered multiple flexible printed wiring>
By sandwiching the thermosetting adhesive sheet of the present invention between a plurality of flexible printed wirings and heating / pressurizing the thermosetting adhesive sheet, the thermosetting adhesive sheet can be cured to obtain a multilayer flexible printed wiring board.
<Lasting base film for flexible printed wiring board and copper foil>
For example, the thermosetting adhesive sheet can be cured by sandwiching the thermosetting adhesive sheet of the present invention between the polyimide film and the copper foil and heating and pressurizing the sheet.

<Conductive adhesive sheet>
The thermosetting adhesive sheet of the present invention has a resin (A), a curing agent (B), a specific amount of an alkali metal compound (C), a conductive metal filler such as copper or silver, and a conductive filler such as carbon. Can be used as a conductive thermosetting adhesive sheet in which the thermosetting composition obtained by blending and dispersing the above is formed into a sheet.

<Electromagnetic wave shield>
Further, the thermosetting adhesive sheet of the present invention can also be used as an electromagnetic wave shield by forming a multilayer structure with an insulating layer using the conductive thermosetting adhesive sheet produced above. Further, not only the conductive layer portion but also the thermosetting adhesive sheet of the present invention can be used as an insulating layer.
<Heat conduction adhesive sheet>
Further, in the thermosetting adhesive sheet of the present invention, in addition to the resin (A), the curing agent (B), and a specific amount of the alkali metal compound (C), a thermally conductive inorganic filler, a metal filler, and the like are dispersed. The thermosetting composition obtained by blending and dispersing can be used as a heat-conducting thermosetting adhesive sheet in the form of a sheet.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, and Mw means the mass average molecular weight.

<Measurement method of hydroxyl value (phenolic and alcoholic)>
The phenolic and alcoholic hydroxyl values are the amount of potassium hydroxide required to neutralize the amount of hydroxyl groups contained in 1 g of the resin solid to neutralize acetic acid bonded to the hydroxyl groups when the hydroxyl groups are acetylated (mg). ).
The hydroxyl value is measured according to JIS K0070 and calculated in consideration of the acid value as shown in the following formula.

Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 ml of a cyclohexanone solvent to dissolve the sample. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added, and the mixture was stirred for about 1 hour. Phenolphthalein TS is added as an indicator to this and lasts for 30 seconds. Then titrate with 0.5N alcoholic potassium hydroxide solution until the solution turns pink.
The hydroxyl value was calculated by the following formula (unit: mgKOH / g).
Hydroxy group value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.5N alcoholic potassium hydroxide solution (ml)
b: Consumption (ml) of 0.5N alcoholic potassium hydroxide solution in the blank experiment
F: Titer of 0.5N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)
<Measurement of acid value>
Precisely weigh about 1 g of the sample in an Erlenmeyer flask with a stopper, and add 100 ml of a cyclohexanone solvent to dissolve the sample. Phenolphthalein test solution is added to this as an indicator and held for 30 seconds. Then, titrate with 0.1N alcoholic potassium hydroxide solution until the solution turns pink. The acid value was calculated by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Titer of 0.1N alcoholic potassium hydroxide solution

<Measurement method of acid anhydride price>
Approximately 1 g of the sample was precisely weighed in an Erlenmeyer flask with a stopper, and 100 ml of a 1,4-dioxane solvent was added to dissolve the sample. To this, 10 mL of a mixed solution of octylamine, 1,4-dioxane and water (mixing ratio of 1.49 / 800/80 by weight) was added, and the mixture was stirred for 15 minutes to complete the reaction.
Then, excess octylamine was titrated with a mixed solution of 0.02M perchloric acid and 1,4-dioxane. In addition, 10 mL of a mixed solution of octylamine, 1,4-dioxane, and water (mixing ratio of 1.49 / 800/80 by weight) to which no sample was added was also measured as a blank. The acid anhydride price was calculated by the following formula (unit: mgKOH / g).
Acid anhydride price (mgKOH / g) = 0.02 x (BS) x F x 56.11 / W
B: Blank titration (mL)
S: Sample titration (mL)
W: Sample solid amount (g)
F: 0.02 mol / L Perchloric acid titer

<Measurement method of mass average molecular weight (Mw)>
Mw is measured by GPC (Gel Permeation Chromatography) manufactured by Tosoh Corporation.
HPC-8020 ”was used. GPC is a liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified according to the difference in molecular size. For the measurement in the present invention, two "LF-604" (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID x 150 mm size) are connected in series and used, and the flow rate is 0.6 ml / m.
In, the column temperature was 40 ° C., and the mass average molecular weight (Mw) was determined in terms of polystyrene.

[Synthesis Example 1]
<Example of synthetic acrylic resin>
300 g of methylethyl ketone (hereinafter referred to as MEK) is placed in a 4-neck flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer, and heated to 80 ° C. while injecting nitrogen gas into the container. At the same temperature, 30 g of butyl methacrylate, 28 g of methyl methacrylate, 3 g of a 1: 1 (mass ratio) mixture of lauryl methacrylate and tridecyl methacrylate, 12 g of methacrylic acid, 2,2'-azobisisobutyronitrile 0. A polymerization reaction was carried out by dropping 8 g of the mixture over 1 hour. After completion of the dropping, the mixture was further reacted at 80 ° C. for 3 hours, then 1.2 parts of 2,2'-azobisisobutyronitrile dissolved in 50 g of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour. An acrylic resin solution was obtained. The mass average molecular weight was 52,000 and the acid value was 78.2 mgKOH / g.

[Synthesis Examples 2-3]
Synthesis was carried out in the same manner as in Synthesis Example 1 according to the composition shown in Table 1 to obtain an acrylic resin.

[Synthesis Example 4]
<Polyester resin synthesis example>
57.6 g of sebacic acid, 3.2 g of trimesic acid, 27.5 g of cyclohexanedimethanol, 1.6-hexane in a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. 9.7 g of diol and 0.012 g of tetrabutyl titanate were charged, and the mixture was stirred until the exothermic temperature became constant. When the temperature stabilizes, the temperature is raised to 110 ° C. After confirming that the temperature has stabilized, the temperature is raised to 120 ° C. 30 minutes later, and then the dehydration reaction is carried out while raising the temperature by 10 ° C. every 30 minutes. Continued. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for 1 hour. Then, the temperature was lowered to obtain a polyester resin. The mass average molecular weight was 32,000 and the acid value was 39.8 mgKOH / g.

[Synthesis Examples 5-10]
A polyester resin was obtained by synthesizing according to the composition shown in Table 2 in the same manner as in Synthesis Example 4.

[Synthesis Example 11]
<Synthesis example of polyurethane resin>
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen introduction tube, introduction tube, and thermometer, 1.6-hexanediol 10.6 g, C36 dimerdiol (PRIPL2033: Crowder Japan Co., Ltd., OH value = 207 mgKOH / g) 113.3 g, 44.3 g of tolylene isocyanate, and 240 g of toluene as a solvent were charged, and the temperature was raised to 60 ° C. with stirring under a nitrogen stream to uniformly dissolve the mixture. Subsequently, 0.016 g of dibutyltin dilaurate was charged into this flask as a catalyst, and the mixture was stirred at 100 ° C. for 3 hours to carry out a urethanization reaction. Next, 40 g of toluene and 17.6 g of trimellitic anhydride were added, and the mixture was stirred at 90 ° C. for 1 hour, then heated to 135 ° C. and reacted for 4 hours. It was cooled to room temperature to obtain a polyurethane resin. The mass average molecular weight was 11,000 and the acid value was 55.3 mgKOH / g.

[Synthesis Example 12]
Synthesis was carried out in the same manner as in Synthesis Example 11 according to the composition shown in Table 3 to obtain a polyurethane resin.

[Synthesis Example 13]
<Synthesis example of polyurethane urea resin>
In a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer, 28.4 g of 1.6-hexanediol, 8.9 g of dimethylolbutanoic acid, 55.6 g of tolylene diisocyanate, and a solvent. As a result, 122 g of toluene was charged, and the temperature was 60 ° C. while stirring under a nitrogen stream.
The temperature was raised to the same level, and the mixture was uniformly dissolved. Subsequently, 0.008 g of dibutyltin dilaurate was charged into this flask as a catalyst, and the mixture was stirred at 100 ° C. for 3 hours to carry out a urethanization reaction. Next, 1.9 g of hexylamine dissolved in 20 g of toluene after lowering the temperature to 80 ° C. was added dropwise over 30 minutes, and then the mixture was stirred at 100 ° C. for 6 hours. The mixture was cooled to room temperature to obtain a polyurethane urea 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 in the same manner as in Synthesis Example 13 according to the composition shown in Table 4 to obtain a polyurethane urea resin.

[Synthesis Example 15]
<Synthesis example of polyamide resin>
Sebacic acid 54.5 g, trimesic acid 6.4 g, preamine 1074: manufactured by Crowder Japan Co., Ltd., C36 dimer diamine ( Amine value: 210 mgKOH / g) 148.4 g, 100 g of ion-exchanged water was charged, and the mixture was stirred until the exothermic temperature became constant. When the temperature became stable, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. 30 minutes later, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. .. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for 1 hour. Then, the temperature was lowered to obtain a polyamide resin. The mass average molecular weight was 28,000 and the acid value was 20.0 mgKOH / g.

[Synthesis Examples 16 to 17]
Synthesis was carried out in the same manner as in Synthesis Example 15 according to the composition shown in Table 5 to obtain a polyamide resin.

[Synthesis Example 18]
<Synthesis example of polyimide resin>
88.8 g of 4,4'-(hexafluoroisopropyridene) diphthalic anhydride "6FDA", diisocyanate (BASF) in a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer. Japan Co., Ltd., NCO% = 13.8%) 110.1 g IPDI nurate (nulate form of isophorone diisocyanate) 6.06 g was charged and stirred until the exothermic temperature became constant. When the temperature became stable, the temperature was raised to 110 ° C., and after confirming the outflow of water, the temperature was raised to 120 ° C. 30 minutes later, and then the dehydration reaction was continued while raising the temperature by 10 ° C. every 30 minutes. .. When the temperature reached 230 ° C., the reaction was continued at the same temperature for 3 hours and kept under a vacuum of about 2 kPa for 3 hours. Then, the temperature was lowered to obtain a polyimide resin. The mass average molecular weight was 34,000, and the acid anhydride price was 7.5 mgKOH / g.

[Synthesis Examples 19-23]
Synthesis was carried out in the same manner as in Synthesis Example 18 according to the composition shown in Table 6 to obtain a polyimide resin.

[Synthesis Example 24]
<Synthesis example of polycarbonate resin>
In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer, 25.2 g of ethylene carbonate, 38.9 g of 1,4-cyclohexanedimethanol, 4.0 g of trimethylolpropane, 0.003 g of tetrabutyl titanate was charged, and the transesterification reaction was carried out for 8 hours under normal pressure and stirring while distilling off a mixture of cyclohexanedimethanol and ethylene carbonate. During this period, the reaction temperature was gradually raised to 190 ° C. while raising the temperature by 10 ° C. every 30 minutes so that the composition of the distillate was close to the azeotropic composition of the mixture of cyclohexanedimethanol and ethylene carbonate. Adjusted to. The reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for another 3 hours. Then, 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 are charged in a 4-neck flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer. The transesterification reaction was carried out for 8 hours while distilling off a mixture of 1.6 hexanediol and ethylene carbonate under pressure and stirring. During this period, the reaction temperature is gradually raised to 190 ° C. while raising the temperature by 10 ° C. every 30 minutes, and the composition of the distillate is close to the azeotropic composition of the mixture of 1.6-hexanediol and ethylene carbonate. Adjusted to. The reaction was continued at the same temperature for 3 hours, and kept under a vacuum of about 2 KPa for another 3 hours. Then, the temperature was lowered, 2.2 g of trimellitic anhydride and 30 g of toluene were added, and the mixture was reacted at 110 ° 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 introduction tube, an introduction tube, and a thermometer was placed in a constant temperature water tank at 30 ° C. 9.9 g of copper (I) chloride was added to 2.0 g of pyridine, stirred while blowing oxygen, and 5.0 g of toluene was added to obtain a copper (II) pyridine complex solution as 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. Then, the temperature was maintained at 30 ° C., and both the catalyst and phenol solutions were added dropwise and stirred vigorously in the oxygen-substituted reaction vessel. 66 minutes after the start of monomer addition, oxygen was switched to nitrogen to terminate the polymerization. The reaction solution was added dropwise to 110 g of methanol containing 0.3 g of concentrated hydrochloric acid. The precipitated polymer was filtered and washed with 25.0 g of methanol, followed by 25.0 g of methanol containing 1.0 g of concentrated hydrochloric acid, and finally 25.0 g of methanol. The mixture was dried at 120 ° C. for 3 hours and 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 value was 15.4 mgKOH / g.

[Synthesis Example 27] <Styrene-based Elastomer Synthesis Example>
In terms of polymer block ratio (hereinafter, the same applies), styrene: butadiene = 15: 85 (mass%), maleic anhydride 0.49 g, benzoyl peroxide 0.1 g, and irga with respect to 100 g of a styrene-based elastomer having a mass average molecular weight of 60,000. 0.6 g of Knox 1010 (manufactured by BASF Japan, an antioxidant) was dry-blended, further mixed using a 32 mm twin-screw extruder with a vent, and melt-kneaded to obtain a pellet-shaped sample. The temperature of the twin-screw extruder during mixing and melt-kneading was 40 ° C. at the bottom of the hopper, 80 ° C. in the mixing zone, 170 ° C. in the reaction zone, and 180 ° C. in the die.
To 100 parts by mass of the obtained pellet-shaped sample, 85 parts by mass of acetone and 85 parts by mass of heptane were added, and the mixture was heated and stirred at 85 ° C. for 2 hours in a pressure resistant reactor. After completion of the same operation, pellets were collected with a wire mesh and vacuum dried at 140 ° 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 60,000, and the acid anhydride price was 2.8 mgCH ₃ ONa / g.

[Synthesis Example 28]
An acid anhydride having a mass average molecular weight and an acid anhydride base value as shown in Table 1 in the same manner as in Synthesis Example 1 except that the styrene-based elastomer used was styrene: isoprene = 15: 85 (mass%). A styrene-isoprene block copolymer having a group was obtained.

[Synthesis Example 29]
The mass average molecular weight and acid anhydride base value as shown in Table 9 were set in the same manner as in Synthesis Example 1 except that the styrene-based elastomer used was styrene: [ethylene / butylene] = 15: 85 (mass%). A styrene-ethylene / butylene-styrene block copolymer having an acid anhydride group was obtained.

[Synthesis Examples 30 to 33]
Styrene having an acid anhydride group having a mass average molecular weight and an acid anhydride base value as shown in Table 9 in the same manner as in Synthesis Example 29 except that the amount of maleic anhydride used was changed and the amount of modification was changed. -Ethylene / Butylene-Styrene block copolymer was obtained.

[Synthesis Example 34]
<Synthesis example of fluororesin>
In a 1000 mL stainless steel autoclave, 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 are charged. After cooling to 0 ° C., the air was degassed under reduced pressure. Then 40 under stirring
The mixture was heated to ° C. and reacted for 24 hours. When the internal pressure ^{of the reactor dropped from 5 kg / cm 2} to 2 kg / cm ² , the reaction was stopped to obtain a fluororesin. The mass average molecular weight was 48,000 and the acid value was 4.6 mgKOH / g.

[Synthesis Example 35]
<Synthesis example of fluororesin>
Synthesis was carried out in the same manner as in Synthesis Example 34 according to the composition shown in Table 10 to obtain a fluororesin.

[Synthesis Example 36]
<Synthetic example of styrene maleic anhydride resin>
Put 300 g of MEK in a 4-neck flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, an introduction tube, and a thermometer, and heat to 80 ° C. while injecting nitrogen gas into the container, and 516.1 g of styrene at the same temperature. , 48.4 g of maleic anhydride and 0.2 g of benzoyl peroxide were added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 g of benzoyl peroxide dissolved in 50 g of MEK was added, and the mixture was reacted at 80 ° C. for 1 hour to obtain a styrene maleic anhydride-based resin solution. rice field. The mass average molecular weight was 62,000, and the acid anhydride price was 49.0 mgKOH / g.

[Synthesis Examples 37 to 38]
<Synthetic example of styrene maleic anhydride resin>
Synthesis was carried out in the same manner as in Synthesis Example 36 according to the composition shown in Table 11 to obtain a styrene maleic anhydride-based resin.

Below, in Tables 1 to 11, common BMA: n-butyl methacrylate MMA: methyl methacrylate LMA: lauryl methacrylate TDMA: tridecyl methacrylate LMA / TDMA = 1/1 mixture tBA: ter-butyl acrylate MAA: HEMA methacrylate: 2- Hydroxyethyl Methacrylate AIBN: Azobisisobutyronitrile Nitrile 2033: C36 Dimerdiol (OH value: 20) manufactured by Crowder Japan Co., Ltd.
7mgKOH / g)
Prepole 1009: Made by Croda Japan Co., Ltd., C36 dimer acid (acid value: 195.0 m)
gKOH / g)
TDI: Tolylene diisocyanate TMA: Trimellitic anhydride Priamine 1074: Made by Croda Japan Co., Ltd., C36 dimer diamine (amine value: 2)
10 mgKOH / g)
NBDA: Norbornan diaminebisaniline M: Mitsui Kagaku Fine Co., Ltd., 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene IPDI Nurate: Isophorone diisocyanate nurate Wandamine HM: Shin Nihon Rika 4,4'-Diaminodicyclohexylmethane KF-8010 manufactured by Shinetsu Silicone Co., Ltd., both-terminal amino-modified silicone oil (amine value: 430 mgKOH / g)
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

(Example 1)
For 1 mol of the reactive functional group in the styrene-based elastomer obtained in Synthesis Example 30 which is the resin (A), jER1031S (manufactured by Mitsubishi Chemical Corporation, tetrafunctional tetrakisphenol type epoxy) was used as the curing agent (B). The epoxy group in the compound) is added in an amount of 1.1 mol, lithium carbonate is added as the alkali metal compound (C), and the mixture is dissolved in a cyclohexanone solvent so that the solid content concentration becomes 25% to have a thermosetting composition. I adjusted things.
This thermosetting composition was uniformly applied onto a peeled polyester film so that the film thickness after drying was 30 μm, dried, and an adhesive sheet was provided. Next, another peeled polyester film was laminated on the adhesive sheet to obtain an adhesive sheet with a double-sided protective film.
The amount of lithium in the solid content of the thermosetting composition was determined by ICP emission spectroscopic analysis according to the following procedure and found to be 1000 ppm.

After removing the double-sided protective film from the adhesive sheet prepared above, about 0.25 g is precisely weighed in a Teflon container of a microwave sample decomposition device (TOPwave manufactured by Analytic Jena), 7 ml of nitric acid is added, and the mixture is allowed to stand for 1 hour. , A special lid, put in an outer container and installed in the device. The final heat treatment was performed at 200 ° C. for 10 minutes in the apparatus. After that, cool to room temperature, put the treatment liquid in a 50 ml volumetric flask, put the treated Teflon container in the same volumetric flask while washing with ultrapure water, and if there is insoluble matter, filter with No. 6 filter paper and ultrapure water. The volume was adjusted to 50 ml, and a measurement sample was prepared. Then, the treatment liquid was measured by an ICP analyzer (AECOS manufactured by SPECTRO), and the amount of alkali metal element in the adhesive sheet was quantified by a calibration curve prepared with a standard liquid of the target element.

[Examples 2 to 8]
An adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 1 except that the alkali metal compound (D) shown in Table 12 was added instead of the lithium carbonate used in Example 1.

[Comparative Example 1]
An adhesive sheet with a double-sided 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 with a double-sided protective film was prepared in the same manner as in Example 1 except that the alkaline earth metal compounds and the like shown in Table 12 were added instead of the lithium carbonate used in Example 1.

[Examples 9 to 16], [Comparative Examples 5 to 8]
As shown in Table 13, the same applies to Examples 1 to 8 and Comparative Examples 1 to 4 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used instead of the styrene-based elastomer obtained in Synthesis Example 30. To create an adhesive sheet with a double-sided protective film.

[Examples 17 to 24], [Comparative Examples 9 to 12]
As shown in Table 14, the styrene-based elastomer obtained in Synthesis Example 30 was used, and a double-sided protective film was attached in the same manner as in Example 1 except that the amounts of the alkali metal compound and the alkaline earth metal compound were changed. An adhesive sheet was created.

[Examples 25 to 32], [Comparative Examples 13 to 16]
As shown in Table 15, the polyphenylene ether-based resin obtained in Synthesis Example 26 was used, and a double-sided protective film was attached in the same manner as in Example 9 except that the amounts of the alkali metal compound and the alkaline earth metal compound were changed. I made an adhesive sheet of.

[Examples 33-40]
As shown in Table 16, an adhesive sheet with a double-sided 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 and two types of alkali metal compounds were used in combination.

[Examples 41-48]
As shown in Table 17, an adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 9 except that the polyphenylene ether-based resin obtained in Synthesis Example 26 was used and two types of alkali metal compounds were used in combination.

[Examples 49 to 51], [Comparative Example 17]
As shown in Table 18, the styrene-based elastomer obtained in Synthesis Example 30 was used, and as the epoxy group-containing compound (C), Example 1 was used except that another epoxy group-containing compound described later was used instead of jER1031S. In the same manner as above, an adhesive sheet with a double-sided protective film was prepared.
Table 18 also shows Example 1.

[Examples 52 to 58], [Comparative Example 18]
As shown in Table 19, the polyphenylene ether-based resin obtained in Synthesis Example 26 was used, and as the epoxy group-containing compound (C), an epoxy group-containing compound described later was used instead of jER1031S. An adhesive sheet with a double-sided protective film was prepared in the same manner as in 9.
In addition, Example 9 is also shown in Table 19.

[Examples 59 to 68]
As shown in Table 20, the styrene-based elastomer obtained in Synthesis Example 30 was used, and the curing agent (B) was used.
An adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 1 except that the type and amount of the above were changed.

[Examples 69 to 83]
As shown in Table 21, an adhesive sheet with a double-sided protective film is used in the same manner as in Example 9 except that the type and amount of the curing agent (B) are changed by using the polyphenylene ether-based resin obtained in Synthesis Example 26. It was created.

[Examples 84 to 108], [Examples 115 to 119]
As shown in Tables 22 to 28 and 30 to 31, instead of the styrene-based elastomer obtained in Synthesis Example 30, each resin obtained in Synthesis Examples 1 to 25 and 34 to 38 was used as the resin (A) in jER1031S. As the curing agent (B), BL4265SN: manufactured by Sumika Bayer Urethane Co., Ltd., and an isocyanate obtained by blocking the polyfunctional type of isophorone diisocyanate (hereinafter, also referred to as IPDI) with methylethylketone oxime was used as Example 1. Similarly, an adhesive sheet with a double-sided protective film was prepared.

[Examples 109 to 114]
As shown in Table 29, a double-sided protective film was provided in the same manner as in Example 1 except that the styrene-based elastomers obtained in Synthesis Examples 29 to 33 were used instead of the styrene-based elastomers obtained in Synthesis Example 30. I made an adhesive sheet of.

[Examples 120 to 125]
As shown in Table 32, instead of the styrene-based elastomer obtained in Synthesis Example 30, the resins obtained in Synthesis Examples 29, 26, 15, 20, 34, 11, and 1 were used as the resin (A). An adhesive sheet with a double-sided protective film was prepared in the same manner as in Example 49 except for the above.
In addition, Example 52 is also shown in Table 32.

Hereinafter, it is common in Tables 12 to 32.
jER1031S: Mitsubishi Chemical Co., Ltd., 4-functional tetrakisphenol-type epoxy compound TETRAD-X: Mitsubishi Gas Chemical Co., Ltd., 4-functional glycidylamine compound BL4265SN: Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate (hereinafter, IPDI) Isocyanate BL3175 in which the polyfunctional type of (also referred to as) is blocked with methylethylketone oxime: hexamethylene diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd. (hereinafter, also referred to as).
Isocyanate BL1100 in which a trimer (nulate compound) of HDI) is blocked with methyl ethyl ketone oxyc: ε-, which is a prepolymer type of tolylene diisocyanate (hereinafter, also referred to as TDI) manufactured by Sumika Bayer Urethane Co., Ltd. Isocyanate OXTP blocked with caprolactam: Bifunctional oxetane compound OXT-121 manufactured by Ube Kosan Co., Ltd .: Bifunctional oxetane compound Chemitite PZ manufactured by Toa Synthetic Co., Ltd .: Polyfunctional aziridine compound manufactured by Nippon Catalyst Co., Ltd.

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 21-52.
<Evaluation>

(1) Reworkability An adhesive sheet with a size of 65 mm x 65 mm from which the protective film on one side has been removed is used as a 50 mm x 50 mm two-layer CCL [Espanex MC18-25-00FRM, manufactured by Nippon Steel & Sumitomo Metal Corporation] copper surface. A test piece for evaluation was prepared by laminating on the above at room temperature. The reworkability (removability) was evaluated by peeling off the adhesive layer together with the protective film.
A ... After peeling off the adhesive sheet, the remaining glue area is 1 mm ² or less C ... After peeling off the adhesive sheet, the remaining glue area is larger than ^{1 mm 2 but smaller than 40 mm 2} E ... Adhesive After peeling off the sheet, the remaining area of glue is 40 mm ² or more.

(2) Adhesiveness An adhesive sheet with a size of 65 mm x 65 mm from which the protective film has been removed is sandwiched between polyimide films with a thickness of 75 μm [“Kapton 300H” manufactured by Toray DuPont Co., Ltd.] and at 80 ° C. It was laminated and then crimped for 30 minutes under the conditions of 160 ° C. and 1.0 MPa. Further, this test piece was heat-cured at 160 ° C. for 2 hours, cooled, and then cut into a width of 10 mm and a length of 65 mm to prepare a test piece for evaluation.
This test piece was subjected to a T-peel peeling test at a tensile speed of 300 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%, and the adhesive strength (N / cm) was measured. This test evaluates the adhesive strength of the adhesive layer when used at room temperature, and the results were judged according to the following criteria.
A ... "12 (N / cm) <Adhesive strength"
B ... "8 (N / cm) <Adhesive strength ≤ 12 (N / cm)"
C ... "5 (N / cm) <Adhesive strength ≤ 8 (N / cm)"
D ... "3 (N / cm) <Adhesive strength ≤ 5 (N / cm)"
E ... "Adhesive strength ≤ 3 (N / cm)"

(3) Heat resistance Similar to (2) above, the test piece cut out to a width of 10 mm and a length of 65 mm is stored in an atmosphere of 23 ° C. and a relative humidity of 50% for 24 hours or more, and then melted and soldered at various temperatures. The polyimide film surface was brought into contact with the surface and floated for 1 minute. Then, the appearance of the test piece was visually observed, and the presence or absence of adhesion abnormality such as foaming, floating, and peeling of the cured adhesive layer was evaluated. This test evaluates the thermal stability of the cured adhesive layer at the time of solder contact by appearance. The one with good heat resistance does not change the appearance, while the one with poor heat resistance is solder. Foaming and peeling occur after treatment. These evaluation results were judged according to the following criteria.
A ... "No change in appearance even at 300 ° C"
B ... "No change in appearance at 280 ° C. Foaming is confirmed at 300 ° C."
C ... "No change in appearance at 260 ° C. No change in appearance at 280 ° C." D ... "No change in appearance at 240 ° C. No change in appearance at 260 ° C." E ... "240" Foaming is observed at ° C. "

(4) Flexibility A copper circuit is formed on a polyimide film ["Kapton 100H" manufactured by Toray DuPont Co., Ltd.] with a thickness of 25 μm on an adhesive sheet with a size of 65 mm × 65 mm from which the protective film has been removed. The comb-shaped pattern (conductor pattern width / space width = 50 μm / 50 μm) was sandwiched between the printed wiring board and laminated at 80 ° C., and then crimped for 30 minutes at 160 ° C. and 1.0 MPa. .. Further, this test piece was heat-cured at 160 ° C. for 2 hours to prepare a test piece for evaluation. The evaluation test piece was bent 180 degrees under a load of 500 g with the cured coating film surface on the outside, and the number of times until cracks occurred was evaluated according to the following criteria.
A ... "No cracks can be seen even after bending 20 times."
B ... "No cracks are seen even after bending 14 times. Cracks occur by 20 times."
C ... "No cracks are seen even after bending 8 times. Cracks occur by 14 times."
D ... "No cracks are seen even after bending 3 times. Cracks occur by 8 times."
E ... "Cracks occur before bending 3 times"

(5) Adhesiveness after humidification The test piece cut out to a width of 10 mm and a length of 65 mm prepared in the above (2) was cut out at 85 ° C. and 85% RH (hereinafter referred to as high humidity), 40 ° C. and 90% RH (hereinafter referred to as high humidity). After storing for 7 days and 3 days in each environment of low humidity), a T-peel peeling test was conducted at a tensile speed of 300 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%, as in the case of (2) above. After humidification, the adhesive strength (N / cm) was measured and evaluated according to the following criteria.
A ... High humidity, adhesive strength after 7 days is 3N or more B ... High humidity, adhesive strength after 7 days is less than 3N, but high humidity, adhesive strength after 3 days is 3N or more C ... High Moisture, the adhesive strength after 3 days is less than 3N, but low humidity, the adhesive strength after 7 days is 3N or more D ... Low humidity, the adhesive strength after 7 days is less than 3N, but the adhesive strength after 3 days is low. 3N or more E ・ ・ ・ Low humidity, adhesive strength after 3 days is less than 3N

表１２〜３２に示す実施例と比較例をみてわかる通り、比較例１、５、９、１１、１３、１５では、アルカリ金属化合物（Ｃ）の含有量が１１０ｐｐｍ以下であるため、リワーク性が悪化した。また、比較例２〜４、６〜８では、アルカリ金属化合物（Ｃ）の代わりに別の金属化合物を添加したため、リワーク性が悪化した。さらに、比較例１０、１２、１４、１６のように、１００００ｐｐｍよりも過剰にアルカリ金属化合物（Ｃ）を含有していると、加湿後接着性が悪化した。また、比較例１７、比較例１８からわかるように、硬化剤（Ｂ）を含有していない場合、耐熱性や加湿後接着性が著しく悪化した。

As can be seen from the examples and comparative examples shown in Tables 12 to 32, in Comparative Examples 1, 5, 9, 11, 13, and 15, since the content of the alkali metal compound (C) is 110 ppm or less, the reworkability is improved. It got worse. Further, in Comparative Examples 2 to 4, 6 to 8, since another metal compound was added instead of the alkali metal compound (C), the reworkability was deteriorated. Further, as in Comparative Examples 10, 12, 14, and 16, when the alkali metal compound (C) was contained in an amount exceeding 10,000 ppm, the adhesiveness after humidification deteriorated. Further, as can be seen from Comparative Examples 17 and 18, when the curing agent (B) was not contained, the heat resistance and the adhesiveness after humidification were remarkably deteriorated.

On the other hand, as described in Examples, the resin (A), the curing agent (B), and the alkali metal compound (C) are contained, and the alkali metal compound (C) is more than 110 ppm in terms of mass of the alkali metal element, and is 10,000 ppm. In the case of containing the following, in addition to achieving both reworkability and post-humidification adhesiveness, which were inconsistent with each other in the comparative example, adhesiveness, heat resistance, and flexibility could be satisfied. This is because the resin (A) and the curing agent (B) impart adhesiveness, heat resistance, and flexibility, and by further containing an appropriate amount of the alkali metal compound (C), reworkability and post-humidity adhesiveness are improved. This is because they were compatible.

The thermocurable composition used for forming the adhesive sheet of the present invention provides a cured product having excellent plating solution resistance, adhesiveness, heat resistance after humidification, heat resistance, flexibility, and electrical insulation, and thus printed wiring. Coating agents for electronic materials such as boards, solder resists for circuit coatings, coverlay films, conductive adhesive sheets, adhesives for electromagnetic wave shielding, heat conductive adhesive sheets, plating resists, interlayer electrical insulation materials for printed wiring boards, optical It can be suitably used for a waveguide or the like.

Claims (3)

A thermosetting composition that satisfies all of the following conditions (1) to (6-1) ( excluding an anchor coating agent for a transparent inorganic vapor-deposited film containing polyurethane and a polyisocyanate compound) .
(1) Contains 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-containing compound.
(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 (A) is made of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, styrene elastomer, fluororesin and styrene maleic anhydride resin. It is at least one selected from the group of plastics.
(5) The alkali metal compound (C) is contained in the solid content of the thermosetting composition in an amount of more than 110 ppm and 10,000 ppm or less in terms of mass of the alkali metal element.
(6-1) The total reactive functional group value of 1 g of the resin (A) is 1 to 80 mg in terms of potassium hydroxide. A thermosetting composition that satisfies all of the following conditions (1) to (6-2) ( excluding an anchor coating agent for a transparent inorganic vapor-deposited film containing polyurethane and a polyisocyanate compound) .
(1) Contains 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-containing compound.
(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 (A) is made of acrylic resin, polyester resin, polyurethane resin, polyurethane polyurea resin, polyamide resin, polyimide resin, polycarbonate resin, polyphenylene ether resin, styrene elastomer, fluororesin and styrene maleic anhydride resin. It is at least one selected from the group of plastics.
(5) The alkali metal compound (C) is contained in the solid content of the thermosetting composition in an amount of more than 110 ppm and 10,000 ppm or less in terms of mass of the alkali metal element.
(6-2) 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 with respect to 1 mol of the reactive functional group of the resin (A). The thermosetting composition according to claim 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.