KR102388938B1 - Polyimide, adhesive, film-shaped adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board, and multi-layer board and manufacturing method thereof - Google Patents

Abstract

<task>
An object of the present invention is to provide a polyimide, an adhesive, a film adhesive, an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, a printed wiring board, a multilayer wiring board, and a method for manufacturing the same.
<Solutions>
A polyimide that is a reactant of a group of monomers containing an aromatic tetracarboxylic anhydride and a diamine containing dimerdiamine, and a polyimide containing a fluorenylene group in the polymer main chain, and an adhesive containing a polyimide, a crosslinking agent and an organic solvent, and a film adhesive; A solution is to provide an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a manufacturing method thereof.

Description

Polyimide, adhesive, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, and multi-layer wiring board and manufacturing method thereof {POLYIMIDE, ADHESIVE, FILM-SHAPED ADHESIVE MATERIAL, ADHESIVE LAYER, ADHESIVE SHEET, COPPER FOIL WITH RESIN, COPPER CLAD LAMINATE, PRINTED WIRING BOARD, AND MULTI-LAYER BOARD AND MANUFACTURING METHOD THEREOF}

The present disclosure relates to a polyimide, an adhesive, a film adhesive, an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a manufacturing method thereof.

Various known adhesives are used to manufacture mobile communication devices such as mobile phones and smart phones, base station devices thereof, network-related electronic devices such as servers and routers, printed wiring boards included in large computers, and the like.

The present applicant proposes "a polyimide-based adhesive composition comprising a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent formed by reacting an aromatic tetracarboxylic acid and diamines containing 30 mol% or more of a specific dimer diamine." There is (refer to Patent Document 1).

Japanese Patent No. 5534378

In recent years, in the network-related electronic devices, it is necessary to transmit and process large amounts of information with low loss and high speed, and electrical signals handled by printed wiring boards of these products are also increasing in frequency. Since a high-frequency electric signal is easily attenuated, it is necessary to further reduce the transmission loss in the printed wiring board. For this reason, adhesives generally used for printed wiring boards are required to have low dielectric constant and low dielectric loss tangent (also referred to as low dielectric properties).

However, in Patent Document 1, the low dielectric loss tangent has not been studied. In addition, in recent years, there has been a problem in that an adhesive having a low dielectric loss tangent is particularly required along with the increase in the frequency of electric signals.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solved with a predetermined|prescribed polyimide, as a result of earnestly examining.

The present disclosure provides the following items.

(Item 1)

aromatic tetracarboxylic anhydride;

and diamines including dimerdiamines.

It is a reactant of a group of monomers comprising a fluorenylene group in the polymer main chain

A polyimide comprising a.

(Item 2)

The diamine is a diamine containing a fluorene skeleton

(In the formula, either one of R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, any one of R ³ or R ⁴ represents a group having an amino group, and another One represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom)

The polyimide according to the item comprising a.

(Item 3)

The polyimide according to any one of the above items, wherein the diamine contains diaminopolysiloxane.

(Item 4)

The polyimide according to any one of the above items, wherein the molar ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic acid anhydride to the diamine is 1.0 to 1.5.

(Item 5)

An adhesive comprising the polyimide according to any one of the above items, a crosslinking agent, and an organic solvent.

(Item 6)

The adhesive according to the above item, wherein the crosslinking agent is at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides and cyanate esters.

(Item 7)

The epoxide is an epoxide of the structure

(wherein Y represents a phenylene group or a cyclohexylene group)

The adhesive according to the above item.

(Item 8)

The adhesive according to any one of the above items, comprising 5 to 900 parts by mass of the crosslinking agent and 150 to 900 parts by mass of the organic solvent with respect to 100 parts by mass of the polyimide (in terms of solid content).

(Item 9)

A film adhesive comprising the heat-cured product of the adhesive according to any one of the preceding items.

(Item 10)

An adhesive layer comprising the adhesive according to any one of the above items or the film-like adhesive of the above items.

(Item 11)

An adhesive sheet comprising the adhesive layer according to the above and a support film.

(Item 12)

A copper foil with a resin comprising the adhesive layer according to the above item and copper foil.

(Item 13)

A copper-clad laminate comprising the copper foil with resin according to the above item and the copper foil.

(Item 14)

A copper-clad laminate comprising the copper foil with resin according to the above and an insulating sheet.

(Item 15)

The printed wiring board which has a circuit pattern on the copper foil surface of the copper clad laminated board in any one of the said items.

(Item 16)

printed wiring board (1) or printed circuit board (1);

The adhesive layer described in the above item, and

A printed wiring board (2) or a multilayer wiring board comprising a printed circuit board (2).

(Item 17)

A method for manufacturing a multilayer wiring board comprising the following steps 1 and 2.

Step 1: A step of producing a base material with an adhesive layer by bringing the adhesive according to any one of the above items or the film adhesive material according to the above items into contact with at least one surface of the printed wiring board 1 or the printed circuit board 1

Step 2: A step of laminating a printed wiring board 2 or a printed circuit board 2 on the substrate with an adhesive layer and pressing under heating and pressure

In the present disclosure, one or more features described above may be provided in further combination in addition to the specified combination.

By using the polyimide of the present invention, an adhesive having a low dielectric loss tangent can be provided. The adhesive can be suitably used for high-frequency electronic components such as high-function mobile terminals such as printed wiring boards.

Throughout the present disclosure, ranges of numerical values such as respective physical properties and content may be appropriately set (eg, by selecting from the values of the upper and lower limits described in each item below). Specifically, for the numerical value α, when the upper limit of the numerical value α is exemplified by A1, A2, A3, etc., and the lower limit of the numerical value α is exemplified by B1, B2, B3, etc., the range of the numerical value α is A1 or less, A2 or less, A3 Hereinafter, B1 or more, B2 or more, B3 or more, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. are exemplified. .

[Polyimide]

The present disclosure relates to an aromatic tetracarboxylic acid anhydride,

and diamines including dimerdiamines.

It is a reactant of a group of monomers comprising a fluorenylene group in the polymer main chain

It provides a polyimide comprising a.

In the present disclosure, "including a fluorenylene group in the polymer main chain" means that the longest chain constituting the polymer includes a fluorenylene group.

<Aromatic tetracarboxylic acid anhydride>

The aromatic tetracarboxylic anhydride may be used alone or in combination of two or more. Examples of the aromatic tetracarboxylic acid anhydride include fluorene skeleton-containing tetracarboxylic acid anhydride and symmetric aromatic tetracarboxylic acid anhydride.

(tetracarboxylic anhydride containing fluorene skeleton)

In one embodiment, the fluorene skeleton-containing tetracarboxylic anhydride is represented by the following general formula

(wherein, either one of R ¹ or R ² represents a group having an acid anhydride group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either one of R ³ or R ⁴ represents a group having an acid anhydride group , the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, or R ¹ and R ² and/or R ³ and R ⁴ represent a group forming an acid anhydride group as one).

Examples of the group having an acid anhydride group include a 3,4-dicarboxyphenoxy group and a 3,4-dicarboxyphenyl group.

When R ¹ and R ² and/or R ³ and R ⁴ become one to form an acid anhydride group, the formed acid anhydride group is exemplified by a 3,4-dicarboxyphenyl group.

Examples of the alkyl group include a straight-chain alkyl group, a branched alkyl group, and a cycloalkyl group.

Although the number of carbon atoms of the alkyl group is not particularly limited, the upper limit is exemplified by 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc., and the lower limit is 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 and the like are exemplified. In one embodiment, about 1-30 are preferable, as for carbon number of an alkyl group, about 1-20 are more preferable, about 1-16 are more preferable, and about 1-12 are especially preferable.

Examples of the straight-chain alkyl group include a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. .

The branched alkyl group is exemplified by an isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, and an isodecyl group.

As for the cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc. are illustrated. In the cycloalkyl group, one or more hydrogen atoms in each ring may be substituted with a straight-chain alkyl group (such as the group in the above example) or a branched alkyl group (such as the group in the above example).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Tetracarboxylic acid anhydride containing a fluorene skeleton is 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 9,9'-bis(3,4-dicarboxyphenoxy) Fluorenic acid dianhydride etc. are illustrated.

100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 mol%, etc. are exemplified as the upper limit of the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mol% of aromatic tetracarboxylic acid anhydride, and the lower limit is 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mol% and the like are exemplified. In one embodiment, about 0-100 mol% is preferable and, as for content of the fluorene skeleton containing tetracarboxylic-acid anhydride in 100 mol% of aromatic tetracarboxylic-acid anhydride, about 50-100 mol% is more preferable.

100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 mass % etc. are illustrated as an upper limit of content of a fluorene skeleton containing tetracarboxylic acid anhydride in 100 mass % of aromatic tetracarboxylic acid anhydride, and a lower limit is 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mass % etc. are illustrated. In one embodiment, about 0-100 mass % is preferable and, as for content of the fluorene skeleton containing tetracarboxylic acid anhydride in 100 mass % of aromatic tetracarboxylic-acid anhydride, about 50-100 mass % is more preferable.

The upper limit of the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mol% of the monomer group is exemplified by 75, 70, 60, 50, 40, 30, 20, 10, 5 mol% and the like, and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mol% and the like are exemplified. In one embodiment, as for content of the fluorene skeleton containing tetracarboxylic acid anhydride in 100 mol% of monomer groups, about 0-75 mol% is preferable.

75, 70, 60, 50, 40, 30, 20, 10, 5 mass % etc. are illustrated as for the upper limit of content of the fluorene skeleton containing tetracarboxylic acid anhydride in 100 mass % of monomer groups, The lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mass % etc. are illustrated. In one embodiment, as for content of fluorene skeleton containing tetracarboxylic acid anhydride in 100 mass % of monomer groups, about 0-75 mass % is preferable.

(Symmetric aromatic tetracarboxylic acid anhydride)

In the present disclosure, "symmetric aromatic tetracarboxylic acid anhydride" means an aromatic tetracarboxylic acid anhydride having an axis of symmetry (eg, C2 symmetry axis) in a molecule. Symmetrical aromatic tetracarboxylic acid anhydrides have the following general formula

(wherein X is a single bond, -SO ₂ -, -CO-, -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -COO-(CH ₂ ) ) _p -OCO-, or -COO-H ₂ C-HC (-O-C(=O)-CH ₃ )-CH ₂ -OCO- is represented, and p represents the integer of 1-20)

Indicated by , etc. are exemplified.

The symmetric aromatic tetracarboxylic anhydride represented by the above general formula is 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride, 3, 3', 4, 4'-diphenylsulfonetetracarboxylic dianhydride, 3, 3 ', 4, 4'-benzophenone tetracarboxylic dianhydride, 3, 3', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 4, 4'- [propane-2, 2-diylbis (1, 4) -Phenyleneoxy)]diphthalic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropanedianhydride, 2,2-bis(3,4-dicarboxy Phenyl) propane dianhydride, 2, 2'-bis (3, 4- dicarboxyphenoxy phenyl) sulfonic anhydride, 2, 2', 3, 3'-biphenyltetracarboxylic dianhydride, 2, 2-bis ( 2, 3-dicarboxyphenyl) propane dianhydride, pyromellitic dianhydride, 1, 2, 3, 4-benzenetetracarboxylic anhydride, 1, 4, 5, 8-naphthalenetetracarboxylic anhydride, 2, 3, 6, 7-naphthalenetetracarboxylic anhydride etc. are illustrated.

Among the symmetric aromatic tetracarboxylic acid anhydrides, 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride, 4, 4' -[propane-2,2-diylbis(1,4-phenyleneoxy)] At least 1 sort(s) chosen from the group which consists of diphthalic dianhydride and 4,4'- oxydiphthalic anhydride is preferable.

The upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100 mol% of the aromatic tetracarboxylic acid anhydride is exemplified by 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 mol%, and the like, and the lower limit is 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mol% and the like are exemplified. In one embodiment, the content of the symmetric aromatic tetracarboxylic acid anhydride in 100 mol% of the aromatic tetracarboxylic acid anhydride is preferably about 50 to 100 mol%.

The upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100% by mass of the aromatic tetracarboxylic acid anhydride is exemplified by 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10% by mass, etc., and the lower limit is 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mass % etc. are illustrated. In one embodiment, about 0-100 mass % is preferable and, as for content of the symmetric aromatic tetracarboxylic-acid anhydride in 100 mass % of aromatic tetracarboxylic-acid anhydride, about 50-100 mass % is more preferable.

Examples of the upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group include 75, 70, 60, 50, 40, 30, 20, 10, 5 mol%, and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mol% and the like are exemplified. In one embodiment, the content of the symmetric aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably about 0 to 75 mol%.

Examples of the upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100% by mass of the monomer group are 75, 70, 60, 50, 40, 30, 20, 10, 5% by mass, and the like, and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mass %, etc. are illustrated. In one embodiment, as for content of the symmetric aromatic tetracarboxylic anhydride in 100 mass % of monomer groups, about 0-75 mass % is preferable.

(Other aromatic tetracarboxylic anhydrides)

In one embodiment, the monomer group may include an aromatic tetracarboxylic anhydride (also referred to as other aromatic tetracarboxylic anhydrides) that is neither the fluorene skeleton-containing tetracarboxylic anhydride nor the symmetric aromatic tetracarboxylic anhydride.

In one embodiment, as for content of the other acid anhydride in an aromatic tetracarboxylic acid anhydride, less than 5, 4, 1, 0.9, 0.5, 0.1 mol%, about 0 mol%, etc. are illustrated.

In one embodiment, as for content of the other acid anhydride in an aromatic tetracarboxylic acid anhydride, less than 5, 4, 1, 0.9, 0.5, 0.1 mass %, about 0 mass %, etc. are illustrated.

In one embodiment, the content of the other acid anhydride in a monomer group is less than 5, 4, 1, 0.9, 0.5, 0.1 mol%, about 0 mol%, etc. are illustrated.

In one embodiment, as for content of the other acid anhydride in a monomer group, less than 5, 4, 1, 0.9, 0.5, 0.1 mass %, about 0 mass %, etc. are illustrated.

The upper limit of the content of the aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group is exemplified by 75, 70, 65, 60, 55 mol% or the like, and the lower limit is exemplified by 70, 65, 60, 55, 50 mol% or the like. In one embodiment, the content of the aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group is preferably about 50 to 75 mol%.

75, 70, 65, 60, 55 mass % etc. are illustrated as for the upper limit of content of aromatic tetracarboxylic acid anhydride in 100 mass % of monomer groups, and 70, 65, 60, 55, 50 mass % etc. are illustrated as for a lower limit. In one embodiment, as for content of the aromatic tetracarboxylic-acid anhydride in 100 mass % of monomer groups, about 50-75 mass % is preferable.

<diamine>

Diamines may be used alone or in combination of two or more. Examples of the diamine include dimer diamine, fluorene skeleton-containing diamine, and diaminopolysiloxane.

(dimerdiamine)

In the present disclosure, dimerdiamine refers to all carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, substituted with primary amino groups (see Japanese Patent Application Laid-Open No. 1997-12712, etc.), and various known ones can be used without particular limitation. can Hereinafter, a non-limiting general formula of dimerdiamine is shown (in each formula, m+n=6 to 17 is preferable, p+q=8 to 19 is preferable, and the broken line represents a carbon-carbon single bond or a carbon-carbon double bond. it means).

Commercial products of dimerdiamine are vasamine 551 (manufactured by Cognix Japan Co., Ltd.), vasamine 552 (manufactured by Cognics Japan Co., Ltd.; hydrogenated product of vasamine 551), PRIAMINE1075, PRIAMINE1074 (all manufactured by Kuroda Japan Co., Ltd.) etc. are exemplified.

The upper limit of content of the dimerdiamine component in 100 mol% of diamine 100, 90, 80, 70, 60, 50, 40, 30, 25 mol% etc. are illustrated, and a lower limit is 90, 80, 75, 70, 60, 50 , 40, 30, 25, 20 mol% and the like are exemplified. In one embodiment, as for content of the dimer diamine component in 100 mol% of diamine, from a viewpoint of a softness|flexibility, adhesiveness, and solvent solubility improvement, about 20-100 mol% is preferable.

As for the upper limit of content of the dimer diamine component in 100 mass % of diamine, 100, 90, 80, 70, 60, 50, 40, 30, 25 mass % etc. are illustrated, and a minimum is 90, 80, 75, 70, 60, 50 , 40, 30, 25, 20 mass % etc. are illustrated. In one embodiment, as for content of the dimer diamine component in 100 mass % of diamine, from a viewpoint of a softness|flexibility, adhesiveness, and a solvent solubility improvement, about 20-100 mass % is preferable.

The upper limit of the content of dimerdiamine in 100 mol% of the monomer group is exemplified by 50, 40, 30, 20, 10, 8 mol%, etc., and the lower limit is exemplified by 40, 30, 20, 10, 8, 5 mol%, etc. . In one embodiment, as for content of dimerdiamine in 100 mol% of monomer groups, 5-50 mol% is preferable.

50, 40, 30, 20, 10, 8 mass % etc. are illustrated as for the upper limit of content of dimerdiamine in 100 mass % of monomer group, 40, 30, 20, 10, 8, 5 mass % etc. are illustrated as for a lower limit . In one embodiment, as for content of dimerdiamine in 100 mass % of monomer groups, 5-50 mass % is preferable.

(Diamine containing fluorene skeleton)

In one embodiment, the fluorene skeleton-containing diamine has the following general formula

(In the formula, either one of R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, any one of R ³ or R ⁴ represents a group having an amino group, and another One represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom).

In the present disclosure, the "group having an amino group" means a group in which at least one hydrogen atom of an amino group and a functional group is substituted with an amino group. Examples of the group having an amino group include an amino group, an alkylamino group, an arylamino group, an alkoxyamino group, and an aryloxyamino group.

Examples of the aryl group include a monocyclic aryl group and a condensed cyclic aryl group. In the aryl group, one or more hydrogen atoms may be substituted with a straight-chain or branched alkyl group.

The monocyclic aryl group includes, for example, a phenyl group, a tolyl group, and a mesityl group. Moreover, a naphthyl group etc. are illustrated as a condensed ring aryl group.

Diamine containing fluorene skeleton is 9,9'-bis(aminophenyl)fluorene, 9,9'-bis(4-amino-3-methylphenyl)fluorene, 9,9'-bis(4-amino-3- Fluorophenyl) fluorene, 9, 9'-bis (4-amino-3-hydroxyphenyl) fluorene, 9, 9'-bis (4-methyl-3-aminophenyl) fluorene, 9, 9' -bis(4-fluoro-3-aminophenyl)fluorene, 9,9'-bis(4-hydroxy-3-aminophenyl)fluorene, 9,9'-bis[4-(4-aminophenoxy) C) phenyl] fluorene etc. are illustrated.

80, 70, 60, 50, 40, 30, 25 mol% etc. are illustrated as for the upper limit of content of the fluorene skeleton containing diamine component in 100 mol% of diamine, The lower limit is 75, 70, 60, 50, 40, 30, 25, 20 mol%, etc. are exemplified. In one embodiment, as for content of the diamine component containing a fluorene skeleton in 100 mol% of diamine, from a viewpoint of a dielectric property improvement, about 20-80 mol% is preferable.

80, 70, 60, 50, 40, 30, 25 mass % etc. are illustrated as for the upper limit of content of the fluorene skeleton containing diamine component in 100 mass % of diamine, The lower limit is 75, 70, 60, 50, 40, 30, 25, 20 mass %, etc. are illustrated. In one embodiment, as for content of the fluorene skeleton containing diamine component in 100 mol% of diamine, from a viewpoint of a dielectric property improvement, about 20-80 mass % is preferable.

The upper limit of the content of the fluorene skeleton-containing diamine in 100 mol% of the monomer group is exemplified by 50, 40, 30, 20, 10, 5 mol%, and the like, and the lower limit is 40, 30, 20, 10, 5, 0 mol%, etc. This is exemplified. In one embodiment, as for content of fluorene skeleton containing diamine in 100 mol% of monomer groups, 0-50 mol% is preferable.

As for the upper limit of content of fluorene skeleton containing diamine in 100 mass % of monomer groups, 50, 40, 30, 20, 10, 5 mass % etc. are illustrated, The lower limit is 40, 30, 20, 10, 5, 0 mass %, etc. This is exemplified. In one embodiment, as for content of fluorene skeleton containing diamine in 100 mass % of monomer groups, 0-50 mass % is preferable.

The upper limit of the ratio of the substance amount of the fluorene skeleton-containing diamine to the substance amount of the dimerdiamine (diamine/dimerdiamine containing a fluorene skeleton) is 4.00, 3.00, 2.00, 1.00, 0.50, etc., and the lower limit is 4.00, 3.00, 2.00, 1.00 , 0.50, 0.25, and the like are exemplified. In one embodiment, the ratio of the substance amount of the fluorene skeleton-containing diamine to the substance amount of the dimerdiamine (diamine/dimerdiamine containing the fluorene skeleton) is preferably about 0.25 to 4.00 from the viewpoint of flexibility, adhesion, and improvement of dielectric properties. .

(diaminopolysiloxane)

Diaminopolysiloxanes include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α , ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl] polydimethylsiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, etc. are illustrated.

5, 4, 3, 2, 1 mol% etc. are illustrated as for the upper limit of content of diaminopolysiloxane in 100 mol% of diamine, 4, 3, 2, 1, 0 mol%, etc. are illustrated as for a minimum. In one embodiment, the content of diaminopolysiloxane in 100 mol% of diamine is preferably about 0 to 5 mol% from the viewpoint of improving flexibility.

5, 4, 3, 2, 1 mol% etc. are illustrated as for the upper limit of content of diamino polysiloxane in 100 mass % of diamine, 4, 3, 2, 1, 0 mass %, etc. are illustrated as for a minimum. In one embodiment, as for content of diaminopolysiloxane in 100 mass % of diamine, from a viewpoint of a softness|flexibility improvement, about 0-5 mass % is preferable.

5, 4, 3, 2, 1 mol% etc. are illustrated as for the upper limit of content of diaminopolysiloxane in 100 mol% of monomer groups, and 4, 3, 2, 1, 0 mol%, etc. are illustrated as for a lower limit. In one embodiment, the content of diaminopolysiloxane in 100 mol% of the monomer group is preferably about 0 to 5 mol% from the viewpoint of improving the flexibility.

5, 4, 3, 2, 1 mass % etc. are illustrated as for the upper limit of content of diamino polysiloxane in 100 mass % of monomer groups, and 4, 3, 2, 1, 0 mass % etc. are illustrated as for a minimum. In one embodiment, as for content of the diaminopolysiloxane in 100 mass % of monomer groups, from a viewpoint of a softness|flexibility improvement, about 0-5 mass % is preferable.

(other diamines)

In one embodiment, the monomer group may include diamines other than the above (also referred to as other diamines). Other diamines include alicyclic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diamine. Minophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminoditrifluoromethylbenzylbenzene, aminophenoxybiphenyl, Aminophenoxyphenylketone, aminophenoxyphenylsulfide, aminophenoxyphenylsulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis(aminophenoxybenzoyl)benzene, bis(aminophenoxy-α, α- Dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenyl ether, bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, bis[amino-α,α-dimethylbenzylphenoxy]diphenylsulfone , 4,4'-bis[aminophenoxyphenoxy]diphenylsulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis(aminoaryloxy)-3,3,3 ', 3'-tetramethyl-1, 1'-spirobindane, bis(aminoalkyl)ether, bis(aminoalkoxyalkyl)ether, bis(aminoalkoxy)alkane, bis[(aminoalkoxy)alkoxy]alkane, ( Poly)ethylene glycol bis(aminoalkyl)ether, bis(aminoaryloxy)pyridine, diaminoalkylene, etc. are illustrated.

Alicyclic diamine is diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2. 2. 1] Heptane, 3(4), 8(9)-bis(aminomethyl)tricyclo[5. 2. 1. 02, 6] Decane, isophorone diamine, 4, 4'- diamino dicyclohexyl methane, 1, 3-bisamino methyl cyclohexane, etc. are illustrated.

Examples of the bisaminophenoxyphenylpropane include 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

Examples of diaminodiphenyl ether include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether.

Examples of the phenylenediamine include phenylenediamines such as p-phenylenediamine and m-phenylenediamine.

Examples of the diaminodiphenyl sulfide include 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, and 4,4′-diaminodiphenylsulfide.

Examples of diaminodiphenyl sulfone include 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenylsulfone.

Examples of diaminobenzophenone include 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, and 3,4'-diaminobenzophenone.

Examples of diaminodiphenylmethane include 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-diaminodiphenylmethane.

Diaminophenylpropane includes 2,2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, etc. This is exemplified.

Diaminophenylhexafluoropropane is 2,2-di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1 , 1, 1, 3, 3, 3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1, 1, 1, 3, 3, 3-hexafluoropropane etc. are exemplified.

Diaminophenylphenylethane is 1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1 -(4-aminophenyl)-1-phenylethane etc. are illustrated.

Bisaminophenoxybenzene is 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1, 4-bis(4-aminophenoxy)benzene etc. are illustrated.

Bisaminobenzoylbenzene includes 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis( 4-aminobenzoyl)benzene etc. are illustrated.

Bisaminodimethylbenzylbenzene includes 1,3-bis(3-amino-α, α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α, α-dimethylbenzyl)benzene, 1,4-bis( 3-amino-α, α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α, α-dimethylbenzyl)benzene, and the like are exemplified.

Bisaminoditrifluoromethylbenzylbenzene is 1,3-bis(3-amino-α, α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α, α-ditrifluoro Romethylbenzyl)benzene, 1,4-bis(3-amino-α, α-ditrifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α, α-ditrifluoromethylbenzyl) benzene and the like are exemplified.

Aminophenoxybiphenyl is 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)bi phenyl and the like are exemplified.

Examples of the aminophenoxyphenyl ketone include bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone.

Examples of the aminophenoxyphenyl sulfide include bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide.

Examples of aminophenoxyphenylsulfone include bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone.

Examples of aminophenoxyphenyl ether include bis[4-(3-aminophenoxy)phenyl]ether and bis[4-(4-aminophenoxy)phenyl]ether.

Aminophenoxyphenylpropane is 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3 , 3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1, 1, 1, 3, 3, 3-hexafluoropropane, etc. are illustrated.

Bis(aminophenoxybenzoyl)benzene is 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,4 -bis[4-(3-aminophenoxy)benzoyl]benzene, 1, 4-bis[4-(4-aminophenoxy)benzoyl]benzene, etc. are illustrated.

Bis(aminophenoxy-α, α-dimethylbenzyl)benzene is 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4) -Aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4) -aminophenoxy)-α, α-dimethylbenzyl]benzene and the like are exemplified.

Examples of the bis[(aminoaryloxy)benzoyl]diphenyl ether include 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether.

Examples of the bis(amino-α, α-dimethylbenzylphenoxy)benzophenone include 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone.

Examples of the bis[amino-α, α-dimethylbenzylphenoxy]diphenylsulfone include 4,4′-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone.

4,4'-bis[aminophenoxyphenoxy]diphenylsulfone, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone etc. are illustrated.

Examples of diaminodiaryloxybenzophenone include 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3'-diamino-4,4'-dibiphenoxybenzophenone.

Examples of diaminoaryloxybenzophenone include 3,3'-diamino-4-phenoxybenzophenone and 3,3'-diamino-4-biphenoxybenzophenone.

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobindan is 6,6'-bis(3-aminophenoxy)-3, 3, 3', 3'-tetramethyl-1, 1'-spirobindane, 6, 6'-bis(4-aminophenoxy)-3, 3, 3', 3'-tetramethyl-1, 1 '- spirobiindan and the like are exemplified.

Examples of the bis(aminoalkyl)ether include bis(aminomethyl)ether, bis(2-aminoethyl)ether, and bis(3-aminopropyl)ether.

Bis(aminoalkoxyalkyl)ether is bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether etc. are exemplified.

Examples of the bis(aminoalkoxy)alkane include 1,2-bis(aminomethoxy)ethane and 1,2-bis(2-aminoethoxy)ethane.

Examples of bis[(aminoalkoxy)alkoxy]alkanes include 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, etc. do.

Examples of the (poly) ethylene glycol bis (aminoalkyl) ether include ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, and triethylene glycol bis (3-aminopropyl) ether. .

Examples of the bis(aminoaryloxy)pyridine include 2,6-bis(3-aminophenoxy)pyridine.

Diaminoalkylene is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1, 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. are illustrated.

In one embodiment, as for content of other diamine in diamine, less than 5, 4, 1, 0.9, 0.5, 0.1 mol%, about 0 mol%, etc. are illustrated.

In one embodiment, as for content of other diamine in diamine, less than 5, 4, 1, 0.9, 0.5, 0.1 mass %, about 0 mass %, etc. are illustrated.

In one embodiment, as for content of other diamine in a monomer group, less than 5, 4, 1, 0.9, 0.5, 0.1 mol%, about 0 mol%, etc. are illustrated.

In one embodiment, as for content of the other diamine in a monomer group, less than 5, 4, 1, 0.9, 0.5, 0.1 mass %, about 0 mass %, etc. are illustrated.

As for the upper limit of content of the diamine in 100 mol% of monomer groups, 50, 45, 40, 35, 30 mol% etc. are illustrated, and 45, 40, 35, 30, 25 mol%, etc. are illustrated as for a lower limit. In one embodiment, as for content of the diamine in 100 mol% of monomer groups, about 25-50 mol% is preferable.

As for the upper limit of content of the diamine in 100 mass % of monomer groups, 50, 45, 40, 35, 30 mass % etc. are illustrated, and 45, 40, 35, 30, 25 mass % etc. are illustrated as for a minimum. In one embodiment, as for content of the diamine in 100 mass % of monomer groups, about 25-50 mass % is preferable.

The upper limit of the molar ratio of the aromatic tetracarboxylic acid anhydride to the diamine [aromatic tetracarboxylic acid anhydride/diamine] is 1.5, 1.4, 1.3, 1.2, 1.1, etc., and the lower limit is 1.4, 1.3, 1.2, 1.1, 1.0 and the like. In one embodiment, the molar ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic acid anhydride to the diamine is preferably about 1.0 to 1.5 from the viewpoints of solvent solubility and solution stability.

The upper limit of the mass ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic acid anhydride to the diamine is 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, etc., and the lower limit is 1.4, 1.2, 1.0, 0.9, 0.7, 0.6 , 0.5 and the like are exemplified. In one embodiment, the mass ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic acid anhydride to the diamine is preferably 0.5 to 1.5.

<Other monomers>

In one embodiment, the monomer group may include a monomer that is neither an aromatic tetracarboxylic acid anhydride nor a diamine (also referred to as another monomer). As for other monomers, an aliphatic tetracarboxylic anhydride etc. are illustrated.

In one embodiment, as for content of the other monomer in a monomer group, less than 5, 4, 1, 0.9, 0.5, 0.1 mol%, about 0 mol%, etc. are illustrated.

In one embodiment, as for content of the other monomer in a monomer group, less than 5, 4, 1, 0.9, 0.5, 0.1 mass %, about 0 mass %, etc. are illustrated.

<Physical properties of polyimide, etc.>

The upper limit of the weight average molecular weight of the polyimide is exemplified by 50000, 40000, 30000, 20000, 10000, 7500, 5500, and the like, and the lower limit is exemplified by 45000, 40000, 30000, 20000, 10000, 7500, 5000, and the like. In one embodiment, the weight average molecular weight of the polyimide is preferably 5000-50000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The upper limit of the number average molecular weight of the polyimide is exemplified by 40000, 30000, 20000, 10000, 7500, 5000, 3000, and the like, and the lower limit is exemplified by 35000, 30000, 20000, 10000, 7500, 5000, 3000, 2000, and the like. In one embodiment, the number average molecular weight of the polyimide is preferably 2000 to 40,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The weight average molecular weight and the number average molecular weight can be determined as, for example, polystyrene conversion values measured by gel permeation chromatography (GPC).

The upper limit of the softening point of the polyimide is exemplified by 220, 200, 150, 100, 50, 25°C, and the like, and the lower limit is exemplified by 210, 200, 150, 100, 50, 25, 20°C, and the like. In one embodiment, as for the softening point of the said polyimide, 20-220 degreeC is preferable from a viewpoint of workability|operativity, heat resistance, and solvent solubility.

The softening point can be obtained using a commercially available measuring device ("ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific) or the like.

<The manufacturing method of polyimide, etc.>

The said polyimide can be manufactured by various well-known methods. In the method for producing polyimide, a monomer group containing an aromatic tetracarboxylic anhydride and a diamine including dimerdiamine, etc., is preferably at a temperature of about 60 to 120 ° C, more preferably about 80 to 100 ° C. Preferably for about 0.1 to 2 hours, more preferably for about 0.1 to 0.5 hours, the polyaddition reaction is carried out to obtain a polyaddition product, and the obtained polyaddition product is preferably about 80 to 250° C., more preferably 100 to 200° C. At the temperature of the degree, Preferably it is about 0.5-50 hours, More preferably, it is about 1-20 hours, The method etc. including the process of imidation reaction, ie, dehydration ring closure reaction, are illustrated.

In addition, various well-known reaction catalysts, a dehydrating agent, and the organic solvent mentioned later can be used in the imidation process. Various known reaction catalysts, dehydrating agents, and organic solvents to be described later may be used alone or in combination of two or more. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline. Moreover, as a dehydrating agent, aliphatic acid anhydrides, such as acetic anhydride, aromatic acid anhydrides, such as benzoic anhydride, etc. are illustrated.

The imide closure rate of the polyimide is not particularly limited. Here, "imide ring closure rate" means content of the cyclic imide bond in a polyimide, For example, it can determine by various spectroscopic means, such as NMR and IR analysis. From a viewpoint of improving room temperature adhesiveness and heat-resistant adhesiveness, about 70 % or more is preferable and, as for the imide ring closure rate of the said polyimide, about 85-100 % is more preferable.

[glue]

The present disclosure provides an adhesive comprising the polyimide, a crosslinking agent, and an organic solvent.

As for the upper limit of content of the said polyimide in 100 mass % of the said adhesive agent, 90, 80, 70, 60, 50, 40, 30, 20, 10 mass % etc. are illustrated, The lower limit is 80, 70, 60, 50, 40, 30, 20, 10, 5 mass % etc. are illustrated. As for content of the said polyimide in 100 mass % of the said adhesive agent, about 5-90 mass % is preferable.

<crosslinking agent>

Various known crosslinking agents can be used without particular limitation, as long as they function as a crosslinking agent for polyimide. The crosslinking agent may be used alone or in combination of two or more. The crosslinking agent is preferably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides and cyanate esters.

(epoxide)

Epoxides are phenol novolac epoxide, cresol novolak epoxide, bisphenol A epoxide, bisphenol F epoxide, bisphenol S epoxide, hydrogenated bisphenol A epoxide, hydrogenated bisphenol F epoxide, stilbene type Epoxide, triazine skeleton-containing epoxide, fluorene skeleton-containing epoxide, linear aliphatic epoxide, alicyclic epoxide, glycidylamine-type epoxide, triphenolmethane-type epoxide, alkyl-modified triphenolmethane-type epoxide , biphenyl type epoxide, dicyclopentadiene skeleton containing epoxide, naphthalene skeleton containing epoxide, arylalkylene type epoxide, tetraglycidyl xylylenediamine, dimer acid modified epoxide which is a dimer acid modified product of the epoxide; Dimer acid diglycidyl ester etc. are illustrated. In addition, commercial products of epoxide are "jER828", "jER834", "jER807" manufactured by Mitsubishi Chemical Co., Ltd., "ST-3000" manufactured by Nippon Chemical Co., Ltd., "ST-3000" manufactured by Daicel Chemical Industries, Ltd. Ceroxide 2021P", "YD-172-X75" manufactured by Nippon Chemical Co., Ltd., "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. are illustrated. Among these, at least one selected from the group consisting of bisphenol A type epoxide, bisphenol F type epoxide, hydrogenated bisphenol A type epoxide and alicyclic epoxide is preferable from the viewpoint of the balance of heat adhesion resistance, moisture absorption solder heat resistance and low dielectric properties. Do.

In particular, tetraglycidyldiamine of the structure

(wherein Y represents a phenylene group or a cyclohexylene group)

Silver has good compatibility with the polyimide. Moreover, when this is used, it becomes easy to make the low loss elastic modulus of an adhesive layer, and the heat-resistant adhesiveness and low dielectric characteristic also become favorable.

When using an epoxide as a crosslinking agent, various well-known hardening|curing agents for epoxides can be used together. The curing agent for epoxide may be used alone or in combination of two or more. The curing agent for epoxides is succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 4-methyl-hexahydrophthalic anhydride, or 4- Mixture of methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane- Acid anhydride curing agents such as 2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine (trade name "LonzacureM-DEA"; "LonzacureM-DETDA" etc. All manufactured by Lonza Japan Co., Ltd.) and amine curing agents such as aliphatic amines; Phenolic curing agents such as hydroxyl-containing phosphazenes (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd., etc.), cyclic phosphazene compounds, rosin-based crosslinking agents such as maleic acid-modified rosin and hydrides thereof, etc. are illustrated. . Among these, a phenolic hardening|curing agent, especially a phenolic hydroxyl group containing phosphazene type|system|group hardening|curing agent is preferable. Although the usage-amount of a hardening|curing agent is not specifically limited, When the solid content of the said adhesive agent is 100 mass %, about 0.1-120 mass % is preferable, and about 10-40 mass % is more preferable.

When using together an epoxide and the hardening|curing agent for epoxides as a crosslinking agent, a reaction catalyst can further be used together. The reaction catalyst may be used alone or in combination of two or more. The reaction catalyst is 1,8-diazabicyclo[5. 4. 0] Tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole imidazoles such as , 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. of organic phosphine; tetraphenyl boron salts such as tetraphenylphosphonium/tetraphenylborate, 2-ethyl-4-methylimidazole/tetraphenylborate, and N-methylmorpholine/tetraphenylborate are exemplified. Moreover, the usage-amount of the said reaction catalyst is although it does not restrict|limit, When solid content of the said adhesive agent is 100 mass %, about 0.01-5 mass % is preferable.

(benzox picture)

Benzoxazine is 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene) den)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) etc. are illustrated. Moreover, a phenyl group, a methyl group, a cyclohexyl group, etc. may couple|bond with the nitrogen of an oxazine ring. Moreover, "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Airwater, etc. are illustrated as a commercial item of benzoxazine. .

(bismaleimide)

Bismaleimide is 4,4'-diphenylmethanebismaleimide, m-phenylenebismaleimide, bisphenol A diphenyletherbismaleimide, 3,3'-dimethyl-5, 5'-diethyl-4, 4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide (2,2,4-trimethyl)hexane, 4,4'-diphenyl Etherbismaleimide, 4,4'-diphenylsulfonebismaleimide, etc. are illustrated. Moreover, "BAF-BMI" by JFE Chemical Co., Ltd. product etc. are illustrated as a commercial item of bismaleimide.

(cyanate ester)

The cyanate ester is 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanatophenol)-1, 1, 1, 3, 3, 3-hexafluoropropane , Bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1, 1, 1-tris (4-cyanatophenyl) ethane, 4-cumyl phenol cyanate ester, 1, 1 -bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, 2, 2-bis(4-cyanatophenyl)propane, etc. are illustrated. Moreover, "PRIMASET BTP-6020S (Lonza Japan Co., Ltd. product)" etc. are illustrated as a cyanate ester commercial item.

The upper limit of the content of the crosslinking agent with respect to 100 parts by mass (in terms of solid content) of the polyimide in the adhesive is 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, 10 parts by mass, etc. exemplified, and the lower limit is exemplified by 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, 10, 5 parts by mass and the like. In one embodiment, as for content of the crosslinking agent with respect to 100 mass parts (solid content conversion) of the said polyimide, about 5-900 mass parts is preferable.

The upper limit of the content of the crosslinking agent in 100% by mass of the adhesive is exemplified by 80, 70, 60, 50, 40, 30, 20, 10, 5% by mass, and the like, and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 2 mass %, etc. are illustrated. In one embodiment, as for content of the crosslinking agent in 100 mass % of the said adhesive agent, about 2-80 mass % is preferable.

<Organic solvent>

As the organic solvent, various known organic solvents may be used alone or in combination of two or more. The organic solvent is an aprotic polar solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme, or methyldiglyme, or cyclo alicyclic solvents, such as hexanone and methylcyclohexane, alcohol solvents, such as methanol, ethanol, propanol, benzyl alcohol, cresol, aromatic solvents, such as toluene, etc. are illustrated.

Moreover, although content in particular of the organic solvent in an adhesive agent is not restrict|limited, The quantity used as solid content mass of 10-60 mass % with respect to 100 mass % of adhesive agents is preferable.

As for the upper limit of content of the organic solvent with respect to 100 mass parts (solid content conversion) of the said polyimide in the said adhesive agent, 900, 800, 700, 600, 500, 400, 300, 200 mass parts etc. are illustrated, The lower limit is 800, 700, 600, 500, 400, 300, 200, 150 mass parts etc. are illustrated. In one embodiment, as for content of the organic solvent with respect to 100 mass parts (solid content conversion) of the said polyimide in the said adhesive agent, 150-900 mass parts is preferable.

<flame retardant>

In one embodiment, the adhesive includes a flame retardant. The flame retardant may be used alone or in combination of two or more. Examples of the flame retardant include a phosphorus-based flame retardant, an inorganic filler, and the like.

(Phosphorus-based flame retardant (phosphorus-containing flame retardant))

Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives not containing a phenolic hydroxyl group. Among the phosphazene derivatives, a cyclic phosphazene derivative is preferable in terms of flame retardancy, heat resistance, bleed-out resistance, and the like. Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., and Labitol FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

(inorganic filler)

In one embodiment, as an inorganic filler, a silica filler, a phosphorus filler, a fluorine-type filler, an inorganic ion exchanger filler, etc. are illustrated. Commercial products include FB-3SDC manufactured by Denka Corporation, Exolit OP935 manufactured by Clariant Chemicals Corporation, KTL-500F manufactured by Kitamura Corporation, IXE manufactured by Toa Synthesis Corporation, and the like.

150, 100, 50, 10, 5 mass parts etc. are illustrated as for the upper limit of content of a flame retardant with respect to 100 mass parts (solid content conversion) of polyimide in the said adhesive agent, The lower limit is 125, 100, 50, 10, 5, 1 mass and the like are exemplified. In one embodiment, as for content of the flame retardant with respect to 100 mass parts (solid content conversion) of polyimide in the said adhesive agent, 1-150 mass parts is preferable.

<Reactive Alkoxysilyl Compound>

In one embodiment, the adhesive has the general formula: Z-Si(R ¹ ) _a (OR ² ) _{3 -a} (wherein Z is a group containing a functional group reactive with an acid anhydride group, R ¹ is hydrogen or carbon number The reactive alkoxysilyl compound represented by the hydrocarbon group of 1-8, R< ² > represents a C1-C8 hydrocarbon group, and a represents 0, 1 or 2) is further contained. With the reactive alkoxysilyl compound, the melt viscosity can be adjusted while maintaining the low dielectric properties of the adhesive layer made of the adhesive of the present invention. As a result, while increasing the interfacial adhesion between the adhesive layer and the substrate (so-called anchor effect), the exudation of the cured layer from the end of the substrate can be suppressed.

Examples of the reactive functional group included in Z of the general formula include an amino group, an epoxy group, and a thiol group.

The compound in which Z contains an amino group is N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethyl oxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, etc. are illustrated. Examples of the compound in which Z contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. are illustrated. Examples of the compound in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldie Toxysilane and the like are exemplified. Among these, compounds in which Z contains an amino group are preferable from the viewpoint of good reactivity and flow control effects.

As for the upper limit of content of the reactive alkoxysilyl compound with respect to 100 mass parts (solid content conversion) of the polyimide in the said adhesive agent, 5, 2.5, 1, 0.5, 0.1, 0.05 mass parts etc. are illustrated, The lower limit is 4, 2.5, 1, 0.5 , 0.1, 0.05, 0.01 parts by mass, etc. are exemplified. In one embodiment, as for content of the reactive alkoxysilyl compound with respect to 100 mass parts (solid content conversion) of polyimide in the said adhesive agent, 0.01-5 mass parts is preferable.

The adhesive may include, as an additive, none of the polyimide, the crosslinking agent, the organic solvent, the flame retardant, and the reactive alkoxysilyl compound.

Examples of additives include ring-opening esterification reaction catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity regulators, silica fillers and fluorine fillers. do.

In one embodiment, as for content of an additive, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated with respect to 100 mass parts of adhesive agents.

In another embodiment, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated as content of an additive with respect to 100 mass parts (solid content conversion) of the said polyimide.

The adhesive may be obtained by dissolving the polyimide and the crosslinking agent and, if necessary, a flame retardant, a reactive alkoxysilyl compound and an additive in an organic solvent.

[Film-like adhesive material]

The present disclosure provides a film-like adhesive material including a heat-cured product of the adhesive. Examples of the method for producing the film adhesive include a step of applying the adhesive to a suitable support, a step of curing by heating to volatilize the organic solvent, and a step of peeling from the support. Although the thickness of the said adhesive material is not specifically limited, About 3-40 micrometers is preferable. The support is exemplified by the following.

[Adhesive layer]

The present disclosure provides an adhesive or an adhesive layer comprising the film-like adhesive. When manufacturing the said adhesive layer, you may use together the said adhesive agent and various well-known adhesive agents other than the said adhesive agent. Similarly, you may use together the said film adhesive and various well-known film adhesives other than the said film adhesive.

[Adhesive sheet]

The present disclosure provides an adhesive sheet including the adhesive layer and the support film.

As for the said support film, a plastic film is illustrated. Plastics include polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, and aromatic polyester resins obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, and parahydroxybenzoic acid (so-called liquid crystal polymer; Kurarese, "Vexstar", etc.) etc. are illustrated.

Moreover, when apply|coating the said adhesive agent to the said support film, the said application|coating means is employable. Although the thickness of an application layer is not specifically limited, either, About 1-100 micrometers is preferable and, as for the thickness after drying, about 3-50 micrometers is more preferable. Moreover, you may protect the adhesive layer of the said adhesive sheet with various protective films.

[Copper foil with resin]

The present disclosure provides a resin-attached copper foil including the adhesive layer and the copper foil. Specifically, the said copper foil with resin apply|coated or bonded the said adhesive agent or the said film adhesive material to copper foil. As for the said copper foil, a rolled copper foil and an electrolytic copper foil are illustrated. The thickness is not specifically limited, About 1-100 micrometers is preferable, and about 2-38 micrometers is more preferable. Moreover, the thing to which various surface treatment (roughening, rust prevention, etc.) was made may be sufficient as the said copper foil. Examples of the rust prevention treatment include a plating treatment using a plating solution containing Ni, Zn, Sn, or the like, or a so-called mirror finish treatment such as a chromate treatment. Moreover, an above-described method is illustrated as an application|coating means.

Moreover, non-hardening may be sufficient as the adhesive layer of the said copper foil with resin, and what was made to partially harden thru|or completely harden under heating may be sufficient as it. The partially cured adhesive layer is in a state called the so-called B stage. Moreover, the thickness of a contact bonding layer is not specifically limited, either, About 0.5-30 micrometers is preferable. Moreover, copper foil can be further bonded together to the adhesive surface of the said copper foil with resin, and it can also be set as double-sided copper foil with resin.

[Copper-clad laminate]

The present disclosure provides a copper-clad laminate including the above-mentioned resin-coated copper foil and copper foil or insulating sheet. Copper clad laminates are also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is obtained by pressing the resin-coated copper foil on at least one or both surfaces of various well-known copper foils or insulating sheets under heating. When bonding together on one surface, you may crimp a thing different from the said copper foil with resin on the other surface. In addition, the number of the copper foil with resin and the insulating sheet in the said copper clad laminated board is not restrict|limited in particular.

In one embodiment, the insulating sheet is preferably prepreg. Preprec refers to a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with resin and curing it to the B stage (JIS C 5603). Insulating resins, such as a polyimide resin, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, and an aramid resin, are used for the said resin. The thickness of the said prepreg is not specifically limited, About 20-500 micrometers is preferable. Heating/compression conditions are not particularly limited, and preferably about 150 to 280°C (more preferably about 170°C to 240°C), and preferably about 0.5 to 20 MPa (more preferably about 1 to 8 MPa). .

[printed wiring board]

The present disclosure provides a printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate. As the patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate, a subtractive method and a semiadditive method are exemplified. Examples of the semi-additive method include patterning the copper foil surface of a copper-clad laminate with a resist film, then electrolytic copper plating, removing the resist, and etching with an alkali solution. Moreover, the thickness of the circuit pattern layer in the said printed wiring board is not specifically limited. Moreover, a multilayer board can also be obtained by using the said printed wiring board as a core base material, and laminating|stacking the same printed wiring board or another well-known printed wiring board or printed circuit board on it. At the time of lamination, it is possible to use together the above-mentioned adhesive and other known adhesives other than the above-mentioned adhesive. Moreover, the number of lamination|stacking in a multilayer board|substrate is not specifically limited. In addition, a via hole may be inserted every time lamination|stacking, and the inside may be plated. Although the line/space ratio of the said circuit pattern is not specifically limited, About 1 micrometer/1 micrometer - 100 micrometers/100 micrometer is preferable. Moreover, although the height of the said circuit pattern is not specifically limited, either, About 1-50 micrometers is preferable.

[Multilayer wiring board]

The present disclosure provides a printed wiring board (1) or a multilayer wiring board including a printed circuit board (1), the adhesive layer, and a printed wiring board (2) or printed circuit board (2). The said printed wiring boards (1)-(2) may be the said printed wiring board, and various well-known things may be sufficient as them. Similarly, the printed circuit boards (1) to (2) may be the above printed circuit boards, or various well-known ones may be used. Moreover, the printed wiring board 1 and the printed wiring board 2 may be the same or different. Similarly, the printed circuit board 1 and the printed circuit board 2 may be the same or different.

[Method for manufacturing a multilayer wiring board]

The present disclosure is the following steps 1 and 2

Step 1: Step of manufacturing a base material with an adhesive layer by bringing the adhesive or the film-like adhesive material into contact with at least one surface of the printed wiring board 1 or the printed circuit board 1

Step 2: A step of laminating a printed wiring board 2 or a printed circuit board 2 on the substrate with an adhesive layer and pressing under heating and pressure

It provides a method of manufacturing a multilayer wiring board comprising a.

The said printed wiring boards (1)-(2) may be the said printed wiring board, and various well-known things may be sufficient as them. Similarly, the printed circuit boards (1) to (2) may be the above printed circuit boards, or various well-known ones may be used.

In step 1, the means for contacting the adhesive or film-like adhesive to the adherend is not particularly limited, and various well-known coating means, curtain coaters, roll coaters, laminators, and presses ) and the like are exemplified.

The heating temperature and compression time in step 2 are not particularly limited, but (A) after the adhesive or film adhesive of the present invention is brought into contact with at least one surface of the core substrate, heated to about 70 to 200° C. and for about 1 to 10 minutes After curing reaction, (B) in order to advance the curing reaction of the crosslinking agent, it is preferable to further heat treatment at about 150°C to 250°C, for about 10 minutes to 3 hours. Moreover, although a pressure is not specifically limited, either, Through steps (A) and (B), about 0.5-20 MPa is preferable, and about 1-8 MPa is more preferable.

Example

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the description of the above-mentioned preferred embodiment and the following examples are provided only for the purpose of illustration, and are not provided for the purpose of limiting the present invention. Accordingly, the scope of the present invention is not limited to the embodiments specifically described herein nor to the examples, but is limited only by the claims. In addition, in each Example and a comparative example, unless there is particular explanation, numerical values, such as a part, %, are based on mass.

<Production of polyimide>

production example One

In a reaction vessel equipped with a stirrer, a water fountain, a thermometer, and a nitrogen gas introduction tube, 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride (trade name) "BPF-PA", manufactured by JFE Chemical Co., Ltd. (hereinafter abbreviated as BPF-PA) 290.00 g, 980.20 g of cyclohexanone, and 196.04 g of methylcyclohexane were added and heated to 60°C. Next, 236.60 g of commercially available dimerdiamine (trade name "PRIAMINE1075", manufactured by Kuroda Japan Co., Ltd.) was added dropwise, followed by imidization reaction at 140° C. for 12 hours, resulting in polyimide (1-1) solution (fire 31.6% of volatile matter) was obtained. In addition, the molar ratio of the acid component/amine component of the said polyimide was 1.03.

Production examples and comparative production examples other than Production Example 1 were performed in the same manner as in Production Example 1, except that the composition of the resin solution was changed as described in Table 1 to obtain polyimide.

BPAF: 9,9'-bis(3,4-dicarboxyphenoxy)fluorene dianhydride (brand name "BPAF", manufactured by JFE Chemicals Co., Ltd.)

BAFL: 9, 9'-bis (aminophenyl) fluorene (brand name "BAFL", manufactured by JFE Chemicals)

BisDA-1000: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Co., Ltd.)

1, 3-BAC: 1, 3-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

Example One

10.00 g of polyimide resin (1-1) solution, 0.35 g of N,N-diglycidyl-4-glycidyloxyaniline (manufactured by Mitsubishi Chemical Co., Ltd., trade name “jER630”) as a crosslinking agent, and toluene as an organic solvent 1.35 g was mixed and stirred well to obtain an adhesive having a non-volatile content of 30.0%.

Examples and comparative examples other than Example 1 were carried out in the same manner as in Example 1, except that the composition of the adhesive was changed as shown in Table 2 to obtain an adhesive.

In addition, the organic solvent may include an organic solvent used when manufacturing the polyimide.

<Production of adhesive sheet>

The obtained adhesive was applied to a polyimide film (trade name: "Kapton 50EN", manufactured by Toray DuPont Co., Ltd.; film thickness: 12.5 µm; coefficient of thermal expansion: 15 ppm/°C) with a gap coater so that the thickness after drying was 20 µm, 180 An adhesive sheet was obtained by drying at °C for 3 minutes.

<Production of copper-clad laminates>

The copper foil with resin which laminated|stacked the adhesive surface of the obtained adhesive sheet on the roughening side of a commercially available electrolytic copper foil (brand name "F2-WS", Furukawa Circuit Kit Foil Co., Ltd. product, 18 micrometers thickness) was produced.

Next, the obtained copper foil with resin was placed on a press support, and a copper-clad laminate was produced by hot pressing from above through a support obtained from the copper material at a pressure of 5 MPa, 200° C., and 60 minutes.

<Adhesiveness test>

For the obtained copper-clad laminate, peel strength (N/cm) was measured in accordance with JIS C 6481 (Test method for copper-clad laminate for flexible printed wiring boards). A result is shown in a table.

<Measurement of permittivity and dielectric loss tangent>

About 7 g of the adhesives of Examples and Comparative Examples were poured into a fluororesin PFA flat plate (diameter 75 mm, manufactured by Sogoi Chemical Co., Ltd.), respectively, 30 ° C. × 10 hours, 70 ° C. × 10 hours, 100 ° C. × 6 hours, By curing under the conditions of 120° C.×6 hours, 150° C.×6 hours, and 180° C.×12 hours, a resin and cured product sample having a film thickness of about 300 μm for measuring the dielectric constant was obtained.

Next, the dielectric constant and dielectric loss tangent at 10 GHz were measured for the obtained dielectric constant measurement resin and cured material samples in accordance with JIS C2565 using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by ATE). A result is shown in a table.

Claims (20)

aromatic tetracarboxylic anhydride;
and diamines including dimerdiamines.
It is a reactant of a group of monomers comprising a fluorenylene group in the polymer main chain

40 mol% or less of a fluorene skeleton-containing diamine is contained in 100 mol% of the diamine, and the molar ratio of the aromatic tetracarboxylic acid anhydride and the diamine [aromatic tetracarboxylic acid anhydride/diamine] is 1.0 to 1.5, and the aromatic tetra A polyimide wherein the carboxylic acid anhydride is 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride. According to claim 1,
The diamine is a diamine containing a fluorene skeleton

(In the formula, either one of R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, any one of R ³ or R ⁴ represents a group having an amino group, and another One represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom)
Polyimide comprising a. 3. The method of claim 1 or 2,
Polyimide, characterized in that the diamine comprises diaminopolysiloxane. An adhesive comprising the polyimide according to claim 1, a crosslinking agent, and an organic solvent. 5. The method of claim 4,
An adhesive comprising 5 to 900 parts by mass of the crosslinking agent and 150 to 900 parts by mass of the organic solvent with respect to 100 parts by mass of the polyimide (in terms of solid content). A film adhesive comprising the heat-cured product of the adhesive according to claim 4. An adhesive layer comprising the adhesive according to claim 4. An adhesive layer comprising the film adhesive according to claim 6 . An adhesive sheet comprising the adhesive layer according to claim 7 and a support film. An adhesive sheet comprising the adhesive layer according to claim 8 and a support film. Copper foil with resin containing the adhesive layer of Claim 7, and copper foil. Copper foil with resin containing the adhesive layer of Claim 8, and copper foil. A copper-clad laminate comprising the copper foil with resin according to claim 11 and the copper foil or an insulating sheet. A copper-clad laminate comprising the copper foil with resin according to claim 12 and the copper foil or insulating sheet. The printed wiring board which has a circuit pattern on the copper foil surface of the copper-clad laminated board of Claim 13. The printed wiring board which has a circuit pattern on the copper foil surface of the copper-clad laminated board of Claim 14. printed wiring board (1) or printed circuit board (1);
The adhesive layer according to claim 7, and
A printed wiring board (2) or a multilayer wiring board comprising a printed circuit board (2). printed wiring board (1) or printed circuit board (1);
The adhesive layer according to claim 8, and
A printed wiring board (2) or a multilayer wiring board comprising a printed circuit board (2). A method for manufacturing a multilayer wiring board comprising the following steps 1 and 2.
Process 1: The process of manufacturing a base material with an adhesive layer by making the adhesive agent of Claim 4 or 5 contact at least one surface of the printed wiring board 1 or the printed circuit board 1
Step 2: A step of laminating a printed wiring board 2 or a printed circuit board 2 on the substrate with an adhesive layer and pressing under heating and pressure A method for manufacturing a multilayer wiring board comprising the following steps 1 and 2.
Process 1: The process of manufacturing a base material with an adhesive layer by making the film-form adhesive material of Claim 6 contact at least one surface of the printed wiring board 1 or the printed circuit board 1
Step 2: A step of laminating a printed wiring board 2 or a printed circuit board 2 on the substrate with an adhesive layer and pressing under heating and pressure