KR102485693B1 - 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

＜Tasks＞
It is an object to provide a polyimide, an adhesive agent, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper foil with a resin, a copper clad laminate, a printed wiring board, and a multilayer wiring board and a manufacturing method thereof.
<Solution>
Polyimide, which is a reactant of a monomer group including aromatic tetracarboxylic acid anhydride and diamine including dimer diamine, and includes a fluorenylene group in the polymer main chain, and an adhesive containing polyimide, a crosslinking agent and an organic solvent, and a film adhesive, The solution is to provide an adhesive layer, an adhesive sheet, a copper foil with resin, a copper clad laminate, a printed wiring board, a multilayer wiring board, and a manufacturing method thereof.

Description

Polyimide, adhesive, film-like adhesive, adhesive layer, adhesive sheet, resin-coated copper foil, copper-clad laminate, printed wiring board, and multilayer wiring board and manufacturing method thereof FOIL WITH RESIN, COPPER CLAD LAMINATE, PRINTED WIRING BOARD, AND MULTI-LAYER BOARD AND MANUFACTURING METHOD THEREOF}

The present disclosure relates to polyimide, an adhesive, a film-like adhesive, an adhesive layer, an adhesive sheet, a copper foil with a resin, 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, and printed wiring boards included in large computers and the like.

The present applicant proposes "a polyimide-based adhesive composition containing a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent formed by reacting diamines containing 30 mol% or more of aromatic tetracarboxylic acids and specific dimerdiamine" Yes (see Patent Document 1).

Japanese Patent No. 5534378

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

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

As a result of intensive studies, the present inventors have found that the above problems can be solved by a given polyimide.

The following items are provided by this disclosure.

(item 1)

Aromatic tetracarboxylic acid anhydrides,

and diamines including dimer diamines.

It is a reactant of a monomer group containing a fluorenylene group in the polymer main chain

Polyimide containing.

(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, and either one of R ³ or R ⁴ represents a group having an amino group, and the other one represents a hydrogen atom, a hydroxyl group, an alkyl group, or a halogen atom)

The polyimide described in the above item containing

(item 3)

The polyimide according to any one of the above items in which the diamine includes diaminopolysiloxane.

(item 4)

The polyimide according to any one of the above items, wherein the molar ratio of the aromatic tetracarboxylic anhydride and the diamine [aromatic tetracarboxylic anhydride/diamine] is from 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 epoxide, benzoxazine, bismaleimide and cyanate ester.

(item 7)

The epoxide has the following structure

(In the formula, Y represents a phenylene group or a cyclohexylene group)

The adhesive described in the above item which is phosphorus.

(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 based on 100 parts by mass of the polyimide (in terms of solid content).

(item 9)

A film-like adhesive material comprising a heat-cured product of the adhesive according to any one of the above items.

(item 10)

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

(item 11)

An adhesive sheet comprising the adhesive layer and support film described in the above item.

(item 12)

Copper foil with resin containing the adhesive layer and copper foil as described in the said item.

(item 13)

A copper clad laminate comprising the copper foil and copper foil with resin described in the above item.

(item 14)

A copper clad laminate comprising the resin-clad copper foil and insulating sheet described in the above item.

(item 15)

A printed wiring board having a circuit pattern on the copper foil surface of the copper clad laminate according to any one of the above items.

(item 16)

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

The adhesive layer described in the above item, and

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

(item 17)

The manufacturing method of the multilayer wiring board including the following process 1 and 2.

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

Step 2: A step of laminating the printed wiring board 2 or the printed circuit board 2 on the base material with the adhesive layer and crimping under heating and pressure

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

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-functioning mobile terminals such as printed wiring boards.

Throughout the present disclosure, ranges of numerical values such as each physical property and content may be appropriately set (for example, by selecting from the upper and lower limit values 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 dimer diamines.

It is a reactant of a monomer group containing a fluorenylene group in the polymer main chain

It provides a polyimide containing.

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

<Aromatic tetracarboxylic acid anhydride>

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

(Tetracarboxylic acid anhydride containing fluorene skeleton)

In one embodiment, the fluorene skeleton-containing tetracarboxylic acid anhydride has the following general formula

(In the formula, either 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 R ³ or R ⁴ represents a group having an acid anhydride group, , wherein the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, or represents a group in which R ¹ and R ² and/or R ³ and R ⁴ combine to form an acid anhydride group).

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 are combined 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.

The number of carbon atoms in the alkyl group is not particularly limited, but the upper limit is 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, etc. are exemplified. In one embodiment, the number of carbon atoms in the alkyl group is preferably about 1 to 30, more preferably about 1 to 20, still more preferably about 1 to 16, and particularly preferably about 1 to 12.

Examples of straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. .

An isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group, an isodecyl group, etc. are illustrated as a branched alkyl group.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. In the cycloalkyl group, one or more hydrogen atoms on each ring may be substituted with a straight-chain alkyl group (such as the groups illustrated above) or a branched alkyl group (such as the groups illustrated above).

As for a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are illustrated.

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

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

The upper limit of the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100% by mass of the aromatic tetracarboxylic acid anhydride is 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, the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100% by mass of the aromatic tetracarboxylic acid anhydride is preferably about 0 to 100% by mass, and more preferably about 50 to 100% by mass.

The upper limit of the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mol% of the monomer group is 75, 70, 60, 50, 40, 30, 20, 10, 5 mol%, etc., and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mol%, etc. are illustrated. In one embodiment, the content of the fluorene backbone-containing tetracarboxylic acid anhydride in 100 mol% of the monomer group is preferably about 0 to 75 mol%.

The upper limit of the content of the fluorene backbone-containing tetracarboxylic acid anhydride in 100% by mass of the monomer group is 75, 70, 60, 50, 40, 30, 20, 10, 5% by mass, etc., and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mass % etc. are illustrated. In one embodiment, the content of the fluorene backbone-containing tetracarboxylic acid anhydride in 100 mass% of monomer groups is preferably about 0 to 75 mass%.

(Symmetrical aromatic tetracarboxylic acid anhydride)

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

(In the formula, 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 represents -OCO-, and p represents an integer from 1 to 20)

What is indicated by is exemplified.

Symmetric aromatic tetracarboxylic acid dianhydrides represented by the above formula are 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfotetracarboxylic acid dianhydride, 3,3 ',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid dianhydride, 4,4'-[propane-2,2-diylbis(1,4 -phenyleneoxy)]diphthalic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2-bis(3,4-dicarboxy Phenyl) propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfonic dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis( 2,3-dicarboxyphenyl)propane dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic acid anhydride, 2,3,6, 7-naphthalene tetracarboxylic acid anhydride etc. are illustrated.

Among the above-mentioned symmetric aromatic tetracarboxylic acid anhydrides, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4' from the viewpoints of compatibility between aromatic tetracarboxylic acid anhydride and diamine, room temperature adhesion, heat resistance adhesion, etc. -At least one selected from the group consisting of [propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride and 4,4'-oxydiphthalic anhydride is preferred.

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

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

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

(Other aromatic tetracarboxylic acid anhydrides)

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

In one embodiment, the content of the other acid anhydrides in the aromatic tetracarboxylic acid anhydride is 5, 4, 1, 0.9, 0.5, less than 0.1 mol%, about 0 mol%, and the like.

In one embodiment, the content of the other acid anhydrides in the aromatic tetracarboxylic acid anhydride is 5, 4, 1, 0.9, 0.5, less than 0.1% by mass, about 0% by mass, and the like.

In one embodiment, the content of the other acid anhydrides in the monomer group is 5, 4, 1, 0.9, 0.5, less than 0.1 mol%, about 0 mol%, and the like.

In one embodiment, the content of other acid anhydrides in the monomer group is 5, 4, 1, 0.9, 0.5, less than 0.1% by mass, about 0% by mass, and the like.

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

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

<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 is one in which all carboxyl groups of dimer acids, which are dimers of unsaturated fatty acids such as oleic acid, are substituted with primary amino groups (see Japanese Patent 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 are preferable, p + q = 8 to 19 are preferable, and the broken line indicates a carbon-carbon single bond or a carbon-carbon double bond. it means).

Commercially available products of dimerdiamine are Basamine 551 (manufactured by Cognix Japan Co., Ltd.), Basamine 552 (manufactured by Cognix Japan Co., Ltd.; hydrogenated product of Basamine 551), PRIAMINE1075, PRIAMINE1074 (both manufactured by Kuroda Japan Co., Ltd.) etc. are exemplified.

The upper limit of the content of the dimerdiamine component in 100 mol% of diamine is 100, 90, 80, 70, 60, 50, 40, 30, 25 mol%, etc., and the lower limit is 90, 80, 75, 70, 60, 50 , 40, 30, 25, 20 mol% and the like are exemplified. In one embodiment, the content of the dimerdiamine component in 100 mol% of diamine is preferably about 20 to 100 mol% from the viewpoint of improving flexibility, adhesiveness, and solvent solubility.

The upper limit of the content of the dimerdiamine component in 100% by mass of diamine is 100, 90, 80, 70, 60, 50, 40, 30, 25% by mass, etc., and the lower limit is 90, 80, 75, 70, 60, 50 , 40, 30, 25, 20% by mass and the like are exemplified. In one embodiment, the content of the dimerdiamine component in 100% by mass of diamine is preferably about 20 to 100% by mass from the viewpoint of improving flexibility, adhesiveness, and solvent solubility.

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.

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

(Diamine containing a fluorene skeleton)

In one embodiment, the fluorene backbone-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, and either one of R ³ or R ⁴ represents a group having an amino group, and the other one represents a hydrogen atom, a hydroxyl group, an alkyl group, or a halogen atom).

In the present disclosure, "group having an amino group" means a group in which at least one hydrogen atom in 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 ring aryl group. In the aryl group, one or more hydrogen atoms may be substituted with a straight-chain or branched alkyl group.

A phenyl group, a tolyl group, a mesityl group etc. are illustrated as a monocyclic aryl group. Moreover, a naphthyl group etc. are illustrated as a condensed-ring aryl group.

The fluorene skeleton-containing diamine 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-aminophenone) cy) phenyl] fluorene and the like.

The upper limit of the content of the fluorene skeleton-containing diamine component in 100 mol% of diamine is 80, 70, 60, 50, 40, 30, 25 mol%, etc., and the lower limit is 75, 70, 60, 50, 40, 30, 25, 20 mol% etc. are illustrated. In one embodiment, the content of the fluorene backbone-containing diamine component in 100 mol% of diamine is preferably about 20 to 80 mol% from the viewpoint of improving the dielectric properties.

The upper limit of the content of the fluorene skeleton-containing diamine component in 100% by mass of diamine is 80, 70, 60, 50, 40, 30, 25% by mass, etc., and the lower limit is 75, 70, 60, 50, 40, 30, 25, 20 mass % etc. are illustrated. In one embodiment, the content of the fluorene skeleton-containing diamine component in 100 mol% of diamine is preferably about 20 to 80% by mass from the viewpoint of improving the dielectric properties.

The upper limit of the content of the fluorene skeleton-containing diamine in 100 mol% of the monomer group is 50, 40, 30, 20, 10, 5 mol%, etc., and the lower limit is 40, 30, 20, 10, 5, 0 mol%, etc. this is exemplified In one embodiment, the content of the fluorene skeleton-containing diamine in 100 mol% of monomer groups is preferably 0 to 50 mol%.

The upper limit of the content of the fluorene skeleton-containing diamine in 100 mass% of the monomer group is 50, 40, 30, 20, 10, 5 mass%, etc., and the lower limit is 40, 30, 20, 10, 5, 0 mass%, etc. this is exemplified In one embodiment, the content of the fluorene skeleton-containing diamine in 100% by mass of the monomer group is preferably 0 to 50% by mass.

The upper limit of the ratio of the substance amount of the fluorene skeleton-containing diamine to the substance amount of dimerdiamine (fluorene skeleton-containing diamine/dimerdiamine) 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, etc. are exemplified. In one embodiment, the ratio of the substance amount of the fluorene skeleton-containing diamine to the substance amount of the dimer diamine (fluorene skeleton-containing diamine/dimerdiamine) is preferably about 0.25 to 4.00 from the viewpoint of improving flexibility, adhesiveness, and dielectric properties. .

(diaminopolysiloxane)

Diaminopolysiloxane is 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.

As for the upper limit of content of diaminopolysiloxane in 100 mol% of diamine, 5, 4, 3, 2, 1 mol% etc. are illustrated, and as for the lower limit, 4, 3, 2, 1, 0 mol% etc. are illustrated. 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.

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

The upper limit of the content of diaminopolysiloxane in 100 mol% of the monomer group is exemplified by 5, 4, 3, 2, 1 mol% and the like, and the lower limit is 4, 3, 2, 1 and 0 mol% and the like. In one embodiment, the content of diaminopolysiloxane in 100 mol% of monomer groups is preferably about 0 to 5 mol% from the viewpoint of improving flexibility.

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

(other diamines)

In one embodiment, the monomer group may contain diamines other than the above (also referred to as other diamines). Other diamines include alicyclic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, and diamine. Minophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminoditrifluoromethylbenzene, aminophenoxybiphenyl, Aminophenoxyphenyl ketone, aminophenoxyphenyl sulfide, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenyl propane, 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'-spirobiindan, 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 diamines include 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, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, etc. are illustrated.

Examples of 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.

As for phenylenediamine, phenylenediamine, such as p-phenylenediamine and m-phenylenediamine, etc. are illustrated.

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

Examples of diaminodiphenylsulfone 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.

Diaminophenyl propane is 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 is 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 is 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, etc. are illustrated.

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 etc. are illustrated.

Aminophenoxybiphenyl is 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)bi phenyl etc. are illustrated.

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

Examples of 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.

As for aminophenoxyphenyl ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, etc. are illustrated.

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, etc. are illustrated.

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

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

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

Examples of 4,4'-bis[aminophenoxyphenoxy]diphenylsulfone include 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone.

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

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

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindan is 6,6'-bis(3-aminophenoxy)-3, 3,3',3'-tetramethyl-1,1'-spirobiindan, 6,6'-bis(4-aminophenoxy)-3,3,3',3'-tetramethyl-1,1 '-spirobiindan etc. are exemplified.

Examples of 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-aminoprotoxy) ethyl] ether etc. are exemplified.

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

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

(Poly) ethylene glycol bis (aminoalkyl) ethers include ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, and triethylene glycol bis (3-aminopropyl) ether. .

Examples of 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 the 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, 5, 4, 1, 0.9, 0.5, less than 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.

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

50, 45, 40, 35, 30 mass % etc. are illustrated as the upper limit of content of diamine in 100 mass % of monomer groups, and 45, 40, 35, 30, 25 mass % etc. are illustrated as a lower limit. In one embodiment, the content of diamine in 100% by mass of monomer groups is preferably about 25 to 50% by mass.

The upper limit of the molar ratio of aromatic tetracarboxylic anhydride and diamine [aromatic tetracarboxylic anhydride/diamine] is exemplified by 1.5, 1.4, 1.3, 1.2, 1.1 and the like, and the lower limit by 1.4, 1.3, 1.2, 1.1, 1.0 and the like. In one embodiment, the molar ratio of aromatic tetracarboxylic anhydride to diamine [aromatic tetracarboxylic anhydride/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 of aromatic tetracarboxylic acid anhydride and diamine [aromatic tetracarboxylic acid anhydride/diamine] is exemplified by 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, etc. are exemplified. In one embodiment, the mass ratio [aromatic tetracarboxylic anhydride/diamine] of aromatic tetracarboxylic acid anhydride and diamine is preferably 0.5 to 1.5.

<Other monomers>

In one embodiment, the monomer group may contain a monomer that is neither an aromatic tetracarboxylic acid anhydride nor a diamine (also referred to as other monomers). Examples of other monomers include aliphatic tetracarboxylic acid anhydrides.

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

In one embodiment, as for content of the other monomers 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, etc., and the lower limit is exemplified by 45000, 40000, 30000, 20000, 10000, 7500, 5000, etc. In one embodiment, the weight average molecular weight of the polyimide is preferably 5000 to 50000 from the viewpoints of dielectric properties, solvent solubility, and flexibility.

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

The weight average molecular weight and number average molecular weight can be obtained as values in terms of polystyrene measured, for example, 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, etc., and the lower limit is exemplified by 210, 200, 150, 100, 50, 25, 20°C, etc. In one embodiment, the softening point of the polyimide is preferably 20 to 220°C from the viewpoints of workability, 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.

<Method for producing 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 acid anhydride and a diamine including dimer diamine is preferably heated at a temperature of preferably about 60 to 120 ° C., more preferably about 80 to 100 ° C. Preferably about 0.1 to 2 hours, more preferably about 0.1 to 0.5 hours, a step of obtaining a polyadduct by subjecting the polyadduct to a reaction, preferably about 80 to 250°C, more preferably about 100 to 200°C. A method including a step of an imidation reaction, that is, a dehydration ring closure reaction, at a temperature of about 0.5 to 50 hours, more preferably about 1 to 20 hours, is exemplified.

In addition, in the imidization process, various known reaction catalysts, dehydrating agents, and organic solvents described later may be used. Various known reaction catalysts, dehydrating agents, and organic solvents 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, aromatic acid anhydrides, such as aliphatic acid anhydrides, such as acetic anhydride, and benzoic acid anhydride, etc. are illustrated.

The imide closure rate of the polyimide is not particularly limited. Here, "imide closure rate" means the content of cyclic imide bonds in polyimide, and can be determined by various spectroscopic means such as NMR and IR analysis, for example. From the viewpoint of improving room temperature adhesion and heat resistance adhesion, the imide closure rate of the polyimide is preferably about 70% or more, and more preferably about 85 to 100%.

[glue]

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

The upper limit of the content of the polyimide in 100% by mass of the adhesive is exemplified by 90, 80, 70, 60, 50, 40, 30, 20, 10% by mass, etc., and 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>

As the crosslinking agent, various known crosslinking agents can be used without particular limitation as long as they function as a crosslinking agent for polyimide. A 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 include phenol novolak type epoxide, cresol novolak type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide, hydrogenated bisphenol A type epoxide, hydrogenated bisphenol F type 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, tetraglycidylxylylenediamine, dimer acid-modified epoxide that is a dimer acid-modified product of the above epoxide, Dimer acid diglycidyl ester etc. are illustrated. In addition, commercially available products of epoxide include "jER828", "jER834", and "jER807" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd., and " Ceroxide 2021P", "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd., "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like are exemplified. 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 preferred from the viewpoint of the balance of heat resistance, moisture absorption solder heat resistance and low dielectric properties. Do.

In particular, tetraglycidyldiamine of the structure

(In the formula, Y represents a phenylene group or a cyclohexylene group)

Silver has good compatibility with the polyimide. In addition, when this is used, it is easy to reduce the loss elastic modulus of the adhesive layer, and the heat resistance and low dielectric properties thereof are also improved.

When using an epoxide as a crosslinking agent, various well-known hardening|curing agents for epoxides can be used together. Curing agents for epoxide may be used alone or in combination of two or more. The curing agent for epoxide is succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 4- A mixture of methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic acid anhydride, methylnorbornane- Acid anhydride curing agents such as 2,3-dicarboxylic acid anhydride, methylcyclohexenedicarboxylic acid anhydride, 3-dodecenylsuccinic anhydride, and octenylsuccinic anhydride; dicyandiamide (DICY), aromatic diamine (trade name "LonzacureM-DEA", "Lonzacure M-DETDA", etc., all manufactured by Lonza Japan Co., Ltd.), amine curing agent such as aliphatic amine; Phenol-based curing agents such as phosphazene containing a hydroxyl group (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene-based compounds, rosin-based crosslinking agents such as maleic acid-modified rosin and hydrides thereof, and the like are exemplified. . Among these, a phenol-based curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable. The amount of the curing agent used is not particularly limited, but is preferably about 0.1 to 120% by mass, and more preferably about 10 to 40% by mass, when the solid content of the adhesive is 100% by mass.

When an epoxide and a curing agent for epoxide are used in combination as a crosslinking agent, a reaction catalyst can be further used in combination. The reaction catalyst may be used singly 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 , 2-phenyl-4-methylimidazole, imidazoles such as 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. Organic phosphine of; Tetraphenyl boron salts, such as tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methyl imidazole tetraphenyl borate, and N-methylmorpholine tetraphenyl borate, etc. are illustrated. In addition, the amount of the reaction catalyst used is not particularly limited, but is preferably about 0.01 to 5% by mass when the solid content of the adhesive is 100% by mass.

(Benzox picture)

Benzoxazine is 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethyl den)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. are illustrated. In addition, a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. Examples of commercial products of benzoxazine include "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Air Water Co., Ltd. .

(bismaleimide)

Bismaleimide is 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenylether bismaleimide, 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 Ether bismaleimide, 4,4'-diphenyl sulfone bismaleimide, etc. are illustrated. Moreover, as for the commercial item of bismaleimide, "BAF-BMI" by JFE Chemical Co., Ltd., etc. are illustrated.

(cyanate ester)

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-cumylphenol cyanate ester, 1,1 -Bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, 2,2-bis(4-cyanatophenyl)propane, etc. are illustrated. Moreover, as for the commercial item of cyanate ester, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)" etc. are illustrated.

The upper limit of the content of the crosslinking agent relative to 100 parts by mass of the polyimide (in terms of solid content) in the adhesive is 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, 10 parts by mass, etc. It is illustrated, and the lower limit is 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, 10, 5 parts by mass or the like. In one embodiment, the content of the crosslinking agent relative to 100 parts by mass of the polyimide (in terms of solid content) is preferably about 5 to 900 parts by mass.

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

<organic solvent>

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

In addition, the content of the organic solvent in the adhesive is not particularly limited, but the amount such that the solid mass is 10 to 60 mass% with respect to 100 mass% of the adhesive is preferable.

The upper limit of the content of the organic solvent relative to 100 parts by mass of the polyimide (in terms of solid content) in the adhesive is exemplified by 900, 800, 700, 600, 500, 400, 300, 200 parts by mass, and the lower limit is 800; 700, 600, 500, 400, 300, 200, 150 parts by mass and the like are exemplified. In one embodiment, the content of the organic solvent relative to 100 parts by mass of the polyimide (in terms of solid content) in the adhesive is preferably 150 to 900 parts by mass.

<Flame Retardant>

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

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

Examples of phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain phenolic hydroxyl groups. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferable in terms of flame retardancy, heat resistance, bleed-out resistance and the like. As for the commercial item of a cyclic phosphazene derivative, SPB-100 by Otsuka Chemical Co., Ltd., Labitol FP-300B by Fushimi Pharmaceutical Co., Ltd., etc. are illustrated.

(inorganic filler)

In one embodiment, inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion exchanger fillers, and the like. Examples of commercially available products include FB-3SDC manufactured by Denka Corporation, Exolit OP935 manufactured by Clariant Chemicals Corporation, KTL-500F manufactured by Kitamura Corporation, and IXE manufactured by Toa Synthetic Industries Co., Ltd.

The upper limit of the content of the flame retardant relative to 100 parts by mass of the polyimide (in terms of solid content) in the adhesive is 150, 100, 50, 10, 5 parts by mass, etc., and the lower limit is 125, 100, 50, 10, 5, 1 mass. wealth, etc. are exemplified. In one embodiment, the content of the flame retardant relative to 100 parts by mass of polyimide (in terms of solid content) in the adhesive is preferably 1 to 150 parts by mass.

<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 an acid anhydride group-reactive functional group, R ¹ is hydrogen or carbon atoms) A reactive alkoxysilyl compound represented by a hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2) is further included. With the reactive alkoxysilyl compound, the melt viscosity of the adhesive layer made of the adhesive of the present invention can be adjusted while maintaining the low dielectric properties. As a result, while increasing the interfacial adhesion between the adhesive layer and the substrate (a so-called anchor effect), oozing of the cured layer from the end of the substrate can be suppressed.

An amino group, an epoxy group, a thiol group, etc. are illustrated as a reactive functional group included in Z of the said general formula.

Compounds in which Z contains an amino group are N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Toxysilane, 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-mercaptopropylmethyldieter. Toxysilane etc. are illustrated. Among these, compounds in which Z contains an amino group are preferred because of their good reactivity and flow control effect.

The upper limit of the content of the reactive alkoxysilyl compound relative to 100 parts by mass of the polyimide (in terms of solid content) in the adhesive is 5, 2.5, 1, 0.5, 0.1, 0.05 parts by mass, etc., and the lower limit is 4, 2.5, 1, 0.5. , 0.1, 0.05, 0.01 parts by mass and the like are exemplified. In one embodiment, the content of the reactive alkoxysilyl compound with respect to 100 parts by mass of polyimide (in terms of solid content) in the adhesive is preferably 0.01 to 5 parts by mass.

The adhesive may include additives other than any of the polyimide, crosslinking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound.

Exemplary additives include a ring-opening esterification catalyst, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a release agent, a surface treatment agent, a viscosity control agent, a silica filler, and a fluorine filler. do.

In one embodiment, content of an additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, or the like with respect to 100 parts by mass of the adhesive.

In another embodiment, the additive content is exemplified as less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, or the like with respect to 100 parts by mass of the polyimide (in terms of solid content).

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 comprising a heat-cured product of the adhesive. Examples of the method for producing the film-like adhesive include a step of applying the adhesive to a suitable support, a step of heating to volatilize an organic solvent to harden, and a method including a step of peeling from the support. The thickness of the adhesive material is not particularly limited, but is preferably about 3 to 40 μm. As for a support body, the following thing etc. are illustrated.

[Adhesive layer]

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

[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, Aromatic polyester resins obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, and para-hydroxybenzoic acid (so-called liquid crystal polymers; Kuraray Co., Ltd., "Bexta", etc.) and the like are exemplified.

In addition, when applying the adhesive to the support film, the above application means can be employed. The thickness of the coating layer is not particularly limited either, but the thickness after drying is preferably about 1 to 100 μm, and more preferably about 3 to 50 μm. 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-coated 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-like 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 particularly limited, and is preferably about 1 to 100 μm, and more preferably about 2 to 38 μm. Further, the copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). As for the anti-rust treatment, a so-called mirror surface treatment such as a plating treatment using a plating solution containing Ni, Zn, Sn, or the like, or a chromate treatment is exemplified. Moreover, as an application|coating means, the method mentioned above is illustrated.

Further, the adhesive layer of the copper foil with resin may be uncured or partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B-stage state. Also, the thickness of the adhesive layer is not particularly limited, and is preferably about 0.5 to 30 μm. Moreover, copper foil can be bonded further to the adhesive surface of the said copper foil with resin, and it can also be set as copper foil with double-sided resin.

[copper clad laminate]

The present disclosure provides a copper clad laminate comprising the resin-coated copper foil and the copper foil or insulating sheet. The copper clad laminate is also called CCL (Copper Clad Laminate). Specifically, the copper clad laminate is obtained by pressing the above resin-coated copper foil on at least one or both surfaces of various known copper foils or insulating sheets under heating. In the case of bonding to one surface, you may press something different from the said copper foil with resin on the other surface. In addition, the number of sheets of copper foil with resin and insulating sheet in the copper clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. Prepreg refers to a sheet-like material made 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 polyimide resins, phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and aramid resins are used as the resin. The thickness of the prepreg is not particularly limited, and is preferably about 20 to 500 μm. Heating/pressing conditions are not particularly limited, and are 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 the 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. The semi-additive method is exemplified by a method of patterning the copper-clad laminate with a resist film on the copper foil surface, then performing 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|substrate can also be obtained by using the said printed wiring board as a core base material, and laminate|stacking the same printed wiring board, another well-known printed wiring board, or a printed circuit board on it. At the time of lamination, the said adhesive and other well-known adhesives other than the said adhesive can be used together. Moreover, the number of laminated layers in a multi-layer board is not particularly limited. In addition, a via hole may be inserted for each lamination, and the inside may be plated. The line/space ratio of the circuit pattern is not particularly limited, but is preferably about 1 µm/1 µm to 100 µm/100 µm. Also, the height of the circuit pattern is not particularly limited, but is preferably about 1 to 50 μm.

[Multilayer Wiring Board]

The present disclosure provides a multilayer wiring board including a printed wiring board (1) or printed circuit board (1), the adhesive layer, and a printed wiring board (2) or printed circuit board (2). The printed wiring boards (1) to (2) may be the printed wiring boards or may be known in various types. Similarly, the printed circuit boards 1 to 2 may be the above printed circuit boards or may be of various known types. In addition, 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.

[Manufacturing method of multilayer wiring board]

In the present disclosure, the following steps 1 and 2

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

Step 2: A step of laminating the printed wiring board 2 or the printed circuit board 2 on the base material with the adhesive layer and crimping under heating and pressure

It provides a manufacturing method of a multi-layer wiring board comprising a.

The printed wiring boards (1) to (2) may be the printed wiring boards or may be known in various types. Similarly, the printed circuit boards 1 to 2 may be the above printed circuit boards or may be of various known types.

In step 1, the means for bringing the adhesive or film-like adhesive into contact with the adherend is not particularly limited, and various known application means, curtain coater, roll coater, laminator, press ), etc. are exemplified.

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

Example

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. However, the description in the above 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. Therefore, the scope of the present invention is not limited to the embodiments or examples specifically described herein, but is limited only by the claims. In each Example and Comparative Example, unless otherwise specified, numerical values such as parts and % are based on mass.

<Manufacture of polyimide>

Preparation Example 1

Into a reaction vessel equipped with a stirrer, a water fountain, a thermometer and a nitrogen gas inlet tube, 9,9'-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorenic acid dianhydride (trade name) 290.00 g of "BPF-PA", manufactured by JFE Chemical Co., Ltd., hereinafter abbreviated as BPF-PA), 980.20 g of cyclohexanone, and 196.04 g of methylcyclohexane were put 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 an imidation reaction at 140 ° C. over 12 hours to obtain a solution of polyimide (1-1) Volatile content 31.6%) was obtained. In addition, the molar ratio of the acid component/amine component of the polyimide was 1.03.

Production examples other than Production Example 1 and Comparative Production Examples were carried out by the same method as Production Example 1 except for changing the composition of the resin solution as shown in Table 1 to obtain polyimide.

BPAF: 9,9'-bis(3,4-dicarboxyphenoxy)fluorenic acid dianhydride (trade name "BPAF", manufactured by JFE Chemical Co., Ltd.)

BAFL: 9,9'-bis(aminophenyl)fluorene (trade name "BAFL", manufactured by JFE Chemical Co., Ltd.)

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 1

10.00 g of polyimide resin (1-1) solution, 0.35 g of N,N-diglycidyl-4-glycidyloxyaniline (manufactured by Mitsubishi Chemical Corporation, trade name "jER630") as a crosslinking agent, and toluene as an organic solvent An adhesive having a non-volatile content of 30.0% was obtained by mixing 1.35 g and stirring well.

Examples and comparative examples other than Example 1 were carried out by the same method as in Example 1, except that the composition of the adhesive was changed as shown in Table 2, and adhesives were obtained.

Moreover, the organic solvent used when manufacturing polyimide can also be included in the organic solvent.

<Manufacture of adhesive sheet>

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

<Manufacture of copper-clad laminate>

The adhesive side of the obtained adhesive sheet was laminated on the roughened side of a commercially available electrodeposited copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 µm thick) to prepare a resin-coated copper foil.

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

<Adhesion test>

The peel strength (N/cm) of the obtained copper-clad laminate was measured according to JIS C 6481 (Test method for copper-clad laminate for flexible printed wiring boards). Results are shown in a table.

<Measurement of permittivity and dielectric loss tangent>

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

Then, the dielectric constant and dielectric loss tangent at 10 GHz of the obtained resin and cured samples for measuring dielectric constant were measured according to JIS C2565 using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AT). Results are shown in a table.

Claims (10)

It is a reactant of a monomer group containing aromatic tetracarboxylic acid anhydride and diamine including dimer diamine, and has a fluorenylene group on the polymer main chain.

Including, wherein the tetracarboxylic acid anhydride is 3,3',4,4'-biphenyltetracarboxylic acid dianhydride,
0 to 5% by mass of diaminopolysiloxane is contained with respect to 100% by mass of the monomer group,
A polyimide wherein the molar ratio [aromatic tetracarboxylic anhydride/diamine] of the aromatic tetracarboxylic acid anhydride and the diamine is 1.0 to 1.5. An adhesive comprising the polyimide according to claim 1, a crosslinking agent and an organic solvent. A film-like adhesive material comprising a heat-cured product of the adhesive according to claim 2. An adhesive layer comprising the adhesive according to claim 2 or the film adhesive according to claim 3. An adhesive sheet comprising the adhesive layer according to claim 4 and a support film. Copper foil with resin containing the adhesive layer and copper foil of Claim 4. A copper clad laminate comprising the copper foil with resin according to claim 6 and the copper foil or insulating sheet. A printed wiring board having a circuit pattern on the copper foil surface of the copper clad laminate according to claim 7. a printed wiring board (1) or a printed circuit board (1);
The adhesive layer according to claim 4, and
A multilayer wiring board comprising a printed wiring board (2) or a printed circuit board (2). The manufacturing method of the multilayer wiring board including the following process 1 and 2.
Step 1: A step of manufacturing a substrate with an adhesive layer by bringing the adhesive according to claim 2 or the film-like adhesive according to claim 3 into contact with at least one surface of the printed wiring board 1 or printed circuit board 1
Step 2: A step of laminating the printed wiring board 2 or the printed circuit board 2 on the base material with the adhesive layer and crimping under heating and pressure