KR102330421B1 - 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 an adhesive, a film adhesive, 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 method for manufacturing the same.
<Solutions>
A high softening point polyimide with a softening point of 140° C. or higher, a low softening point polyimide with a softening point of 100° C. or less, an adhesive containing a crosslinking agent, 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; It is taken as a solution means to provide the manufacturing method.

Description

Adhesives, film-like adhesives, adhesive layers, adhesive sheets, copper foil with resin, copper-clad laminates, printed wiring boards, and multilayer wiring boards and manufacturing methods thereof {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 invention relates to an adhesive, a film adhesive, an adhesive layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method for manufacturing the same.

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 (see Patent Document 1).

Japanese Patent No. 5534378

In recent years, the network-related electronic devices need 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. Therefore, 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, heat resistance and low dielectric properties of the moisture absorption solder were not examined. Moreover, before a reflow process, in order to suppress foaming and swelling by moisture absorption, a printed wiring board is pre-dried at the temperature of 100-120 degreeC in many cases. However, in order to improve production efficiency, the number of cases in which the solder reflow process is performed without predrying has increased these days. When a solder reflow process is performed without performing a predrying process, the solder heat resistance in about 260 degreeC reflow temperature is calculated|required, for example. Therefore, there has been a demand for an adhesive capable of forming an adhesive layer (cured product) excellent in room temperature adhesiveness, solder heat resistance in a moisture absorption state (moisture absorption solder heat resistance), and low dielectric properties.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solved by the adhesive agent containing a predetermined|prescribed polyimide as a result of earnest examination.

The present disclosure provides the following items.

(Item 1A)

An adhesive comprising a high softening point polyimide with a softening point of 140° C. or higher, a low softening point polyimide with a softening point of 100° C. or less, and a crosslinking agent.

(Item 1B)

The adhesive according to the above item comprising an organic solvent.

(Item 1)

An adhesive comprising a high softening point polyimide with a softening point of 140° C. or higher, a low softening point polyimide with a softening point of 100° C. or less, a crosslinking agent, and an organic solvent.

(Item 2)

The adhesive according to the above item, comprising two or more types of the low softening point polyimide.

(Item 3)

The adhesive according to any one of the above items, wherein the low softening point polyimide is 65 to 400 parts by mass based on 100 parts by mass (in terms of solid content) of the high softening point polyimide.

(Item 4)

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

(Item 5)

The epoxide has the structure

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

The adhesive according to any one of the above items, which is an epoxide of

(Item 6)

5 to 900 parts by mass of a crosslinking agent and 150 to 900 parts by mass of an organic solvent with respect to a total of 100 parts by mass (in terms of solid content) of the high softening point polyimide and the low softening point polyimide. The adhesive according to any one of the above items.

(Item 7)

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

(Item 8)

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

(Item 9)

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

(Item 10)

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

(Item 11)

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

(Item 12)

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

(Item 13)

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 14)

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 15)

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-like 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 combination of the disclosure.

By using the adhesive of the present invention, it is possible to provide an adhesive layer having good room temperature adhesiveness, solder heat resistance in a moisture absorption state (moisture absorption solder heat resistance), and low dielectric properties. The said adhesive can be used suitably with respect to high frequency electronic components, such as high-function mobile terminals, such as a printed wiring board.

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. .

[glue]

The present disclosure provides an adhesive comprising a high softening point polyimide having a softening point of 140° C. or higher, a low softening point polyimide having a softening point of 100° C. or less, and a crosslinking agent. In one embodiment, the adhesive may include an organic solvent to be described later.

<Polyimide>

A high softening point polyimide and a low softening point polyimide are collectively referred to as a polyimide.

In one embodiment, the polyimide is a reactant of a group of monomers comprising an aromatic tetracarboxylic anhydride and a diamine.

(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 a symmetric aromatic tetracarboxylic acid anhydride.

(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)

What is indicated by , etc. are exemplified.

The symmetric aromatic tetracarboxylic acid anhydride represented by the above general formula is 3,3′,4,4′-biphenyltetracarboxylic acid dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic acid 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) tetrafluoropropane dianhydride, 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'-benzophenonetetracarboxylic dianhydride, 4,4' At least 1 sort(s) chosen from the group which consists of -[propane-2,2-diylbis(1,4-phenyleneoxy)]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%, etc., 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 mass% of the aromatic tetracarboxylic acid anhydride is exemplified by 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 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.

The upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group is exemplified by 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% 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 an aromatic tetracarboxylic anhydride) that is not a symmetric aromatic tetracarboxylic anhydride.

In one embodiment, content of the other acid anhydride in an aromatic tetracarboxylic acid anhydride 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 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, as for content of the other acid anhydride 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, content of the other acid anhydride in a monomer group is 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 group, 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, alicyclic 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 means a carbon-carbon single bond or a carbon-carbon double bond. do).

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

As for 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 exemplified. 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.

As for the upper limit of content of the structural unit derived from dimerdiamine in 100 mol% of the structural unit derived from diamine in a high softening point polyimide, 50, 40, 30, 25 mol% etc. are illustrated, and a lower limit is 45, 40, 30, 25 , 20 mol% and the like are exemplified. In one embodiment, as for content of the structural unit derived from dimerdiamine in 100 mol% of structural units derived from diamine in a high softening point polyimide, 20-50 mol% is preferable.

As for the upper limit of content of the structural unit derived from dimerdiamine in 100 mass % of the structural unit derived from diamine in a high softening point polyimide, 50, 40, 30, 25 mass % etc. are illustrated, and a lower limit is 45, 40, 30, 25 , 20 mass %, etc. are illustrated. In one embodiment, as for content of the structural unit derived from dimerdiamine in 100 mass % of structural units derived from diamine in a high softening point polyimide, 20-50 mass % is preferable.

The upper limit of the content of the structural unit derived from dimerdiamine in 100 mol% of the structural unit derived from diamine in the low softening point polyimide is 100, 90, 80, 70, 60 mol%, etc., and the lower limit is 95, 90, 80 , 70, 60, 55 mol% and the like are exemplified. In one embodiment, as for content of the structural unit derived from dimerdiamine in 100 mol% of structural units derived from diamine in a low softening point polyimide, 55-100 mol% is preferable.

100, 90, 80, 70, 60 mass % etc. are illustrated as for the upper limit of content of the structural unit derived from dimerdiamine in 100 mass % of the structural unit derived from diamine in a low softening point polyimide, The lower limit is 95, 90, 80 , 70, 60, 55 mass %, etc. are illustrated. In one embodiment, as for content of the structural unit derived from dimerdiamine in 100 mass % of structural units derived from diamine in a low softening point polyimide, 55-100 mass % is preferable.

(alicyclic diamine)

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.

As an example of the method of adjusting the softening point of a polyimide, the method of adjusting the quantity of the alicyclic diamine which occupies for diamine, etc. are illustrated. The softening point of a polyimide becomes high, so that the quantity of the alicyclic diamine which occupies for a diamine increases. The said adjustment example is only one example, and it is possible to adjust the softening point of a polyimide by various well-known methods.

80, 70, 60, 50 mol% etc. are illustrated as for the upper limit of content of the structural unit derived from alicyclic diamine in a high softening point polyimide, and 75, 70, 60, 50, 45 mol% etc. are illustrated as for a lower limit. In one embodiment, when manufacturing a high softening point polyimide, it is preferable to contain 45-80 mol% of alicyclic diamines in diamine.

The upper limit of the content of the structural unit derived from the alicyclic diamine in the low softening point polyimide is exemplified by 40, 30, 20, 10, 5 mol%, and the lower limit is 35, 30, 20, 10, 5, 0 mol%, etc. is exemplified In one embodiment, when manufacturing a low softening point polyimide, it is preferable to contain 0-40 mol% of alicyclic diamines in diamine.

When producing a high softening point polyimide, the upper limit of the material amount ratio (dimerdiamine/alicyclic diamine) of dimerdiamine and alicyclic diamine is 1.3, 1.0, 0.5, 0.3, etc., and the lower limit is 1.2, 1.0, 0.5, 0.3, 0.2 and the like are exemplified. In one embodiment, when manufacturing a high softening point polyimide, the substance amount ratio (dimerdiamine/alicyclic diamine) of dimerdiamine and alicyclic diamine is 0.2-1.3 preferably.

In one embodiment, when manufacturing a low softening point polyimide, the material amount ratio of dimerdiamine and alicyclic diamine (dimerdiamine/alicyclic diamine) is 1.4 or more (for example, 2 or more, 5 or more, 10 or more, 100 or more) ) is preferred.

(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 diamino polysiloxane 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 mass % etc. are illustrated as for the upper limit of content of diamino polysiloxane in 100 mass % of diamine, and 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.

(other diamines)

Diamines other than the above include bisaminophenoxyphenylpropane, diaminodiphenylether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane , diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminoditrifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxy Phenyl ketone, aminophenoxyphenyl sulfide, 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 Glycolbis(aminoalkyl)ether, bis(aminoaryloxy)pyridine, diaminoalkylene, 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 the 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 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 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 includes 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 the 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 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 a monomer group, 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, etc. 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 obtained as polystyrene conversion values measured by, for example, Gel Permeation Chromatography (GPC).

The softening point of the high softening point polyimide is not particularly limited as long as it is 140°C or higher. The upper limit of the softening point of the high softening point polyimide is exemplified by 220, 210, 200, 190, 180, 170, 160, 150, 145 ° C., and the lower limit is 210, 200, 190, 180, 170, 160, 150, 145, 140 degreeC etc. are illustrated. In one embodiment, 140 degreeC or more is preferable and, as for the softening point of a high softening point polyimide, 140-220 degreeC is more preferable.

The softening point of the low softening point polyimide is not particularly limited as long as it is 100° C. or less. The upper limit of the softening point of the low softening point polyimide is exemplified by 100, 90, 80, 70, 60, 50, 40, 30, 25° C., and the lower limit is 90, 80, 70, 60, 50, 40, 30, 25, 20 degreeC etc. are illustrated. In one embodiment, 100 degrees C or less is preferable and, as for the softening point of a low softening point polyimide, 20-100 degreeC is more preferable.

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 acid 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 to 50 hours, More preferably, it is about 1 to 20 hours, the imidation reaction, ie, the method including the process of dehydration ring closure reaction, etc. are illustrated.

In addition, in the imidation reaction step, various known reaction catalysts, dehydrating agents, and organic solvents to be described later may be used. 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 normal temperature adhesiveness and heat-resistant adhesiveness becoming favorable, about 70 % or more is preferable and, as for the imide ring closure rate of the said polyimide, about 85-100 % is more preferable.

60, 50, 40, 30, 25 mass % etc. are illustrated as an upper limit of content of high softening point polyimide occupying the whole polyimide, and a lower limit is 55, 50, 40, 30, 25, 20 mass % etc. are illustrated . In one embodiment, as for content of the high softening point polyimide which occupies the whole polyimide, 20-60 mass % is preferable from a viewpoint of heat resistance, a softness|flexibility, and adhesiveness.

As for the upper limit of content of the low softening point polyimide occupying the whole polyimide, 80, 70, 60, 50, 45 mass % etc. are illustrated, and 75, 70, 60, 50, 40 mass % etc. are illustrated as for a lower limit. In one embodiment, 40-80 mass % is preferable from a viewpoint of heat resistance, a softness|flexibility, and adhesiveness of content of the low softening point polyimide occupying the whole polyimide.

As for the upper limit of the ratio of the low softening point polyimide with respect to 100 mass parts (solid content conversion) of a high softening point polyimide, 400, 300, 200, 100, 75, 70 mass parts etc. are illustrated, and a lower limit is 350, 300, 200, 100, 75, 70, 65 mass parts, etc. are illustrated. The range of the said ratio can be set suitably (for example, selecting from the value of the said upper limit and a lower limit). In one embodiment, it is preferable that it is 65-400 mass parts of low softening point polyimides with respect to 100 mass parts (solid content conversion) of a high softening point polyimide.

In one embodiment, the low softening point polyimide contains two or more types in a polyimide.

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, and a 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. 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 include 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, commercially available epoxide products include "jER828", "jER834", and "jER807" manufactured by Mitsubishi Chemical Co., Ltd., "ST-3000" manufactured by Nippon Chemical Co., Ltd., and "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 epoxide, bisphenol F epoxide, hydrogenated bisphenol A 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. In addition, when this is used, the low loss elastic modulus of the adhesive layer can be easily reduced, and the heat-resisting adhesive properties and low dielectric properties are also improved.

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- A 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-based 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 amount of the curing agent to be used is not particularly limited, when the solid content of the adhesive is 100% by mass, it is preferably about 0.1 to 120% by mass, and more preferably about 10 to 40% by mass.

When an epoxide and a curing agent for epoxide are used in combination as a crosslinking agent, a reaction catalyst may be further used in combination. 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, especially 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 photo)

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. Further, commercial products of benzoxazine include "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., "RLV-100" manufactured by Air Water Corporation, etc. .

(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. 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 10-60 mass % of solid content 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, and IXE manufactured by Toa Synthesis Corporation.

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 Part and the like are exemplified. In one embodiment, as for content of a 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 reacting 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. The melt viscosity can be controlled by the reactive alkoxysilyl compound 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. As the compound in which Z contains a thiol group, for example, 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 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, and the like. 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, any of the polyimide, a crosslinking agent, an organic solvent, a flame retardant, and a 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, 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 (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 including 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 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, 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 the said copper foil was made various surface treatment (roughening, rust prevention, etc.) may be sufficient. 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, uncured 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 copper foil with double-sided 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 laminate is 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 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. Moreover, the number in particular of the copper foil with resin and the insulating sheet in the said copper clad laminated board is not restrict|limited.

In one embodiment, the insulating sheet is preferably prepreg. Preprec refers to a sheet-like material that is hardened up to the B stage by impregnating a reinforcing material such as glass cloth with resin (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. The 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 a method of patterning the copper foil surface of a copper-clad laminate with a resist film, followed by 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|stacking, the said adhesive agent and other well-known adhesive agent other than the said adhesive agent can be used together. In addition, 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. 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: A step of manufacturing a base material with an adhesive layer by bringing the adhesive or the film adhesive 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.

In step 1, the means for contacting the adhesive or the film-like adhesive to the adherend is not particularly limited, and various known coating means, a curtain coater, a roll coater, a laminator, and a press are not particularly limited. ) and the like are exemplified.

The heating temperature and compression time in step 2 are not particularly limited, but (a) the adhesive or film adhesive of the present invention is brought into contact with at least one surface of the core substrate, and then heated to about 70 to 200° C. 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-treat 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 description, numerical values, such as a part, %, are based on mass.

<Production of polyimide>

manufacturing example One

4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride in a reaction vessel equipped with a stirrer, a water fountain, a thermometer and a nitrogen gas inlet tube 65.00 g of (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hereinafter abbreviated as BisDA) and 144.19 g of cyclohexanone were added, and the solution was heated to 60°C. Next, 19.29 g of dimerdiamine (trade name "PRIAMINE1075", manufactured by Kuroda Japan Co., Ltd.) and 11.85 g of 1,3-bis(aminomethyl)cyclohexane (trade name "1,3-BAC", manufactured by Mitsubishi Gas Chemicals) After gradually adding 26.22 g of methylcyclohexane and 91.8 g of ethylene glycol dimethyl ether (DMG), heating to 140° C. and imidation reaction over 3 hours, polyimide (1A-1) solution (non-volatile matter) 26.8%) was obtained. Moreover, the molar ratio of the acid component/amine component of the said polyimide resin was 1.05, and the softening point was 140 degreeC.

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 shown in Table 1 to obtain polyimide.

BisDA: 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride

PRIAMINE1075: Dimerdiamine, manufactured by Kuroda Japan Co., Ltd.

1, 3-BAC: 1, 3-bis (aminomethyl) cyclohexane

BTDA: 3, 3', 4, 4'-benzophenone tetracarboxylic dianhydride

Example One

Polyimide (1A-1) solution 5.69 g, polyimide (1B-1) solution 4.50 g, polyimide (1B-2) solution 2.53 g, N,N-diglycidyl-4-glycidyloxy as a crosslinking agent Aniline (manufactured by Mitsubishi Chemical Co., Ltd., trade name "jER630") 0.12 g, cyanate ester resin (trade name "TA", manufactured by Mitsubishi Chemical Gas Co., Ltd.) in methyl ethyl ketone solution (40% nonvolatile matter) 0.21 g, ( 3) 2.30 g of toluene as an organic solvent, (4) 2.30 g of a methyl ethyl ketone dispersion (50% non-volatile content) of spherical silica (trade name "FB-3SDC", manufactured by Denki Chemical Industry Co., Ltd.) as a flame retardant and a phosphorus flame retardant (trade name) "Exolit OP935", Clariant Japan Co., Ltd. methyl ethyl ketone solution (40% non-volatile matter) 1.44 g, and (5) N-2-(aminoethyl)-3-aminopropyl trime as reactive alkoxysilyl compound 0.08 g of oxysilane (trade name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd.) 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 copper-clad laminates>

The adhesive of Example 1 was applied to a rolled copper foil (trade name "GHF5", manufactured by JX Metals Co., Ltd.) with a gap coater so that the thickness after drying was 12 μm, and then dried at 150° C. for 5 minutes to obtain a copper foil with resin. . Using these two copper foils with resin, with the adhesive side on the inside, a polyimide film (trade name: "Kapton 50EN", manufactured by Toray DuPont Co., Ltd.) dehumidified at 120°C for 10 minutes was sandwiched, 170°C, A copper-clad laminate was obtained by thermal lamination at 5 MPa for 30 minutes, and then by applying a drying machine to 150°C and 12.5 MPa conditions for 1 minute, followed by curing at 180°C for 4 hours.

<Solder heat resistance test>

After curing, the copper-clad laminate was floated for 30 seconds with the copper foil side down in a solder bath at 288° C. to check whether there was any change in appearance. The case where there was no change was made into ○, and the case where there was foaming and swelling was made into x. A result is shown in a table.

<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>

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

Next, for the obtained dielectric constant measurement resin and cured material samples, the dielectric constant and dielectric loss tangent at 10 GHz were measured 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 (13)

A high softening point polyimide with a softening point of 140° C. or higher, a low softening point polyimide with a softening point of 100° C. or lower, and a crosslinking agent,
The high softening point polyimide and the low softening point polyimide are polyimides prepared by using dimer diamine without using silicone diamine,
Both the weight average molecular weight of the high softening point polyimide and the weight average molecular weight of the low softening point polyimide are less than 24000, or all of the adhesives are 24000 or more. According to claim 1,
An adhesive comprising an organic solvent. 3. The method of claim 1 or 2,
An adhesive comprising two or more types of the low softening point polyimide. 3. The method of claim 1 or 2,
The amount of the low softening point polyimide is 25 to 400 parts by mass based on 100 parts by mass (in terms of solid content) of the high softening point polyimide. A film adhesive comprising a heat-cured product of the adhesive according to claim 1 . An adhesive layer comprising the adhesive according to claim 1 or 2 or the film adhesive according to claim 5. An adhesive sheet comprising the adhesive layer according to claim 6 and a support film. Copper foil with resin containing the adhesive layer of Claim 6, and copper foil. A copper-clad laminate comprising the copper foil with resin according to claim 8 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 9. printed wiring board (1) or printed circuit board (1);
The adhesive layer according to claim 6, 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.
Step 1: Step of producing a base material with an adhesive layer by bringing the adhesive according to claim 1 or 2 or the film adhesive according to claim 5 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 crimping under heating and pressure delete