CN108690194B

CN108690194B - Polyimide, adhesive material, adhesive layer, adhesive sheet, copper foil, copper-clad laminate, wiring board, and method for producing same

Info

Publication number: CN108690194B
Application number: CN201810273039.9A
Authority: CN
Inventors: 杦本启辅; 山口贵史; 盐谷淳; 田崎崇司
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2017-03-29
Filing date: 2018-03-29
Publication date: 2022-11-01
Anticipated expiration: 2038-03-29
Also published as: JP2018168371A; CN108690194A; JP7003795B2; TWI795394B; KR20180110633A; TW201840649A; KR102323830B1

Abstract

The invention provides a polyimide, an adhesive material, an adhesive layer, an adhesive sheet, a copper foil, a copper-clad laminate, a wiring board, and a manufacturing method. The invention provides a polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride containing a symmetrical aromatic tetracarboxylic anhydride and a diamine containing an aromatic diamine and a dimer diamine, an adhesive containing the polyimide, a crosslinking agent and an organic solvent, a film-shaped adhesive material, 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 material, adhesive layer, adhesive sheet, copper foil, copper-clad laminate, wiring board, and method for producing same

Technical Field

The present invention relates to a polyimide, an adhesive, a film-like adhesive material, 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 producing the same.

Background art

Flexible Printed Wiring Boards (FPWB) and Printed Circuit Boards (PCB) and multilayer Wiring boards using the same are widely used in mobile communication devices such as mobile phones and smart phones, network-related electronic devices such as base station devices and servers and routers, and products such as large computers.

The present applicant has proposed "a polyimide-based adhesive composition comprising a polyimide resin obtained by reacting an aromatic tetracarboxylic acid with a diamine containing 30 mol% or more of a specific dimer diamine, a thermosetting resin, a flame retardant, and an organic solvent" (see patent document 1).

Documents of the prior art

Patent literature

Patent document 1: japanese patent No. 5534378

Disclosure of Invention

Problems to be solved by the invention

In recent years, with the development of measures for lead-free solder materials used for mounting components, solder heat resistance at a reflow temperature of about 260 ℃. However, the adhesive composition of patent document 1 has not been investigated for solder heat resistance in a moisture-absorbing state (moisture-absorbing solder heat resistance). Therefore, there is a problem that an adhesive having solder heat resistance in a moisture-absorbing state (moisture-absorbing solder heat resistance) is required.

Means for solving the problems

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

The present invention provides the following items.

(item 1)

A polyimide which is a reaction product of a monomer group comprising an aromatic tetracarboxylic anhydride and a diamine,

the aromatic tetracarboxylic anhydride contains a symmetrical aromatic tetracarboxylic anhydride represented by the following structural formula,

(wherein X represents a single bond or-SO)₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_p-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, p represents an integer from 1 to 20)

The diamine contains dimer diamine and aromatic diamine shown in the following structural formula.

(wherein Y represents a single bond, -SO₂-、-CO-、-O-、-O-C₆H₄-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_q-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, q represents an integer of 1 to 20. )

(item 2)

The polyimide according to the above item, wherein X and Y are-O-C₆H₄-C(CH₃)₂-C₆H₄-O-。

(item 3)

The polyimide according to any one of the above items, wherein the weight average molecular weight is 5000 to 50000.

(item 4)

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

(item 5)

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

(item 6)

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

(item 7)

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

(item 8)

The adhesive according to the above item, wherein the crosslinking agent is selected from the group consisting of epoxy compounds and benzophenones

At least one member selected from the group consisting of oxazines, bismaleimides, and cyanate esters.

(item 9)

The adhesive according to the above item, wherein the epoxy compound is an epoxy compound having the following structure.

(wherein Z represents a phenylene group or a cyclohexylene group.)

(item 10)

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

(item 11)

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

(item 12)

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 13)

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

(item 14)

A copper foil with resin, comprising the adhesive layer and the copper foil.

(item 15)

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

(item 16)

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

(item 17)

A printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate as described in any one of the above items.

(item 18)

A multilayer wiring board, comprising:

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

The adhesive layer described in the above item, and

a printed wiring board (2) or a printed circuit board (2).

(item 19)

A method for manufacturing a multilayer wiring board includes 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 item into contact with at least one surface of a printed wiring board (1) or a printed circuit board (1);

and a step 2: and a step of laminating a printed wiring board (2) or a printed wiring board (2) on the base material with the adhesive layer and pressing the same under heat and pressure.

In the present invention, one or more of the above-described features may be provided in further combination in addition to the combinations explicitly described.

Effects of the invention

By using the polyimide of the present invention, an adhesive having high heat resistance can be provided for a moisture-absorbing solder. Therefore, the adhesive can be particularly suitably used for a flexible printed board.

Detailed Description

Throughout the specification of the present invention, ranges of numerical values such as physical property values and contents may be appropriately set (for example, selected from upper and lower limits described in the following items). Specifically, the numerical value α can be, for example, A1, A2, A3, etc., as the upper limit of the numerical value α, B1, B2, B3, etc., as the lower limit of the numerical value α, the range of the numerical value α can be, for example, A1 or less, A2 or less, A3 or less, 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.

[ polyimide ]

The present invention provides a polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride and a diamine, wherein the aromatic tetracarboxylic anhydride contains a symmetrical aromatic tetracarboxylic anhydride represented by the following structural formula,

(wherein X represents a single bond or-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_p-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, p represents an integer from 1 to 20),

the diamine contains dimer diamine and aromatic diamine shown in the following structural formula,

(wherein Y represents a single bond, -SO₂-、-CO-、-O-、-O-C₆H₄-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_q-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, q represents an integer of 1 to 20).

< aromatic tetracarboxylic anhydride >

The aromatic tetracarboxylic anhydride may be used alone or in combination of two or more. Examples of the aromatic tetracarboxylic anhydride include symmetrical aromatic tetracarboxylic anhydride and the like.

(symmetrical aromatic tetracarboxylic acid anhydride)

In the present invention, the "symmetrical aromatic tetracarboxylic anhydride" refers to an aromatic tetracarboxylic anhydride having an axis of symmetry (e.g., C2 axis of symmetry) in the molecule. Examples of the symmetrical aromatic tetracarboxylic anhydride include symmetrical aromatic tetracarboxylic anhydrides represented by the following general formulae.

(wherein X represents a single bond or-SO)₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_p-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, p represents an integer from 1 to 20. )

Examples of the symmetric aromatic tetracarboxylic acid anhydride represented by the above general formula include 3,3', 4' -biphenyltetracarboxylic acid dianhydride, 3', 4' -diphenylsulfonetetracarboxylic acid dianhydride, 3',4,4' -benzophenonetetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 4'- [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride, 2-bis (3, 3',4,4 '-Tetracarboxyphenyl) tetrafluoropropane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2' -bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2', 3' -biphenyltetracarboxylic acid dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, pyromellitic acid dianhydride, 1,2,3, 4-benzenetetracarboxylic acid anhydride, 1,4,5, 8-naphthalenetetracarboxylic acid anhydride, 2,3,6, 7-naphthalenetetracarboxylic acid anhydride, and the like.

Among the above symmetrical aromatic tetracarboxylic acid anhydrides, at least one selected from the group consisting of 3,3', 4' -benzophenonetetracarboxylic acid dianhydride, 4'- [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic acid dianhydride and 4,4' -oxydiphthalic anhydride is preferable from the viewpoints of compatibility of the aromatic tetracarboxylic acid anhydride with diamines, room temperature adhesiveness, heat-resistant adhesiveness and the like.

The upper limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100 mol% of the aromatic tetracarboxylic anhydride may be exemplified by 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 55 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, etc., and the lower limit may be exemplified by 95 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, 1 mol%, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the aromatic tetracarboxylic anhydride is preferably 1 to 100 mol%, more preferably about 50 mol% to about 100 mol%.

The upper limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100 mass% of the aromatic tetracarboxylic anhydride may be, for example, 100 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, etc., and the lower limit may be, for example, 95 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, 1 mass%, etc. In one embodiment, the content of the symmetric aromatic tetracarboxylic anhydride in 100% by mass of the aromatic tetracarboxylic anhydride is preferably 1 to 100% by mass, and more preferably about 50% by mass to about 100% by mass.

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

Examples of the upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100 mass% of the monomer group include 75 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass% and the like, and examples of the lower limit thereof include 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass% and the like. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably from about 5% by mass to about 75% by mass.

(other aromatic tetracarboxylic acid anhydrides)

In one embodiment, the monomer group may contain an aromatic tetracarboxylic anhydride (also referred to as another aromatic tetracarboxylic anhydride) other than the aromatic tetracarboxylic anhydride.

In one embodiment, the content of the other acid anhydride in the aromatic tetracarboxylic anhydride may be, for example, less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, or about 0 mol%.

In one embodiment, the content of the other acid anhydride in the aromatic tetracarboxylic anhydride may be, for example, less than 5 mass%, less than 4 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.5 mass%, less than 0.1 mass%, or about 0 mass%.

In an embodiment, the content of the other anhydride in the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, and the like.

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

Examples of the upper limit of the content of the aromatic tetracarboxylic acid anhydride in 100 mol% of the monomer group include 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, etc., and examples of the lower limit thereof include 70 mol%, 65 mol%, 60 mol%, 55 mol%, 50 mol%, etc. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably about 50 mol% to about 75 mol%.

The upper limit of the content of the aromatic tetracarboxylic anhydride in 100% by mass of the monomer group may be, for example, 75% by mass, 70% by mass, 65% by mass, 60% by mass, or 55% by mass, and the lower limit may be, for example, 70% by mass, 65% by mass, 60% by mass, 55% by mass, or 50% by mass. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably from about 50% by mass to about 75% by mass.

< diamine >

The diamine may be used alone or in combination of two or more. Examples of the diamine include dimer diamine, aromatic diamine, and diaminopolysiloxane.

(dimer diamine)

In the present invention, the dimer diamine is obtained by substituting all carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acid such as oleic acid, with primary amino groups (see, for example, japanese unexamined patent application publication No. 9-12712), and various known dimer diamines can be used without particular limitation. A non-limiting general formula of the dimer diamine is shown below (in each formula, m + n =6 to 17 is preferable, p + q =8 to 19 is preferable, and the dotted line portion represents a carbon-carbon single bond or a carbon-carbon double bond).

The commercially available products of dimer diamine are exemplified by the groups consisting of: 1249612569551 (124671246491\\ 1246312531975 (manufactured by 1251125699, 1251125975, 1251125699 (manufactured by 1251125125198552).

Examples of the upper limit of the content of the dimer diamine component in 100 mol% of the diamine include 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, and the like, and examples of the lower limit thereof include 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, 20 mol%, and the like. In one embodiment, the content of the dimer diamine component in 100 mol% of the diamine is preferably from about 20 mol% to about 80 mol% from the viewpoint of improving flexibility, adhesiveness, and solvent solubility.

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

Examples of the upper limit of the content of the dimer diamine in 100 mol% of the monomer group include 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, and the like, and examples of the lower limit thereof include 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, 5 mol%, and the like. In one embodiment, the content of the dimer diamine in 100 mol% of the monomer group is preferably 5 to 50 mol%.

Examples of the upper limit of the content of the dimer diamine in 100% by mass of the monomer group include 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, and 8% by mass, and examples of the lower limit thereof include 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, and 5% by mass. In one embodiment, the content of the dimer diamine in 100% by mass of the monomer group is preferably 5 to 50% by mass.

(aromatic diamine)

In one embodiment, the aromatic diamine is represented by the following general formula.

(wherein Y represents a single bond or-SO)₂-、-CO-、-O-、-O-C₆H₄-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_q-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, q represents an integer from 1 to 20. )

Examples of the aromatic diamine include 4,4 '-diaminobiphenyl, 4' -diaminobenzophenone, 4 '-diaminodiphenyl ether, and 4,4' - (4, 4 '-isopropylidenediphenyl-1, 1' -diyldioxy) diphenylamine.

Examples of the upper limit of the content of the aromatic diamine in 100 mol% of the diamine include 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, and the like, and examples of the lower limit thereof include 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, 20 mol%, and the like. In one embodiment, the content of the aromatic diamine in 100 mol% of the diamine is preferably from 20 to 80 mol% from the viewpoints of solvent solubility, workability, and flexibility.

The upper limit of the content of the aromatic diamine in 100 mass% of the diamine may be, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 25 mass%, etc., and the lower limit may be, for example, 75 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 25 mass%, 20 mass%, etc. In one embodiment, the content of the aromatic diamine in 100 mass% of the diamine is preferably 20 to 80 mass% from the viewpoints of solvent solubility, workability, and flexibility.

Examples of the upper limit of the content of the aromatic diamine in 100 mol% of the monomer group include 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, etc., and examples of the lower limit thereof include 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, 5 mol%, etc. In one embodiment, the content of the aromatic diamine in 100 mol% of the monomer group is preferably 5 to 50 mol%.

The upper limit of the content of the aromatic diamine in 100% by mass of the monomer group may be, for example, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, or 8% by mass, and the lower limit may be, for example, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, or 5% by mass. In one embodiment, the content of the aromatic diamine in 100% by mass of the monomer group is preferably 5 to 50% by mass.

The upper limit of the ratio of the amount of the aromatic diamine to the amount of the dimer diamine (aromatic diamine/dimer diamine) may be exemplified by 4.0, 3.0, 2.0, 1.0, 0.50, etc., and the lower limit may be exemplified by 4.0, 3.0, 2.0, 1.0, 0.50, 0.25, etc. In one embodiment, the ratio of the amount of the aromatic diamine to the amount of the dimer diamine (aromatic diamine/dimer diamine) is preferably 0.25 to 4.0 from the viewpoints of solvent solubility, workability, flexibility, adhesiveness, and dielectric properties.

(Diaminopolysiloxane)

Examples of the diaminopolysiloxane 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, and 1, 3-bis (4-aminobutyl) tetramethyldisiloxane.

Examples of the upper limit of the content of the diaminopolysiloxane in 100 mol% of the diamine include 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, and the like, and examples of the lower limit thereof include 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, and the like. In one embodiment, the content of the diaminopolysiloxane in 100 mol% of the diamine is preferably from about 0 mol% to about 5 mol%, from the viewpoint of improving flexibility.

Examples of the upper limit of the content of the diaminopolysiloxane in 100% by mass of the diamine include 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and the like, and examples of the lower limit thereof include 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0% by mass, and the like. In one embodiment, the content of the diaminopolysiloxane in 100% by mass of the diamine is preferably from about 0% by mass to about 5% by mass from the viewpoint of improving flexibility.

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

Examples of the upper limit of the content of the diaminopolysiloxane in 100% by mass of the monomer group include 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass and the like, and examples of the lower limit thereof include 4% by mass, 3% by mass, 2% by mass, 1% by mass, 0% by mass and the like. In one embodiment, the content of the diaminopolysiloxane in 100% by mass of the monomer group is preferably from about 0% by mass to about 5% by mass from the viewpoint of improving flexibility.

(other diamines)

In one embodiment, the monomer group may contain a diamine other than those described above (also referred to as other diamines). <xnotran> , , , , , , , , , , , , , , , , , , , , , ( ) , ( - α, α - ) , [ ( ) ] , ( - α, α - ) , [ - α, α - ] ,4,4' - [ ] , , ,6,6 ' - ( ) -3,3,3',3' - -1,1' - , ( ) , ( ) , ( ) , [ ( ) ] , () ( ) , ( ) , </xnotran> Alkylene diamines, and the like.

As the alicyclic diamine, 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' -diaminodicyclohexylmethane, 1, 3-bisaminomethylcyclohexane, and the like can be given.

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

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

The phenylenediamine includes, for example, phenylenediamine such as p-phenylenediamine and m-phenylenediamine.

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

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

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

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

Examples of the diaminophenylpropane include 2, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane, and 2- (3-aminophenyl) -2- (4-aminophenyl) propane.

Examples of the diaminophenylhexafluoropropane include 2, 2-bis (3-aminophenyl) -1, 3-hexafluoropropane 2, 2-bis (4-aminophenyl) -1, 3-hexafluoropropane 2- (3-aminophenyl) -2- (4-aminophenyl) -1, 3-hexafluoropropane, and the like.

Examples of the diaminophenylphenylethane include 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane.

Examples of the bisaminophenoxy benzene include 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene.

Examples of the bisaminobenzoylbenzene include 1, 3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1, 4-bis (3-aminobenzoyl) benzene, and 1, 4-bis (4-aminobenzoyl) benzene.

Examples of the bisaminodimethylbenzyl benzene include 1, 3-bis (3-amino-. Alpha.,. Alpha. -dimethylbenzyl) benzene, 1, 3-bis (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) benzene, 1, 4-bis (3-amino-. Alpha.,. Alpha. -dimethylbenzyl) benzene, and 1, 4-bis (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) benzene.

Examples of the bisaminobistrifluoromethylbenzyl benzene include 1, 3-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene.

Examples of the aminophenoxybiphenyl include 2, 6-bis (3-aminophenoxy) benzonitrile, 4 '-bis (3-aminophenoxy) biphenyl, and 4,4' -bis (4-aminophenoxy) biphenyl.

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, bis [4- (4-aminophenoxy) phenyl ] sulfide and the like.

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

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

Examples of the aminophenoxyphenyl propane include 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, and 2, 2-bis [3- (3-aminophenoxy) phenyl ] -1, 3-hexafluoropropane 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1, 3-hexafluoropropane, and the like.

Examples of the bis (aminophenoxybenzoyl) benzene include 1, 3-bis [4- (3-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) benzoyl ] benzene, and 1, 4-bis [4- (4-aminophenoxy) benzoyl ] benzene.

Examples of bis (aminophenoxy-. Alpha.,. Alpha. -dimethylbenzyl) benzene include 1, 3-bis [4- (3-aminophenoxy) -alpha.,. Alpha. -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) -alpha.,. Alpha. -dimethylbenzyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) -alpha.,. Alpha. -dimethylbenzyl ] benzene, and 1, 4-bis [4- (4-aminophenoxy) -alpha.,. Alpha. -dimethylbenzyl ] benzene.

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

Examples of bis (amino-. Alpha.,. Alpha. -dimethylbenzylphenoxy) benzophenone include 4,4' -bis [4- (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) phenoxy ] benzophenone and the like.

Examples of bis [ amino-. Alpha.,. Alpha. -dimethylbenzylphenoxy ] diphenylsulfone include 4,4' -bis [4- (4-amino-. Alpha.,. Alpha. -dimethylbenzyl) phenoxy ] diphenylsulfone and the like.

Examples of 4,4 '-bis [ aminophenoxy phenoxy ] diphenyl sulfone include 4,4' -bis [4- (4-aminophenoxy) phenoxy ] diphenyl sulfone.

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

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

Examples of 6,6 '-bis (aminoaryloxy) -3, 3' -tetramethyl-1, 1 '-spirobiindane include 6,6' -bis (3-aminophenoxy) -3, 3',3' -tetramethyl-1, 1 '-spirobiindane, 6' -bis (4-aminophenoxy) -3,3 '-tetramethyl-1, 1' -spirobiindane, and the like.

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

Examples of the bis (aminoalkoxyalkyl) ether include bis [2- (aminomethoxy) ethyl ] ether, bis [2- (2-aminoethoxy) ethyl ] ether, and bis [2- (3-aminopropoxy) ethyl ] ether.

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

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

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 and the like.

As the alkylenediamine, 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, and the like can be exemplified.

In one embodiment, the content of the other diamine in the diamine may be, for example, less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, or about 0 mol%.

In one embodiment, the content of the other diamine in the diamine may be, for example, less than 5 mass%, less than 4 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.5 mass%, less than 0.1 mass%, or about 0 mass%.

In one embodiment, the content of the other diamine in the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, or the like.

In one embodiment, the content of the other diamine in the monomer group may be exemplified by less than 5 mass%, less than 4 mass%, less than 1 mass%, less than 0.9 mass%, less than 0.5 mass%, less than 0.1 mass%, about 0 mass%, and the like.

Examples of the upper limit of the diamine content in 100 mol% of the monomer group include 50 mol%, 45 mol%, 40 mol%, 35 mol%, 30 mol%, and the like, and examples of the lower limit thereof include 45 mol%, 40 mol%, 35 mol%, 30 mol%, 25 mol%, and the like. In one embodiment, the diamine content in 100 mole% of the monomer group is preferably from about 25 mole% to about 50 mole%.

Examples of the upper limit of the diamine content in 100% by mass of the monomer group include 50% by mass, 45% by mass, 40% by mass, 35% by mass, and 30% by mass, and examples of the lower limit include 45% by mass, 40% by mass, 35% by mass, 30% by mass, and 25% by mass. In one embodiment, the content of the diamine in 100% by mass of the monomer group is preferably about 25% by mass to about 50% by mass.

The molar ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] can be exemplified by an upper limit of 1.5, 1.4, 1.3, 1.2, 1.1, etc., and a lower limit of 1.4, 1.3, 1.2, 1.1, 1.0, etc. In one embodiment, the molar ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] is preferably from about 1.0 to about 1.5 from the viewpoint of solvent solubility and solution stability.

Examples of the mass ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] include 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, and 0.6 as the upper limit and 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, and 0.5 as the lower limit. In one embodiment, the mass ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] is preferably 0.5 to 1.5.

< other monomers >

In one embodiment, the monomer set may contain monomers (also referred to as other monomers) that are neither aromatic tetracarboxylic anhydrides nor diamines. Examples of the other monomer include aliphatic tetracarboxylic acid anhydrides.

In one embodiment, the content of the other monomer in the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, and the like.

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

< physical Properties of polyimide, etc. >

The upper limit of the weight average molecular weight of the polyimide is 50000, 40000, 30000, 20000, 10000, 7500, 5500, etc., and the lower limit is 45000, 40000, 30000, 20000, 10000, 7500, 5000, etc. In one embodiment, the polyimide preferably has a weight average molecular weight of 5000 to 50000 in terms of dielectric properties, solvent solubility, and flexibility.

Examples of the upper limit of the number average molecular weight of the polyimide include 40000, 30000, 20000, 10000, 7500, 5000, 3000 and the like, and examples of the lower limit thereof include 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 40000 from the viewpoints of dielectric properties, solvent solubility, and flexibility.

The weight average molecular weight and the number average molecular weight can be determined as values converted to polystyrene measured by Gel Permeation Chromatography (GPC), for example.

The upper limit of the softening point of the polyimide is, for example, 250 ℃, 200 ℃, 150 ℃, 130 ℃ or the like, and the lower limit thereof is, for example, 240 ℃, 200 ℃, 150 ℃, 130 ℃, 120 ℃ or the like. In one embodiment, the softening point of the polyimide is preferably 120 to 250 ℃ from the viewpoint of workability, flexibility, and adhesiveness.

The softening point can be obtained by using a commercially available measuring instrument ("ARES-2 KSTD-FCO-STD", manufactured by Rheometric scientific Co., ltd.).

< method for producing polyimide, etc. >

The polyimide can be produced by various known methods. The method for producing polyimide may be exemplified by: comprises a step of obtaining an addition polymer by subjecting a monomer group containing an aromatic tetracarboxylic acid anhydride and a diamine such as a dimer diamine to an addition polymerization reaction at a temperature of preferably from about 60 ℃ to about 120 ℃, more preferably from about 80 ℃ to about 100 ℃, for preferably from about 0.1 hour to about 2 hours, more preferably from about 0.1 hour to about 0.5 hour; and a step of subjecting the resulting addition polymer to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of preferably about 80 to about 250 ℃ and more preferably about 100 to about 200 ℃ for preferably about 0.5 to about 50 hours and more preferably about 1 to about 20 hours.

In the step of conducting the imidization reaction, various known reaction catalysts, dehydrating agents and organic solvents described later can be used. The various known reaction catalysts, dehydrating agents and organic solvents described later may be used singly 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. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The imide ring-closing ratio of the polyimide is not particularly limited. The "imide ring closure ratio" refers to the content of cyclic imide bonds in polyimide, and can be determined by various spectroscopic methods such as NMR and IR analysis. The imide ring-closing ratio of the polyimide is preferably about 70% or more, and more preferably about 85% to about 100%, from the viewpoint of improving the room-temperature adhesiveness and the heat-resistant adhesiveness.

[ Adhesives ]

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

The upper limit of the content of the polyimide in 100 mass% of the adhesive may be, for example, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, etc., and the lower limit may be, for example, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 5 mass%, etc. The content of the polyimide in 100% by mass of the adhesive is preferably about 5% by mass to about 90% by mass.

< crosslinking agent >

The crosslinking agent is not particularly limited, and various known crosslinking agents can be used as long as the crosslinking agent functions 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 selected from the group consisting of epoxy compounds, benzophenones

(epoxy compound)

Examples of the epoxy compound include phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, stilbene type epoxy compounds, triazine skeleton-containing epoxy compounds, fluorene skeleton-containing epoxy compounds, linear aliphatic epoxy compounds, alicyclic epoxy compounds, glycidyl amine type epoxy compounds, triphenol methane type epoxy compounds, alkyl-modified triphenol methane type epoxy compounds, biphenyl type epoxy compounds, dicyclopentadiene skeleton-containing epoxy compounds, naphthalene skeleton-containing epoxy compounds, aryl alkylene type epoxy compounds, tetraglycidyl xylylenediamine, dimer acid-modified epoxy compounds which are dimer acid-modified products of the above epoxy compounds, dimer acid diglycidyl esters, and the like. Examples of commercially available products of the epoxy compound include "jER828", "jER834" and "jER807" manufactured by Mitsubishi chemical corporation, "ST-3000" manufactured by New Nippon iron chemical corporation, "\1247512452124124124124124892021P" manufactured by Darliki chemical corporation, "YD-172-X75" manufactured by Mitsubishi gas chemical corporation, and "TETRAD-X" manufactured by Mitsubishi gas chemical corporation. Among them, from the viewpoint of the balance among heat-resistant adhesiveness, moisture-absorbing solder heat resistance, and low dielectric characteristics, at least one selected from the group consisting of bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, and alicyclic epoxy compounds is preferable.

In particular, tetraglycidyl diamine having the following structure has good compatibility with the polyimide. In addition, when this component is used, the loss elastic modulus of the adhesive layer is easily lowered, and the heat resistant adhesiveness and the low dielectric characteristics thereof are also improved.

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

When an epoxy compound is used as the crosslinking agent, various known curing agents for epoxy compounds may be used in combination. The epoxy compound curing agent may be used alone or in combination of two or more. Examples of the curing agent for epoxy compounds include: acid anhydride curing agents such as succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2, 3-dicarboxylic anhydride, methylnorbornane-2, 3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, and the like; dicyandiamide (DICY), aromatic diamines (trade names "lonzacure m-DEA", "lonzacure m-DETDA", and the like, all of which are manufactured by losa japan), and amine curing agents such as aliphatic amines; phenol curing agents such as phenol novolak resins, cresol novolak resins, bisphenol A novolak resins, triazine-modified phenol novolak resins, phosphazene curing agents such as a phosphazene containing a phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka chemical Co., ltd.), cyclic phosphazene compounds, and rosin crosslinking agents such as maleic acid-modified rosin and hydrogenated products thereof. Among these, phenol curing agents are preferable, and phosphazene curing agents containing a phenolic hydroxyl group are particularly preferable. The amount of the curing agent to be used is not particularly limited, and is preferably from about 0.1 to about 120% by mass, and more preferably from about 10 to about 40% by mass, when the solid content of the adhesive is 100% by mass.

In the case of using an epoxy compound and a curing agent for an epoxy compound 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 may be exemplified by: 1, 8-diaza-bicyclo [5.4.0]Tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenyl radical

Tetraphenylboron salts such as tetraphenylboron salt, 2-ethyl-4-methylimidazotetraphenylboron salt and N-methylmorpholinebetraphenylboron salt. The amount of the reaction catalyst used is not particularly limited, but is preferably from about 0.01% by mass to about 5% by mass, assuming that the solid content of the binder is 100% by mass.

(benzo

Oxazines

Benzo [ b ]

Examples of the oxazine include 6,6- (1-methylethylidene) bis (3, 4-dihydro-3-phenyl-2H-1, 3-benzo

Oxazines), 6- (1-methylethylidene) bis (3, 4-dihydro-3-methyl-2H-1, 3-benzo

Oxazines), and the like. It should be noted that, in the following description,

the nitrogen of the oxazine ring may have a phenyl group, a methyl group, a cyclohexyl group, or the like bonded thereto. In addition, benzene

Examples of commercially available oxazines include "benzo" manufactured by four national chemical industries, ltd

Oxazine F-a type,' benzo

-type oxazine P-d, \ 124565054\\ 12457w- \ 124795 manufactured by the company "RLV-100", etc..

(bismaleimide)

Examples of bismaleimides include 4,4' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6' -bismaleimide- (2, 4-trimethyl) hexane, 4' -diphenyl ether bismaleimide, and 4,4' -diphenylsulfone bismaleimide. Further, examples of commercially available bismaleimides include "BAF-BMI" manufactured by JFE chemical Co.

(cyanate ester)

Examples of the cyanate ester include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2-bis (4-cyanatophenol) -1, 3-hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, and 4-phenylphenol cyanate, 1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate, 1-bis (4-cyanatophenyl) ethane, 4' -bisphenol cyanate, 2-bis (4-cyanatophenyl) propane and the like. Examples of commercially available cyanate esters include "PRIMASETTBTP-6020S (manufactured by LONGSHA Japan K.K.)" and the like.

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

The upper limit of the content of the crosslinking agent in 100% by mass of the adhesive may be, for example, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, or the like, and the lower limit may be, for example, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, or 2% by mass. In one embodiment, the content of the crosslinking agent in 100% by mass of the adhesive is preferably about 2% by mass to about 80% by mass.

Organic solvent

The organic solvent may be used alone or two or more of various known organic solvents may be used. Examples of the organic solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, triethylene glycol dimethyl ether (methylglyme) and diethylene glycol dimethyl ether (methylglyme), alicyclic solvents such as cyclohexanone and methylcyclohexane, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol, and aromatic solvents such as toluene.

The content of the organic solvent in the adhesive is not particularly limited, but is preferably 10 to 60 mass% based on 100 mass% of the adhesive in terms of the mass of the solid content.

The upper limit of the content of the organic solvent in the adhesive with respect to 100 parts by mass (in terms of solid content) of the polyimide may be, for example, 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, etc., and the lower limit may be, for example, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 150 parts by mass, etc. In one embodiment, the content of the organic solvent in the adhesive is preferably 150 to 900 parts by mass with respect to 100 parts by mass (in terms of solid content) of the polyimide.

< flame retardant >

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

(phosphorus flame retardant)

Examples of the phosphorus flame retardant include polyphosphoric acid, phosphoric acid esters, and phosphazene derivatives containing no phenolic hydroxyl group. Among these phosphazene derivatives, cyclic phosphazene derivatives are preferable from the viewpoint of flame retardancy, heat resistance, bleed-out resistance, and the like. Examples of commercially available products of the cyclic phosphazene derivative include SPB-100 manufactured by Otsuka chemical Co., ltd., \ 1252112499.

(inorganic Filler)

In one embodiment, the inorganic filler may be exemplified by silica filler, phosphorus-based filler, fluorine-based filler, inorganic ion exchanger filler, and the like. Examples of commercially available products include FB-3SDC manufactured by Kagaku K.K., exolit OP935 manufactured by Kelaien chemical Co., ltd, KTL-500F manufactured by Kyomura, and IXE manufactured by Toyo chemical Co., ltd.

The upper limit of the content of the flame retardant in the adhesive to 100 parts by mass (in terms of solid content) of the polyimide may be, for example, 150 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass, etc., and the lower limit may be, for example, 125 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, 5 parts by mass, 1 part by mass, etc. In one embodiment, the content of the flame retardant in the adhesive is preferably 1 to 150 parts by mass per 100 parts by mass (in terms of solid content) of the polyimide.

< reactive alkoxysilyl Compound >

In one embodiment, the adhesive further comprises a compound of the formula: Z-Si (R)¹)_a(OR²)_3-a(wherein Z represents a group having a functional group reactive with an acid anhydride group, and R¹Represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R²Represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. ) A reactive alkoxysilyl compound as shown. With the reactive alkoxysilyl compound, it is possible to maintain the low dielectric characteristics and adjust the melt viscosity of the adhesive layer including the adhesive of the present invention. As a result, it is possible to suppress the bleeding of the cured layer from the end portion of the base material while improving the interfacial adhesion (so-called anchor effect) of the adhesive layer to the base material.

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

Examples of the compound in which Z has an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane. Examples of the compound having an epoxy group in Z include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which Z has a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among them, a compound in which Z contains an amino group is preferable from the viewpoint of good reactivity and flow rate control effect.

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

The adhesive may contain, as an additive, one or more other than the polyimide, the crosslinking agent, the organic solvent, the flame retardant, and the reactive alkoxysilyl compound.

Examples of the additives include ring-opening esterification catalysts, dehydrating agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, silica fillers, fluorine fillers, and the like.

In one embodiment, the content of the additive may be 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 content of the additive may be 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, based on 100 parts by mass (in terms of solid content) of the polyimide.

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

[ film-like adhesive Material ]

The present invention provides a film-like adhesive material comprising a heat-cured product of the adhesive. Examples of the method for producing the film-like adhesive material include a method including a step of applying the adhesive to an appropriate support, a step of volatilizing an organic solvent by heating to cure the adhesive, a step of peeling the adhesive from the support, and the like. The thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to about 40 μm. The support may be made of the following materials.

[ adhesive layer ]

The present invention provides an adhesive layer comprising an adhesive or the above film-like adhesive material. In the production of the adhesive layer, the adhesive may be used in combination with various known adhesives other than the adhesive. Similarly, the film-like adhesive material may be used in combination with various known film-like adhesive materials other than the film-like adhesive material.

[ adhesive sheet ]

The present invention provides an adhesive sheet comprising the above adhesive layer and a support film.

The support film may be exemplified by a plastic film. Examples of the plastic include polyester, 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 p-hydroxybenzoic acid and the like (so-called liquid crystal polymers; manufactured by kokura corporation, "v. \\ 124637940794.

In addition, the above coating means may be employed when the adhesive is coated on the support film. The thickness of the coating layer is also not particularly limited, and the thickness after drying is preferably from about 1 μm to about 100 μm, more preferably from about 3 μm to about 50 μm. The adhesive layer of the adhesive sheet may be protected by various protective films.

[ copper foil with resin ]

The present invention provides a resin-coated copper foil comprising the adhesive layer and a copper foil. Specifically, the resin-coated copper foil is obtained by applying or bonding the adhesive or the film-like adhesive material to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, but is preferably from about 1 μm to about 100. Mu.m, more preferably from about 2 μm to about 38 μm. The copper foil may be one subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust-proofing treatment include plating treatment using a plating solution containing Ni, zn, sn, or the like, and so-called mirror-surface treatment such as chromate treatment. The above-described method can be exemplified as the coating means.

The adhesive layer of the resin-coated copper foil may be an uncured adhesive layer, or may be an adhesive layer partially cured or completely cured by heating. The partially cured adhesive layer is in a state called a so-called B-stage. The thickness of the adhesive layer is not particularly limited, and is preferably about 0.5 μm to about 30 μm. Further, a copper foil may be bonded to the adhesive surface of the resin-coated copper foil to form a resin-coated copper foil having a double-sided copper foil.

[ copper-clad laminate ]

The present invention provides a copper-clad laminate comprising the resin-coated copper foil and a copper foil or an insulating sheet. The Copper-Clad Laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is obtained by bonding the resin-coated copper foil to at least one surface or both surfaces of various known copper foils or insulating sheets under heating. When the resin-attached copper foil is bonded to one surface, a material different from the resin-attached copper foil may be pressure-bonded to the other surface. The number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. The prepreg is a sheet material (JIS C5603) obtained by impregnating a reinforcing material such as glass cloth with a resin and curing the resin to the B stage. As the resin, an insulating resin such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, or aramid resin can be used. The thickness of the prepreg is not particularly limited, and is preferably about 20 μm to about 500 μm. The heating and pressure bonding conditions are not particularly limited, but are preferably about 150 ℃ to about 280 ℃ (more preferably about 170 ℃ to about 240 ℃), and preferably about 0.5MPa to about 20MPa (more preferably about 1MPa to about 8 MPa).

[ printed Wiring Board ]

The present invention provides a printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate. Examples of the patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include a subtractive method and a semi-additive method. The semi-additive method may be exemplified by the following method: after patterning the copper foil surface of the copper-clad laminate with a resist film, electrolytic copper plating is performed to remove the resist, and etching is performed with an alkali solution. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer substrate can be obtained by laminating the same printed wiring board or other known printed wiring boards or printed wiring boards on the printed wiring board as a core base material. In the lamination, the adhesive and other known adhesives than the adhesive may be used in combination. The number of layers in the multilayer substrate is not particularly limited. In addition, each time the layers are stacked, a through hole may be inserted to perform plating treatment on the inside. The line width/pitch ratio of the circuit pattern is not particularly limited, and is usually about 1 μm/1 μm to 100 μm/100 μm. The height of the circuit pattern is not particularly limited, and is usually about 1 μm to about 50 μm.

[ multilayer Wiring Board ]

The present invention provides a multilayer wiring board comprising a printed wiring board (1) or a printed circuit board (1), the adhesive layer, and a printed wiring board (2) or a printed circuit board (2). The printed wiring boards (1) to (2) may be the printed wiring boards, or may be various known printed wiring boards. Similarly, the printed circuit boards (1) to (2) may be the above-described printed circuit boards, or may be various known printed circuit boards. 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 multilayer Wiring Board ]

The present invention provides a method for manufacturing a multilayer wiring board including the following steps 1 and 2.

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

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

In the step 1, the means for bringing the adhesive or the film-like adhesive material into contact with the adherend is not particularly limited, and various known coating means such as a curtain coater, a roll coater, a laminator, a press, and the like can be exemplified.

The heating temperature and the pressure-bonding time in step 2 are not particularly limited, (i) after the adhesive or the film-like adhesive material of the present invention is brought into contact with at least one surface of the core substrate, the adhesive or the film-like adhesive material is heated to about 70 to about 200 ℃ to perform a curing reaction for about 1 to about 10 minutes, and then (ii) in order to perform a curing reaction of the crosslinking agent, the heating treatment is preferably further performed at about 150 to about 250 ℃ for about 10 to about 3 hours. The pressure is also not particularly limited, but is preferably from about 0.5MPa to about 20MPa, and more preferably from about 1MPa to about 8MPa, throughout the steps (i) and (ii).

[ examples ]

The present invention will be specifically described below with reference to examples and comparative examples. However, the description of the preferred embodiments and the examples below are provided for illustrative purposes only 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 and examples specifically described in the present specification, but is defined only by the claims. In the examples and comparative examples, the numerical values of parts,% and the like are based on mass unless otherwise specified.

The softening point was measured using a commercially available measuring apparatus ("ARES-2 KSTD-FCO-STD", manufactured by Rheometric Scientfic).

< production of polyimide >

Production example 1

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube, 300.00g of 4,4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative plastics, japan contract Ltd., hereinafter abbreviated as BisDA.), 1008.30g of cyclohexanone and 201.66g of methylcyclohexane were charged and heated to 60 ℃. Next, 157.89g of 4,4' - (4, 4' -isopropylidenediphenyl-1, 1' -diyldioxy) diphenylamine (trade name "BAPP", manufactured by JFE chemical Co., ltd.; hereinafter abbreviated as "BAPP") and 89.01g of a commercially available dimer diamine (trade name "PRIAMINE1075", manufactured by Kagaku Kogyo Co., ltd.) were added dropwise thereto, and then imidization was performed at 140 ℃ for 12 hours to obtain a solution of polyimide (1-1) (non-volatile matter 31.8%). The polyimide had a molar ratio of acid component/amine component of 1.05 and a softening point of 190 ℃.

Polyimide was obtained in the same manner as in production example 1, except that the compositions of the resin solutions were changed as shown in table 1 for the production examples other than production example 1 and comparative production examples.

Example 1

10.00g of the solution of the polyimide resin (1-1), 0.35g of N, N-diglycidyl-4-glycidyloxyaniline (product name "JeR630" manufactured by Mitsubishi chemical corporation) as a crosslinking agent, and 1.42g of toluene as an organic solvent (3) were mixed and sufficiently stirred to obtain a pressure-sensitive adhesive containing 30.0% of nonvolatile matter.

Adhesives were obtained in the same manner as in example 1, except that the composition of the adhesive was changed as shown in table 2 for examples and comparative examples other than example 1.

[ Table 2]

The organic solvent may contain an organic solvent used in the production of polyimide.

< preparation of adhesive sheet >

The obtained adhesive was coated on a polyimide film (trade name "\ 124591250350 EN", manufactured by Tolydu Pont Co., ltd.; film thickness 12.5 μm; thermal expansion coefficient: 15ppm/℃ C.) by a gap coater so that the thickness after drying was 20 μm, and then dried at 180 ℃ for 3 minutes, thereby obtaining an adhesive sheet.

< production of copper-clad laminate >

The adhesive surface of the obtained adhesive sheet was overlaid on the roughened side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Kogaku corporation, 18 μm thick) to prepare a copper foil with a resin.

Next, the obtained resin-attached copper foil was placed on a support for pressing, and heated and pressed from above through a support made of the same raw material under a pressure of 5MPa, 200 ℃, and 60 minutes, thereby producing a copper-clad laminate.

< tackiness test >

The peel strength (N/cm) of the obtained copper-clad laminate was measured in accordance with JIS C6481 (test method for copper-clad laminates for flexible printed wiring boards). The results are shown in the table.

< Heat resistance test of moisture absorption solder >

The obtained copper-clad laminate was left in a thermostatic chamber with a temperature of 23 ℃ and a rh content of 50% for 4 days, and then floated in a solder bath at 288 ℃ so that the copper foil side was downward, and the presence or absence of foaming was confirmed. The symbol "o" indicates no change in appearance, and "x" indicates that foaming and swelling were observed. The results are shown in the table.

[ Table 3]

Claims

1. A polyimide which is a reaction product of a monomer group comprising an aromatic tetracarboxylic anhydride and a diamine,

in the formula, X represents-O-C₆H₄-C(CH₃)₂-C₆H₄-O-，

in the formula, Y represents-O-C₆H₄-C(CH₃)₂-C₆H₄-O-，

The content of the aromatic diamine in 100 mol% of the diamine is 20 to 80 mol%,

the content of the diaminopolysiloxane in 100 mol% of the diamine is 0 mol%,

the molar ratio of the aromatic tetracarboxylic anhydride to the diamine, i.e., aromatic tetracarboxylic anhydride/diamine, is 1.0 to 1.5,

the weight average molecular weight of the polyimide is 5000-50000.

2. The polyimide according to claim 1, wherein the diamine comprises an alicyclic diamine.

3. An adhesive comprising the polyimide of claim 1 or 2, a crosslinking agent, and an organic solvent.

4. The adhesive according to claim 3, wherein the crosslinking agent is 5 to 900 parts by mass and the organic solvent is 150 to 900 parts by mass based on 100 parts by mass of the polyimide in terms of solid content.

5. A film-like adhesive material comprising a heat-cured product of the adhesive according to claim 3 or 4.

6. An adhesive layer comprising the adhesive of claim 3 or 4 or the film-like adhesive material of claim 5.

7. An adhesive sheet comprising the adhesive layer of claim 6 and a support film.

8. A resin-coated copper foil comprising the adhesive layer of claim 6 and a copper foil.

9. A copper-clad laminate comprising the resin-coated copper foil according to claim 8 and a copper foil or an insulating sheet.

10. A printed wiring board having a circuit pattern on a copper foil side of the copper-clad laminate according to claim 9.

11. A multilayer wiring board, comprising:

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

An adhesive layer as defined in claim 6, and

a printed wiring board (2) or a printed circuit board (2).

12. A method of 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 claim 3 or 4 or the film-like adhesive material according to claim 5 into contact with at least one surface of a printed wiring board (1) or a printed circuit board (1);