JP2018168370A - Polyimide, adhesive, film-like adhesive, adhesion layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, and multilayer wiring board and method for producing the same - Google Patents

Abstract

A polyimide, 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. A reaction product of a monomer group including a diamine containing an aromatic tetracarboxylic acid anhydride and a dimer diamine, a polyimide containing a fluorenylene group in the polymer main chain, and an adhesive containing a polyimide, a crosslinking agent and an organic solvent A film-like adhesive, an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, a printed wiring board, a multilayer wiring board, and a method for producing the same. [Selection figure] None

Description

  The present disclosure relates to a polyimide, an adhesive, a film-like 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.

  Various known adhesives are used to manufacture mobile communication devices such as mobile phones and smartphones, their base station devices, network-related electronic devices such as servers and routers, printed wiring boards included in large computers, etc. Yes.

  The present applicant has stated that "a polyimide adhesive composition comprising a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent obtained by reacting a diamine containing 30 mol% or more of an aromatic tetracarboxylic acid and a specific dimer diamine" (See Patent Document 1).

Japanese Patent No. 5534378

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

  However, Patent Document 1 does not discuss the low dielectric loss tangent. In recent years, there has been a problem that an adhesive having a low dielectric loss tangent has been demanded with further increase in the frequency of electric signals.

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

The present disclosure provides the following items.
(Item 1)
Aromatic tetracarboxylic anhydride,
And a reactant of a monomer group including a diamine including dimer diamine and a fluorenylene group in the polymer main chain.
Containing polyimide.
(Item 2)
The diamine is a fluorene skeleton-containing diamine
(In the formula, either R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either R ³ or R ⁴ One represents a group having an amino group, and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom.)
The polyimide according to the above item, comprising:
(Item 3)
The polyimide according to any one of the above items, wherein the diamine comprises diaminopolysiloxane.
(Item 4)
The polyimide according to any one of the above items, wherein the molar ratio of the aromatic tetracarboxylic acid anhydride to the diamine [aromatic tetracarboxylic acid anhydride / diamine] is 1.0 to 1.5.
(Item 5)
The adhesive agent containing the polyimide of any one of the said item, a crosslinking agent, and an organic solvent.
(Item 6)
The adhesive according to the above item, wherein the crosslinking agent is at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides, and cyanate esters.
(Item 7)
The epoxide has the following structure:
(In the formula, Y represents a phenylene group or a cyclohexylene group.)
The adhesive according to the above item.
(Item 8)
The adhesive according to any one of the above items, comprising 5 to 900 parts by mass of the crosslinking agent and 150 to 900 parts by mass of the organic solvent with respect to 100 parts by mass of the polyimide (in terms of solid content).
(Item 9)
A film adhesive comprising the heat-cured product of the adhesive according to any one of the above items.
(Item 10)
The contact bonding layer containing the adhesive agent of any one of the said item, or the film adhesive of the said item.
(Item 11)
The adhesive sheet containing the contact bonding film and support film as described in the said item.
(Item 12)
A copper foil with a resin, including the adhesive layer and the copper foil described in the above item.
(Item 13)
The copper clad laminated board containing the copper foil with resin as described in the said item, and copper foil.
(Item 14)
The copper clad laminated board containing the copper foil with resin as described in the said item, and an insulating sheet.
(Item 15)
The printed wiring board which has a circuit pattern in the copper foil surface of the copper clad laminated board of any one of the said items.
(Item 16)
Printed wiring board (1) or printed circuit board (1),
Including the adhesive layer described in the above items, and the printed wiring board (2) or the printed circuit board (2),
Multilayer wiring board.
(Item 17)
A method for producing a multilayer wiring board, comprising the following steps 1 and 2.
Step 1: Adhesion by bringing the adhesive described in any one of the above items or the film-like adhesive described in the above items into contact with at least one surface of the printed wiring board (1) or the printed circuit board (1). Process step 2 for producing a substrate with a layer: a step of laminating a printed wiring board (2) or a printed circuit board (2) on the substrate with an adhesive layer and press-bonding the substrate with heat and pressure

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

  By using the polyimide of the present invention, an adhesive having a low dielectric loss tangent can be provided. The said adhesive agent can be used suitably with respect to high frequency electronic components, such as highly functional mobile terminals, such as a printed wiring board.

  Throughout the present disclosure, ranges of numerical values such as each physical property value and content can be set as appropriate (for example, selected from the upper limit and lower limit values described in the following items). Specifically, for the numerical value α, the upper limit of the numerical value α is exemplified as A1, A2, A3, etc., and the lower limit of the numerical value α is exemplified as B1, B2, B3, etc., the range of the numerical value α is A1 or less, A2 or less, A3 or less, B1 or more, B2 or more, B3 or more, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 Etc. are exemplified.

[Polyimide]
The present disclosure provides an aromatic tetracarboxylic anhydride,
And a reactant of a monomer group including a diamine including dimer diamine and a fluorenylene group in the polymer main chain.
A polyimide is provided.

  In the present disclosure, “containing a fluorenylene group in the polymer main chain” means that the longest chain constituting the polymer contains a fluorenylene group.

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

(Fluorene skeleton-containing tetracarboxylic anhydride)
In one embodiment, the fluorene skeleton-containing tetracarboxylic acid anhydride has the following general formula:
(In the formula, either R ¹ or R ² represents a group having an acid anhydride group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and R ³ or R ⁴ Either one represents a group having an acid anhydride group and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, or R ¹ and R ² and / or R ³ and R ⁴ are Represents a group which together forms an acid anhydride group.

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

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

  Examples of the alkyl group include a linear alkyl group, a branched alkyl group, and a cycloalkyl group.

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

  Linear alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl. Examples are groups.

  Examples of the branched alkyl group include isopropyl group, isobutyl group, isopentyl group, isohexyl group, and isodecyl group.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like. In the cycloalkyl group, one or more hydrogen atoms on each ring may be substituted with a linear alkyl group (the group exemplified above) or a branched alkyl group (the group exemplified above).

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

  The fluorene skeleton-containing tetracarboxylic anhydride is 9,9′-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride, 9,9′-bis (3,4-dicarboxyphenoxy). ) Fluoric acid dianhydride and the like are exemplified.

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

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

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

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

(Symmetric aromatic tetracarboxylic anhydride)
In the present disclosure, “symmetric aromatic tetracarboxylic anhydride” means an aromatic tetracarboxylic anhydride having a symmetry axis (eg, C2 symmetry axis) in the molecule. Symmetric aromatic tetracarboxylic anhydrides have the general formula
(In the formula, X represents 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) represents a -CH 2 -OCO-, p is an integer of 1-20.)
What is shown by etc. is illustrated.

  Symmetric aromatic tetracarboxylic acid anhydrides represented by the above general formula are 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid dianhydride. Anhydride, 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-dicarboxyphenyl) propane dianhydride, 2,2′-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Anhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5 Examples thereof include 8-naphthalene tetracarboxylic acid anhydride and 2,3,6,7-naphthalene tetracarboxylic acid anhydride.

  Among the above symmetric aromatic tetracarboxylic acid anhydrides, 3,3 ′, 4,4′-benzophenone tetra from the viewpoints of compatibility of aromatic tetracarboxylic acid anhydride and diamine, room temperature adhesion, heat resistance adhesion, and the like. Selected from the group consisting of carboxylic dianhydride, 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride, and 4,4′-oxydiphthalic anhydride. At least one is preferred.

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

  The upper limit of the content of the symmetric aromatic tetracarboxylic acid anhydride in 100% by mass of the aromatic tetracarboxylic acid anhydride is 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10% by mass. Etc., and the lower limit is exemplified by 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0% by mass and the like. In one embodiment, about 0-100 mass% is preferable and, as for content of the symmetrical aromatic tetracarboxylic anhydride in 100 mass% of aromatic tetracarboxylic 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%, and the lower limit is 70. , 60, 50, 40, 30, 20, 10, 5, 0 mol% and the like. 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%.

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

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

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

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

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

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

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

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

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

(Dimeramine)
In the present disclosure, dimer diamine is one obtained by substituting all the carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acid such as oleic acid, with primary amino groups (see JP-A-9-12712, etc.) Various known materials can be used without particular limitation. Hereinafter, non-limiting general formulas of dimeramine are shown (in each formula, m + n = 6 to 17 is preferable, p + q = 8 to 19 is preferable, and a broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. means).

  Commercial products of Dimeramine are Versamine 551 (manufactured by Cognics Japan), Versamine 552 (manufactured by Cognics Japan; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all manufactured by Croda Japan Co., Ltd.) And the like.

  Examples of the upper limit of the content of the dimer diamine component in 100 mol% of diamine include 100, 90, 80, 70, 60, 50, 40, 30, 25 mol%, and the lower limit is 90, 80, 75, 70. , 60, 50, 40, 30, 25, 20 mol% and the like. In one embodiment, the content of the dimer diamine component in 100 mol% of the diamine is preferably about 20 to 100 mol% from the viewpoints of flexibility, adhesion, and solvent solubility.

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

  Examples of the upper limit of the content of dimer diamine in 100 mol% of the monomer group include 50, 40, 30, 20, 10, 8 mol%, and the lower limit is 40, 30, 20, 10, 8, 5 mol%. Etc. are exemplified. In one embodiment, as for content of dimer diamine in 100 mol% of monomer groups, 5-50 mol% is preferred.

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

(Fluorene skeleton-containing diamine)
In one embodiment, the fluorene skeleton-containing diamine has the following general formula:
(In the formula, either R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either R ³ or R ⁴ One represents a group having an amino group, and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom.

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

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

  Examples of the monocyclic aryl group include a phenyl group, a tolyl group, and a mesityl group. Examples of the fused ring aryl group include a naphthyl group.

  Fluorene skeleton-containing diamines are 9,9′-bis (aminophenyl) fluorene, 9,9′-bis (4-amino-3-methylphenyl) fluorene, 9,9′-bis (4-amino-3-fluoro). Phenyl) fluorene, 9,9′-bis (4-amino-3-hydroxyphenyl) fluorene, 9,9′-bis (4-methyl-3-aminophenyl) fluorene, 9,9′-bis (4-fluoro) Examples include -3-aminophenyl) fluorene, 9,9'-bis (4-hydroxy-3-aminophenyl) fluorene, 9,9'-bis [4- (4-aminophenoxy) phenyl] fluorene, and the like.

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

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

  Examples of the upper limit of the content of the fluorene skeleton-containing diamine in 100 mol% of the monomer group include 50, 40, 30, 20, 10, 5 mol%, and the lower limit is 40, 30, 20, 10, 5, 0. A mol% etc. are illustrated. In one embodiment, the content of the fluorene skeleton-containing diamine in 100 mol% of the monomer group is preferably 0 to 50 mol%.

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

  The upper limit of the ratio of the amount of fluorene skeleton-containing diamine and the amount of dimeramine amine (fluorene skeleton-containing diamine / dimeramine) is 4.00, 3.00, 2.00, 1.00, 0.50, etc. The lower limit is exemplified as 4.00, 3.00, 2.00, 1.00, 0.50, 0.25, etc. In one embodiment, the ratio of the amount of the fluorene skeleton-containing diamine to the amount of the dimeramine amine (fluorene skeleton-containing diamine / dimeramine) is 0.25 to 4 from the viewpoint of improving flexibility, adhesiveness, and dielectric properties. About 0.00 is preferable.

(Diaminopolysiloxane)
Diaminopolysiloxane includes 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 and the like are exemplified.

  The upper limit of the content of diaminopolysiloxane in 100 mol% of the diamine is exemplified as 5, 4, 3, 2, 1 mol%, and the lower limit is exemplified as 4, 3, 2, 1, 0 mol%, etc. The 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.

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

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

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

(Other diamines)
In one embodiment, the monomer group may include a diamine other than the above (also referred to as other diamine). Other diamines include cycloaliphatic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane. , Bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminoditrifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, aminophenoxyphenyl sulfide, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, amino Phenoxyphenylpropa 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′-spirobiindane, bis (aminoalkyl) ether, bis (aminoalkoxyalkyl) ether, bis (aminoalkoxy) alkane, bis [(aminoalco Xyl) alkoxy] alkane, (poly) ethylene glycol bis (aminoalkyl) ether, bis (aminoaryloxy) pyridine, diaminoalkylene and the like.

  The alicyclic diamines are diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4). , 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane and the like. .

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

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

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

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

  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, 4,4′-diaminobenzophenone, and 3,4′-diaminobenzophenone.

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

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

  Diaminophenyl hexafluoropropane 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 and the like The

  Diaminophenylphenylethane is 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1 -(4-aminophenyl) -1-phenylethane and the like are exemplified.

  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 and the like are exemplified.

  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 and the like are exemplified.

  Bisaminodimethylbenzylbenzene is 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis. Examples include (3-amino-α, α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene.

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

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

  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 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.

  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 and the like.

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

  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.

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

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

Bis [amino-α, α-dimethylbenzylphenoxy] diphenyl sulfone is
Examples include 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone.

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

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

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

  6,6′-bis (aminoaryloxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane is obtained as 6,6′-bis (3-aminophenoxy) -3,3. 3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindane, etc. Illustrated.

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

  Bis (aminoalkoxyalkyl) ethers include bis [2- (aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl]. An ether etc. are illustrated.

  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.

  (Poly) ethylene glycol bis (aminoalkyl) ether includes ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, etc. Is exemplified.

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

  Diaminoalkylene is ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Examples include 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like.

  In one embodiment, the content of other diamines in the diamine is exemplified as 5, 4, 1, 0.9, 0.5, less than 0.1 mol%, or about 0 mol%.

  In one embodiment, the content of other diamines in the diamine is exemplified as 5, 4, 1, 0.9, 0.5, less than 0.1% by mass, or about 0% by mass.

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

  In one embodiment, the content of other diamines in the monomer group is exemplified as 5, 4, 1, 0.9, 0.5, less than 0.1% by mass, or about 0% by mass.

  The upper limit of the diamine content in 100 mol% of the monomer group is exemplified by 50, 45, 40, 35, 30 mol%, and the lower limit is exemplified by 45, 40, 35, 30, 25 mol%, etc. . In one embodiment, the diamine content in 100 mol% of the monomer group is preferably about 25 to 50 mol%.

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

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

  The upper limit of the mass ratio of the aromatic tetracarboxylic acid anhydride to the diamine [aromatic tetracarboxylic acid anhydride / diamine] is 1.5, 1.4, 1.2, 1.0, 0.9, 0.00. 7 and 0.6 are exemplified, and the lower limit is exemplified by 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5 and the like. In one embodiment, the mass ratio of the aromatic tetracarboxylic acid anhydride to the diamine [aromatic tetracarboxylic acid anhydride / diamine] is preferably 0.5 to 1.5.

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

  In one embodiment, examples of the content of other monomers in the monomer group include 5, 4, 1, 0.9, 0.5, less than 0.1 mol%, and about 0 mol%.

  In one embodiment, the content of other monomers in the monomer group is exemplified as 5, 4, 1, 0.9, 0.5, less than 0.1% by mass, or about 0% by mass.

<Physical properties of polyimide>
Examples of the upper limit of the weight average molecular weight of the polyimide include 50000, 40000, 30000, 20000, 10000, 7500, and 5500, and examples of the lower limit include 45000, 40000, 30000, 20000, 10000, 7500, and 5000. In one embodiment, the weight average molecular weight of the polyimide is preferably 5000 to 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, 10,000, 7500, 5000, 3000, etc., and the lower limit is exemplified by 35000, 30000, 20000, 10000, 7500, 5000, 3000, 2000, etc. The 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.

  A weight average molecular weight and a number average molecular weight can be calculated | required as a polystyrene conversion value measured, for example by gel permeation chromatography (GPC).

  Examples of the upper limit of the softening point of the polyimide include 220, 200, 150, 100, 50, and 25 ° C., and examples of the lower limit include 210, 200, 150, 100, 50, 25, and 20 ° C. In one embodiment, the softening point of the polyimide is preferably 20 to 220 ° C. from the viewpoints of workability, heat resistance, and solvent solubility.

  The softening point can be obtained using a commercially available measuring instrument (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientific).

<Production method of polyimide>
The polyimide can be produced by various known methods. The method for producing polyimide is preferably a monomer group containing an aromatic tetracarboxylic acid anhydride and a diamine containing dimer diamine and the like, preferably at a temperature of about 60 to 120 ° C., more preferably about 80 to 100 ° C., preferably 0. About 1 to 2 hours, more preferably about 0.1 to 0.5 hours, a step of polyaddition reaction to obtain a polyaddition product, the obtained polyaddition product is preferably about 80 to 250 ° C., more preferably Is exemplified by a method including a step of imidization reaction, that is, dehydration ring closure reaction, at a temperature of about 100 to 200 ° C., preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours.

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

  The imide ring closure rate of the polyimide is not particularly limited. Here, “imide ring closure rate” means the content of cyclic imide bonds in polyimide, and can be determined by various spectroscopic means such as NMR and IR analysis. About 70% or more is preferable and about 85-100% is more preferable from the viewpoint from which normal temperature adhesiveness and heat-resistant adhesiveness become favorable.

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

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

<Crosslinking agent>
Any known crosslinking agent can be used without particular limitation as long as it functions as a crosslinking agent for polyimide. A crosslinking agent may be used alone or in combination of two or more. The crosslinking agent is preferably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides, and cyanate esters.

(Epoxide)
Epoxides include phenol novolac epoxides, cresol novolac epoxides, bisphenol A epoxides, bisphenol F epoxides, bisphenol S epoxides, hydrogenated bisphenol A epoxides, hydrogenated bisphenol F epoxides, stilbene epoxides, and triazine skeleton-containing epoxides. Fluorene skeleton-containing epoxide, linear aliphatic epoxide, cycloaliphatic epoxide, glycidylamine-type epoxide, triphenolmethane-type epoxide, alkyl-modified triphenolmethane-type epoxide, biphenyl-type epoxide, dicyclopentadiene skeleton-containing epoxide, naphthalene skeleton-containing Epoxide, aryl alkylene type epoxide, tetraglycidyl xylylenediamine, dimer acid modification of the above epoxide Dimer acid-modified epoxide, and dimer acid diglycidyl ester is exemplified it is. In addition, commercially available products of epoxide include “jER828”, “jER834”, “jER807” manufactured by Mitsubishi Chemical Corporation, “ST-3000” manufactured by Nippon Steel Chemical Co., Ltd., manufactured by Daicel Chemical Industries, Ltd. “Celoxide 2021P”, “YD-172-X75” manufactured by Nippon Steel Chemical Co., Ltd., “TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd. and the like are exemplified. Among these, at least one selected from the group consisting of bisphenol A-type epoxide, bisphenol F-type epoxide, hydrogenated bisphenol A-type epoxide and alicyclic epoxide from the viewpoint of the balance of heat-resistant adhesiveness, moisture-absorbing solder heat resistance and low dielectric properties. Species are preferred.

Especially tetraglycidyldiamine of the following structure
(In the formula, Y represents a phenylene group or a cyclohexylene group.)
Has good compatibility with the polyimide. In addition, when this is used, it is easy to reduce the elastic modulus of the adhesive layer, and the heat resistant adhesiveness 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. Curing agents for epoxides are succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride Acid anhydride curing agents such as methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine (product) Name “Lonacure M- EA ”,“ Lonacure M-DETDA ”, etc., all manufactured by Lonza Japan Co., Ltd.), amine-based curing agents such as aliphatic amines; Phenolic hydroxyl group-containing phosphazenes (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd.), etc., phenolic curing agents, cyclic phosphazene compounds, rosin crosslinking agents such as maleic acid-modified rosin and hydrides thereof, etc. Illustrated. Of these, phenol-based curing agents, particularly phenolic hydroxyl group-containing phosphazene-based curing agents are preferred. Although the usage-amount of a hardening | curing agent is not restrict | limited in particular, When the solid content of the said adhesive agent is 100 mass%, about 0.1-120 mass% is preferable and about 10-40 mass% is more preferable.

  When an epoxide and a curing agent for epoxide are used in combination as a crosslinking agent, a reaction catalyst can be further used in combination. The reaction catalyst may be used alone or in combination of two or more. The reaction catalyst is a tertiary amine such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; organics such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Phosphine; tetraphenylboron such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate Like it is exemplified. The amount of the reaction catalyst used is not particularly limited, but is preferably about 0.01 to 5% by mass when the solid content of the adhesive is 100% by mass.

(Benzoxazine)
Benzoxazine is 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6- (1-methylethylidene) bis (3, 4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like. Note that a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to nitrogen of the oxazine ring. Commercially available benzoxazines include “Benzoxazine Fa type” and “Benzoxazine Pd type” manufactured by Shikoku Kasei Kogyo Co., Ltd., and “RLV-100” manufactured by Air Water Co., Ltd. Etc. are exemplified.

(Bismaleimide)
The bismaleimide is 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4- Examples include methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, etc. Is done. Moreover, the commercial item of bismaleimide is exemplified by “BAF-BMI” manufactured by JFE Chemical Co., Ltd.

(Cyanate ester)
Cyanate ester is 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate Ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis (4-cyanatophenyl) ) Ethane, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane, and the like. Examples of the commercially available cyanate ester include “PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)”.

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

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

<Organic solvent>
As the organic solvent, various known organic solvents can be used alone or in combination of two or more. Organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglyme and methyldiglyme, and alicyclic rings such as cyclohexanone and methylcyclohexane. Illustrative examples include formula solvents, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol, and aromatic solvents such as toluene.

  Moreover, the content of the organic solvent in the adhesive is not particularly limited, but an amount in which the solid content is 10 to 60% by mass with respect to 100% by mass of the adhesive is preferable.

  In the adhesive, the upper limit of the content of the organic solvent with respect to 100 parts by mass of the polyimide (in terms of solid content) is exemplified by 900, 800, 700, 600, 500, 400, 300, 200 parts by mass, etc. Examples are 800, 700, 600, 500, 400, 300, 200, 150 parts by mass. In one embodiment, the content of the organic solvent in the adhesive with respect to 100 parts by mass of the polyimide (in terms of solid content) is preferably 150 to 900 parts by mass.

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

(Phosphorus flame retardant (phosphorus-containing flame retardant))
Examples of the phosphoric flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain a phenolic hydroxyl group. Among the phosphazene derivatives, cyclic phosphazene derivatives are 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 Ravitor FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

(Inorganic filler)
In one embodiment, examples of the inorganic filler include silica filler, phosphorus filler, fluorine filler, inorganic ion exchanger filler, and the like. Examples of commercially available products include FB-3SDC manufactured by Denka Co., Ltd., Exolit OP935 manufactured by Clariant Chemicals Co., Ltd., KTL-500F manufactured by Kitamura Co., Ltd., IXE manufactured by Toagosei Co., Ltd., and the like.

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

<Reactive alkoxysilyl compound>
In one embodiment, the adhesive further includes a general formula: Z—Si (R ¹ ) _a (OR ² ) _3-a (wherein Z includes a group containing a functional group that reacts with an acid anhydride group). , R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2.) Compounds are included. With the reactive alkoxysilyl compound, the melt viscosity can be adjusted while maintaining the low dielectric properties of the adhesive layer comprising the adhesive of the present invention. As a result, it is possible to suppress bleeding of the cured layer that occurs from the edge of the base material while enhancing the interfacial adhesion (so-called anchor effect) between the adhesive layer and the base material.

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

  The compound in which Z contains an amino group includes N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. , 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane and the like. Examples of the compound in which Z contains an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycol. Examples are sidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of compounds in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. . Among these, a compound in which Z contains an amino group is preferable because the reactivity and the effect of flow control are good.

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

  The adhesive may contain an additive that is not any of the polyimide, crosslinking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound.

  Additives include ring-opening esterification reaction catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatments. Examples include agents, viscosity modifiers, silica fillers and fluorine fillers.

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

  In another embodiment, the content of the additive is exemplified by less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, etc. with respect to 100 parts by weight of the polyimide (in terms of solid content). Is done.

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

[Film adhesive]
This indication provides the film adhesive containing the heat hardening thing of the above-mentioned adhesives. The method for producing a film-like adhesive includes a step of applying the above adhesive to a suitable support, a step of curing by heating and volatilizing an organic solvent, a method of peeling from the support, and the like. Illustrated. The thickness of the adhesive is not particularly limited, but is preferably about 3 to 40 μm. Examples of the support are as follows.

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

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

  The support film is exemplified by a plastic film. Plastics are polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, phenol, phthalic acid, Examples thereof include aromatic polyester resins obtained from hydroxynaphthoic acid and the like and parahydroxybenzoic acid (so-called liquid crystal polymer; “Bexter” manufactured by Kuraray Co., Ltd.) and the like.

  Moreover, the said coating means can be employ | adopted when apply | coating the said adhesive agent to this support film. Although the thickness of a coating layer is not specifically limited, About 1-100 micrometers is preferable after drying, and about 3-50 micrometers is more preferable. The adhesive layer of the adhesive sheet may be protected with various protective films.

[Copper foil with resin]
The present disclosure provides a resin-coated copper foil including the adhesive layer and the copper foil. Specifically, the copper foil with resin is obtained by applying or bonding the adhesive or the film adhesive to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, and is preferably about 1 to 100 μm, and more preferably about 2 to 38 μm. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust prevention treatment include so-called mirror finishing treatment such as plating treatment using a plating solution containing Ni, Zn, Sn and the like, and chromate treatment. Moreover, the above-mentioned method is illustrated as a coating means.

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

[Copper laminate]
The present disclosure provides a copper clad laminate including the resin-coated copper foil and the copper foil or the 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 bonding to one side, you may press-bond the thing different from the said resin-coated copper foil to the other side. Moreover, the number of the resin-coated copper foil and the insulating sheet in the copper-clad laminate is not particularly limited.

  In one embodiment, the insulating sheet is preferably a prepreg. A prepreg is a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (JIS C 5603). As the resin, an insulating resin such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, and aramid resin is used. The thickness of the prepreg is not particularly limited, and is preferably about 20 to 500 μm. The heating and pressure bonding conditions are not particularly limited, and are preferably about 150 to 280 ° C (more preferably about 170 ° C to 240 ° C), and preferably about 0.5 to 20 MPa (more preferably about 1 to 8 MPa).

[Printed wiring board]
The present disclosure provides a printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate. 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. Examples of the semi-additive method include a method of patterning a copper foil surface of a copper-clad laminate with a resist film, performing electrolytic copper plating, removing the resist, and etching with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Moreover, a multilayer substrate can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or other known printed wiring boards or printed circuit boards thereon. When laminating, the above adhesive and other known adhesives other than the above adhesive can be used in combination. Further, the number of stacked layers in the multilayer substrate is not particularly limited. Moreover, a via hole may be inserted and the inside may be plated each time it is laminated. The line / space ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is not particularly limited, but is preferably about 1 to 50 μm.

[Multilayer wiring board]
The present disclosure provides a multilayer wiring board including the printed wiring board (1) or the printed circuit board (1), the adhesive layer, and the printed wiring board (2) or the printed circuit board (2). The printed wiring boards (1) to (2) may be the printed wiring boards or various known ones. Similarly, the printed circuit boards (1) to (2) may be the above-described printed circuit boards, or various known ones. The printed wiring board (1) and the printed wiring board (2) may be the same or different. Similarly, the printed circuit board (1) and the printed circuit board (2) may be the same or different.

[Manufacturing method of multilayer wiring board]
The present disclosure includes the following steps 1 and 2
Step 1: Step of manufacturing a substrate with an adhesive layer by bringing the adhesive or the film-like adhesive into contact with at least one surface of the printed wiring board (1) or the printed circuit board (1). Provided is a method for producing a multilayer wiring board, comprising a step of laminating a printed wiring board (2) or a printed circuit board (2) on a layered base material and press-bonding the substrate with heating and pressure.

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

  In step 1, the means for bringing the adhesive or film adhesive into contact with the adherend is not particularly limited, and various known coating means, curtain coaters, roll coaters, laminators, presses and the like are exemplified.

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

  Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the description in the above preferred embodiment and the following examples are provided for illustrative purposes only and are not intended to limit the present invention. Accordingly, the scope of the present invention is not limited to the embodiments or examples specifically described in the present specification, but is limited only by the scope of the claims. Moreover, in each Example and a comparative example, unless there is particular description, numerical values, such as a part and%, are based on mass.

<Manufacture of polyimide>
Production Example 1
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction tube, 9,9′-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride (trade name “ BPF-PA ", manufactured by JFE Chemical Co., Ltd., hereinafter abbreviated as BPF-PA.) 290.00 g, cyclohexanone 980.20 g, and methylcyclohexane 196.04 g were charged and heated to 60 ° C. Next, 236.60 g of commercially available dimer diamine (trade name “PRIAMINE 1075”, manufactured by Croda Japan Co., Ltd.) was added dropwise, and then an imidization reaction was performed at 140 ° C. for 12 hours to obtain a solution of polyimide (1-1). (Nonvolatile content 31.6%) was obtained. The molar ratio of acid component / amine component of the polyimide was 1.03.

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

BPAF: 9,9′-bis (3,4-dicarboxyphenoxy) fluorenic dianhydride (trade name “BPAF”, manufactured by JFE Chemical Co., Ltd.)
BAFL: 9,9′-bis (aminophenyl) fluorene (trade name “BAFL”, manufactured by JFE Chemical Co., Ltd.)
BisDA-1000: 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride (trade name “BisDA-1000”, manufactured by SABIC Innovative Plastics Japan LLC.)
1,3-BAC: 1,3-bis (aminomethyl) cyclohexane (Mitsubishi Gas Chemical Co., Ltd.)

Example 1
10.00 g of polyimide resin (1-1) solution, 0.35 g of N, N-diglycidyl-4-glycidyloxyaniline (trade name “jER630”, manufactured by Mitsubishi Chemical Corporation) as a crosslinking agent, and toluene 1 as an organic solvent .35 g was mixed and stirred well to obtain an adhesive having a nonvolatile content of 30.0%.

  Examples and Comparative Examples other than Example 1 were performed in the same manner as in Example 1 except that the composition of the adhesive was changed as described in Table 2 to obtain an adhesive.

  In addition, the organic solvent used when manufacturing a polyimide may also be included in an organic solvent.

<Preparation of adhesive sheet>
The obtained adhesive is applied to a polyimide film (trade name “Kapton 50EN”, manufactured by Toray Deyupon Co., Ltd .; film thickness 12.5 μm; thermal expansion coefficient: 15 ppm / ° C.) so that the thickness after drying becomes 20 μm. After apply | coating with a gap coater, the adhesive sheet was obtained by making it dry at 180 degreeC for 3 minute (s).

<Preparation of copper-clad laminate>
The adhesive surface of the obtained adhesive sheet was made on a roughened side of a commercially available electrolytic copper foil (trade name “F2-WS”, manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thickness) to produce a resin-coated copper foil. .

  Next, the obtained copper foil with resin is placed on a support for pressing, and is heated and pressed under pressure of 5 MPa, 200 ° C. and 60 minutes through a support obtained from the same material from above. A tension laminate was produced.

<Adhesion test>
About the obtained copper clad laminated board, peeling strength (N / cm) was measured according to JISC6481 (copper clad laminated board test method for flexible printed wiring boards). The results are shown in the table.

<Measurement of dielectric constant and dielectric loss tangent>
About 7 g of each of the adhesives of Examples and Comparative Examples was poured into a fluororesin PFA flat plate (diameter 75 mm, manufactured by Mutual Riken Glass Co., Ltd.), 30 ° C. × 10 hours, 70 ° C. × 10 hours, 100 ° C. × 6 hours. By curing at 120 ° C. for 6 hours, 150 ° C. for 6 hours, and 180 ° C. for 12 hours, a dielectric constant measurement resin having a film thickness of about 300 μm and a cured product sample were obtained.

  Next, the dielectric constant and dielectric loss tangent at 10 GHz of the obtained dielectric constant measurement resin and cured product sample are measured in accordance with JIS C2565 using a commercially available dielectric constant measurement device (cavity resonator type, manufactured by AET). It was measured. The results are shown in the table.

Claims (14)

Aromatic tetracarboxylic anhydride,
And a reactant of a monomer group including a diamine including dimer diamine and a fluorenylene group in the polymer main chain.
Containing polyimide. The diamine is a fluorene skeleton-containing diamine
(In the formula, either R ¹ or R ² represents a group having an amino group, the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either R ³ or R ⁴ One represents a group having an amino group, and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom.)
The polyimide according to claim 1, comprising: The polyimide according to claim 1 or 2, wherein the diamine contains diaminopolysiloxane. The molar ratio [aromatic tetracarboxylic anhydride / diamine] between the aromatic tetracarboxylic anhydride and the diamine is 1.0 to 1.5, according to any one of claims 1 to 3. Polyimide. The adhesive agent containing the polyimide of any one of Claims 1-4, a crosslinking agent, and an organic solvent. The adhesive according to claim 5, comprising 5 to 900 parts by mass of the cross-linking agent and 150 to 900 parts by mass of the organic solvent with respect to 100 parts by mass of the polyimide (in terms of solid content). A film adhesive comprising the heat-cured product of the adhesive according to claim 5 or 6. An adhesive layer comprising the adhesive according to claim 5 or 6 or the film-like adhesive according to claim 7. An adhesive sheet comprising the adhesive layer according to claim 8 and a support film. A copper foil with a resin, comprising the adhesive layer according to claim 8 and a copper foil. The copper clad laminated board containing the copper foil with resin of Claim 10, and copper foil or an insulating sheet. The printed wiring board which has a circuit pattern in the copper foil surface of the copper clad laminated board of Claim 11. Printed wiring board (1) or printed circuit board (1),
The adhesive layer according to claim 8, and a printed wiring board (2) or a printed circuit board (2),
Multilayer wiring board. A method for producing a multilayer wiring board, comprising the following steps 1 and 2.
Step 1: Adhesive layer by bringing the adhesive according to claim 5 or 6 or the film-like adhesive according to claim 7 into contact with at least one surface of the printed wiring board (1) or the printed circuit board (1). Process step 2 for producing a substrate with adhesion: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the substrate with an adhesive layer and press-bonding it under heat and pressure.