KR20180110632A - Polyimide, adhesive, film-shaped adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed wiring board, and multi-layer board and manufacturing method thereof - Google Patents

Abstract

Provided are polyimide, an adhesive, a film-like adhesive, an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper clad laminate, a printed wiring board and a multilayer wiring board, and a production method thereof. More specifically, provided is polyimide which is a reaction product of a monomer group composed of aromatic tetracarboxylic acid anhydride and diamine having dimeric diamine, while containing a fluorenylene group on a polymer main chain. Moreover, provided are an adhesive containing 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 and a multilayer wiring board, and a production method thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide, an adhesive, a film-like adhesive, an adhesive layer, an adhesive sheet, a copper foil with a resin, a copper clad laminate, a printed wiring board and a multilayer wiring board, FOIL WITH RESIN, COPPER CLAD LAMINATE, PRINTED WIRING BOARD, AND MULTI-LAYER BOARD AND MANUFACTURING METHOD THEREOF}

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

Various known adhesives have been used to manufacture mobile communication devices such as cellular phones and smart phones, network-related electronic devices such as base station devices, server and routers, and printed circuit boards included in large-sized computers and the like.

The present applicant has proposed a polyimide-based adhesive composition comprising a polyimide resin, a thermosetting resin, a flame retardant, and an organic solvent, which is obtained by reacting aromatic tetracarboxylic acids and a diamine containing at least 30 mol% of a specific diamine (See Patent Document 1).

Japanese Patent No. 5534378

In recent years, in the network related electronic devices, it is necessary to transfer and process a large amount of information with low loss and high speed, and electric signals handled by the printed wiring boards of these products are also being made higher in frequency. Since the high-frequency electric signal is easy to attenuate, it is necessary to further reduce the transmission loss in the printed wiring board. Therefore, adhesives commonly used in printed wiring boards are required to have low dielectric constant and low dielectric constant tangent (also referred to as low dielectric properties).

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

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

The following items are provided by this disclosure.

(Item 1)

Aromatic tetracarboxylic acid anhydrides,

And diamines including dimer diamines

, And is a reactant of a monomer group containing a fluorenylene group

≪ / RTI >

(Item 2)

When the diamine is a fluorene skeleton-containing diamine

(Wherein either one of R ¹ and R ² represents a group having an amino group and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either one of R ³ or R ⁴ has an amino group; And one of them represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom)

≪ / RTI >

(Item 3)

The polyimide according to any one of the preceding items, wherein the diamine comprises a diaminopolysiloxane.

(Item 4)

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)

An adhesive comprising the polyimide, the cross-linking agent and the organic solvent according to any one of the above items.

(Item 6)

Wherein the crosslinking agent is at least one selected from the group consisting of epoxide, benzoxazine, bismaleimide and cyanate ester.

(Item 7)

Wherein the epoxide is an epoxide of the following structure

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

≪ / RTI >

(Item 8)

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

(Item 9)

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

(Item 10)

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

(Item 11)

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

(Item 12)

A resin-coated copper foil comprising the adhesive layer and the copper foil described in the item.

(Item 13)

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

(Item 14)

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

(Item 15)

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

(Item 16)

The printed wiring board 1 or the printed circuit board 1,

The adhesive layer described in the item

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

(Item 17)

A process for producing a multilayer wiring board comprising the following steps 1 and 2.

Step 1: A step of producing an adhesive layer-adhered base material by bringing the adhesive described in any one of the above items or the film-like adhesive material described in the item into contact with at least one surface of the printed wiring board 1 or the printed circuit board 1

Step 2: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the substrate with the adhesive layer, and pressing and bonding under heating and pressing

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

By using the polyimide of the present invention, an adhesive having a low dielectric tangent can be provided. The adhesive can be suitably used for a high-frequency electronic component such as a high-performance mobile terminal such as a printed wiring board.

Throughout this disclosure, ranges of numerical values such as the respective properties, contents, etc. can be appropriately set (for example, by selecting from values of upper and lower limits described in the following items). Specifically, when the upper limit of the value alpha is A1, A2, A3, and the like, and the lower limit of the value alpha is B1, B2, B3 or the like is exemplified, the range of the value alpha is A1 or less, B2, A2, B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, and the like are exemplified .

[Polyimide]

The present disclosure relates to aromatic tetracarboxylic acid anhydrides,

And diamines including dimer diamines

, And is a reactant of a monomer group containing a fluorenylene group

≪ / RTI >

In the present disclosure, " the fluoreneylene group in the polymer main chain " means that the fluoreneylene group is contained in the longest chain constituting the polymer.

≪ Aromatic tetracarboxylic acid anhydride >

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

(Fluorene skeleton-containing tetracarboxylic acid anhydride)

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

(Wherein either one of R ¹ and R ² 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, and either R ³ or R ⁴ has an acid anhydride group , And the other one represents a hydrogen atom, a hydroxyl group, an alkyl group, or a halogen atom, or R ¹ and R ² and / or R ³ and R ⁴ are taken together to form an acid anhydride group.

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

When R ¹ and R ² and / or R ³ and R ⁴ are combined to form an acid anhydride group, examples of the formed acid anhydride group include 3,4-dicarboxyphenyl group and the like.

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

The number of carbon atoms of the alkyl group is not particularly limited and the upper limit is 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, In one embodiment, the number of carbon atoms of the alkyl group is preferably about 1 to 30, more preferably about 1 to 20, even more preferably about 1 to 16, and particularly preferably about 1 to 12.

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

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

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The cycloalkyl group may have at least one hydrogen atom in each cyclic form substituted by a linear alkyl group (the above-mentioned group) or a branched alkyl group (the above-mentioned group, etc.).

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

Fluorene skeleton-containing tetracarboxylic acid anhydrides can be prepared by reacting 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9'-bis (3,4- Fluorene dianhydride, and the like.

The upper limit of the content of the aromatic tetracarboxylic acid anhydride-containing tetracarboxylic acid anhydride having a fluorene skeleton of 100 mol% is exemplified by 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 mol% 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mol%. 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%, more preferably about 50 to 100 mol%.

The upper limit of the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mass% of the aromatic tetracarboxylic acid anhydride is exemplified by 100, 90, 80, 70, 60, 55, 50, 40, 30, 20 and 10 mass% 95, 90, 80, 70, 60, 50, 40, 30, 20, 10, 0 mass%. In one embodiment, the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mass% of the aromatic tetracarboxylic acid anhydride is preferably about 0 to 100 mass%, more preferably about 50 to 100 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, 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 mass% of the monomer group is exemplified by 75, 70, 60, 50, 40, 30, 20, 10 and 5 mass%, and the lower limit is 70, 60, 50, 40, 30, 20, 10, 5, 0 mass%, and the like. In one embodiment, the content of the fluorene skeleton-containing tetracarboxylic acid anhydride in 100 mass% of the monomer group is preferably about 0 to 75 mass%.

(Symmetrical aromatic tetracarboxylic acid anhydride)

In the present disclosure, " symmetrical aromatic tetracarboxylic acid anhydride " means an aromatic tetracarboxylic acid anhydride having in its molecule an axis of symmetry (e.g., C2 symmetry axis). The symmetrical aromatic tetracarboxylic acid anhydride is represented by the following general formula

(Wherein X is a single _{bond, -SO 2 -, -CO-, -O-} , -O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O-, -COO- (CH 2 ) _p -OCO-, or _{-COO-H 2 C-HC (} -O-C (= O) -CH 3) represents a -CH ₂ -OCO-, p represents an integer of 1 to 20)

And the like are exemplified.

The symmetrical aromatic tetracarboxylic acid anhydride represented by the above general formula is anhydrides such as 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3 ' 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 4,4'- [propane-2,2- 2-bis (3,3 ', 4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2,2-bis (3,4- Bis (3, 4-dicarboxyphenoxyphenyl) sulfone anhydride, 2,2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, 2,2-bis 2, 3, 4-benzenetetracarboxylic acid anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6-trichlorobenzenesulfonic acid anhydride, 7-naphthalene tetracarboxylic Acid anhydrides and the like.

Of the symmetrical aromatic tetracarboxylic acid anhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic acid anhydrides, 4,4', 4'-benzophenone tetracarboxylic anhydrides are preferable from the viewpoints of compatibility of aromatic tetracarboxylic acid anhydrides with diamines, - [propane-2,2-diyl bis (1,4-phenyleneoxy)] diphthalic acid anhydride, and 4,4'-oxydiphthalic anhydride.

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

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

(Other aromatic tetracarboxylic acid anhydrides)

In one embodiment, the monomer group may include an aromatic tetracarboxylic acid anhydride (also referred to as another aromatic tetracarboxylic anhydride), which is neither a fluorene skeleton-containing tetracarboxylic acid anhydride nor a symmetrical aromatic tetracarboxylic acid anhydride.

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

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% by mass, 0% by mass or the like.

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

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

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

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

<Diamine>

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

(Dimer diamine)

In the present disclosure, the dimer diamine is obtained by replacing all the carboxyl groups of the dimer acid, which is an unsaturated fatty acid such as oleic acid, with primary amino groups (see JP-A-1997-12712, etc.) . In the following formulas, m + n = 6 to 17 is preferable, p + q = 8 to 19 is preferable, and the broken line indicates a carbon-carbon single bond or carbon-carbon double bond it means).

PRIMININE 1075 and PRIAMINE 1074 (both manufactured by Kuroda Japan K.K.) are commercially available from Bacillus &lt; (R) &gt; And the like.

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

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

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

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

(Fluorene skeleton-containing diamine)

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

(Wherein either one of R ¹ and R ² represents a group having an amino group and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either one of R ³ or R ⁴ has an amino group; And one of them represents a hydrogen atom, a hydroxyl group, an alkyl group, or a halogen atom.

In the present disclosure, the term "group having an amino group" means an amino group and a group in which at least one hydrogen atom in the functional group is substituted by 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.

The aryl group includes monocyclic aryl groups, condensed ring aryl groups and the like. The aryl group may be substituted with at least one hydrogen atom by a straight-chain or branched alkyl group.

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

The fluorene skeleton-containing diamine can be prepared by reacting 9,9'-bis (aminophenyl) fluorene, 9,9'-bis (4-amino- Fluorophenyl) fluorene, 9,9 '-bis (4-amino-3-hydroxyphenyl) fluorene, 9,9'- Bis (4-fluoro-3-aminophenyl) fluorene, 9,9'-bis Yl) phenyl] fluorene, and the like.

The upper limit of the content of the fluorine skeleton-containing diamine component in 100 mol% of diamine is 80, 70, 60, 50, 40, 30, 25 mol% and the lower limit is 75, 70, 60, 50, 40, 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 the dielectric property.

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

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

3.00, 2.00, 1.00, 0.50 and the like can be exemplified as the upper limit of the ratio of the amount of the fluorene skeleton-containing diamine to the amount of the dimer diamine (diamine / dimer diamine containing fluorene skeleton), and the lower limit is 4.00, 3.00, 2.00, , 0.50, 0.25, and the like are exemplified. In one embodiment, the ratio of the amount of the fluorene skeleton-containing diamine to the amount of the diamine diamine (fluorene skeleton-containing diamine / dimer diamine) is preferably about 0.25 to 4.00 from the viewpoint of flexibility, .

(Diaminopolysiloxane)

Diaminopolysiloxanes include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, bis (3-aminophenyl) propyl] polydimethylsiloxane, [alpha], [omega] -bis [3- 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and 1,3-bis (4-aminobutyl) tetramethyldisiloxane.

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

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

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

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

(Other diamines)

In one embodiment, the monomer group may include diamines other than the above (also referred to as other diamines). The other diamines include alicyclic diamines, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diamine Examples of the aminophenoxybenzene compound include aminophenoxy propane, aminophenyl propane, diaminophenyl hexafluoropropane, diaminophenyl phenethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodymethylbenzylbenzene, bisaminoditrifluoromethylbenzylbenzene, Aminophenoxyphenylsulfone, aminophenoxyphenyl ether, aminophenoxyphenylpropane, bis (aminophenoxybenzoyl) benzene, bis (aminophenoxy-α, Dimethylbenzyl) benzene, bis [(aminoaryloxy) benzoyl] diphenyl ether, bis (amino- alpha, alpha -dimethylbenzylphenoxy) benzophenone, bis [amino- Bis (aminoaryloxy) - diphenylsulfone, diaminodialyloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis (aminoaryloxy) - (Aminoalkoxy) ethers, bis (aminoalkoxy) alkanes, bis [(aminoalkoxy) ethers, Alkoxy] alkane, (poly) ethylene glycol bis (aminoalkyl) ether, bis (aminoaryloxy) pyridine, diaminoalkylene and the like.

The alicyclic diamine is preferably selected from the group consisting of diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) bicyclo [ 2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5. 2,1,2,6,6] decane, isophoronediamine, 4,4'-diaminodicyclohexylmethane, and 1,3-bisaminomethylcyclohexane.

Bisaminophenoxyphenylpropane is exemplified by 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, and 4,4'-diaminodiphenyl ether.

Phenylenediamine includes phenylenediamine such as p-phenylenediamine and m-phenylenediamine.

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

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

The diaminophenyl propane is preferably a compound represented by the following formula (1): 2, 2-di (3-aminophenyl) propane, .

The diaminophenylhexafluoropropane is preferably at least one selected from the group consisting of 2,2-di (3-aminophenyl) -1,1,3,3,3-hexafluoropropane, 2,2-di , 1,1,3,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,3,3,3,3-hexafluoropropane And the like.

Diaminophenylphenyl ethane may be used in combination with at least one compound selected from the group consisting of 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) - (4-aminophenyl) -1-phenylethane and the like.

The bisaminophenoxybenzene may be selected from the group consisting of 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4-bis (4-aminophenoxy) benzene, and the like.

The bisaminobenzoylbenzene may be selected from the group consisting of 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4- 4-aminobenzoyl) benzene, and the like.

The bisaminodymethyl benzyl benzene may be used alone or in combination of two or more selected from the group consisting of 1,3-bis (3-amino-?,? -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene.

Bisaminoditrifluoromethylbenzylbenzene may be prepared by reacting 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3- (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino- Benzene, and the like.

Aminophenoxybiphenyl may be used in combination with 2,6-bis (3-aminophenoxy) benzonitrile, 4,4'-bis (3-aminophenoxy) biphenyl, Phenyl and the like.

Aminophenoxyphenyl ketone includes bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone and the like.

Aminophenoxyphenyl sulfide is exemplified by bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide and the like.

Aminophenoxyphenyl sulfone is exemplified by bis [4- (3-aminophenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone.

Aminophenoxy phenyl ether includes bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether.

Aminophenoxyphenylpropane is a compound which is obtained by reacting 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2- , 3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,3,3,3-hexafluoropropane and the like.

The bis (aminophenoxybenzoyl) benzene may be used alone or in combination with one or more selected from the group consisting of 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, Bis [4- (3-aminophenoxy) benzoyl] benzene, and 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene.

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

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

Bis (amino- alpha, alpha -dimethylbenzylphenoxy) benzophenone includes 4,4'-bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] benzophenone.

Bis [amino-?,? - dimethylbenzylphenoxy] diphenyl sulfone is exemplified by 4,4'-bis [4- (4-amino-?,? - dimethylbenzyl) phenoxy] diphenyl sulfone and the like.

4, 4'-bis [aminophenoxyphenoxy] diphenyl sulfone is exemplified by 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone.

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

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

The 6, 6'-bis (aminoaryloxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane is 6,6'-bis (3-aminophenoxy) 3,3 ', 3'-tetramethyl-1, 1'-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.

Bis (aminoalkoxyalkyl) ethers include bis [2- (aminomethoxy) ethyl] ether, bis [2- And the like.

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

Bis [(aminoalkoxy) alkoxy] alkane is exemplified by 1,2-bis [2- (aminomethoxy) ethoxy] ethane and 1,2-bis [2- (2-aminoethoxy) ethoxy] do.

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

Bis (aminoaryloxy) pyridine is 2,6-bis (3-aminophenoxy) pyridine and the like.

The diaminoalkylene is preferably at least one member selected from the group consisting of ethylenediamine, 1, 3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,2-diaminododecane.

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

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

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

In one embodiment, the content of other diamine in the monomer group is 5, 4, 1, 0.9, 0.5, less than 0.1 mass%, 0 mass% or the like.

The upper limit of the content of the diamine 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 and 25 mol%. In one embodiment, the content of the diamine in 100 mol% of the monomer group is preferably about 25 to 50 mol%.

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

The upper limit of the aromatic tetracarboxylic acid anhydride to diamine molar ratio (aromatic tetracarboxylic acid anhydride / diamine) is exemplified by 1.5, 1.4, 1.3, 1.2 and 1.1, and lower limits of 1.4, 1.3, 1.2, 1.1 and 1.0. In one embodiment, the molar ratio of the aromatic tetracarboxylic acid anhydride and the diamine (aromatic tetracarboxylic acid anhydride / diamine) is preferably about 1.0 to 1.5 from the viewpoint of solvent solubility and solution stability.

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

<Other monomers>

In one embodiment, the monomer groups may include aromatic tetracarboxylic acid anhydrides and non-diamine monomers (also referred to as other monomers). Other monomers include aliphatic tetracarboxylic acid anhydrides and the like.

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

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

<Physical properties of polyimide>

The upper limit of the weight average molecular weight of the polyimide is 50000, 40000, 30000, 20000, 10000, 7500, 5500 and the lower limit is 45000, 40000, 30000, 20000, 10000, 7500, 5000 and the like. In one embodiment, the weight average molecular weight of the polyimide is preferably 5000 to 50,000 from the viewpoints of dielectric properties, solvent availability, and flexibility.

The upper limit of the number average molecular weight of the polyimide is 40000, 30000, 20000, 10000, 7500, 5000, 3000 and the lower limit is 35000, 30000, 20000, 10000, 7500, 5000, 3000, 2000 and the like. In one embodiment, the number average molecular weight of the polyimide is preferably 2,000 to 40,000 from the viewpoints of dielectric properties, solvent availability, and flexibility.

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

The upper limit of the softening point of the polyimide is 220, 200, 150, 100, 50, 25 ° C and the lower limit is 210, 200, 150, 100, 50, 25 and 20 ° C. In one embodiment, the softening point of the polyimide is preferably 20 to 220 占 폚 in terms of workability, heat resistance, and solvent availability.

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

&Lt; Production method of polyimide, etc. &

The polyimide can be produced by various known methods. The production method of the polyimide is preferably carried out in the presence of an aromatic tetracarboxylic acid anhydride and a diamine-containing monomer group at a temperature of preferably about 60 to 120 DEG C, more preferably about 80 to 100 DEG C Preferably 0.1 to 2 hours, more preferably 0.1 to 0.5 hours, to obtain a water-in-water emulsion. The obtained water is preferably heated at a temperature of about 80 to 250 ° C, more preferably about 100 to 200 ° C , For example, a process comprising imidization reaction, that is, dehydration ring-closure reaction at a temperature of about 1 to 20 hours, preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours.

In the step of imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents to be described later can be used. Various known reaction catalysts, dehydrating agents, and organic solvents to be described later may be used alone or in combination of two or more. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline and isoquinoline. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The imide termination rate of the polyimide is not particularly limited. The term &quot; imide waste rate &quot; means the content of the cyclic imide bond in polyimide, and can be determined by various spectroscopic means such as NMR or IR analysis. From the viewpoint of good adhesion at room temperature and good heat-resistant adhesion, the imide ring exchange rate of the polyimide is preferably about 70% or more, and more preferably about 85 to 100%.

[glue]

The present disclosure provides an adhesive comprising the polyimide, the cross-linking agent, and the organic solvent.

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

<Cross-linking agent>

Any known crosslinking agent may be used without particular limitation, provided that it functions as a crosslinking agent for the polyimide. The crosslinking agent may be used alone or in combination of two or more. The crosslinking agent is preferably at least one selected from the group consisting of epoxide, benzoxazine, bismaleimide and cyanate ester.

(Epoxide)

Epoxides include phenol novolac type epoxides, cresol novolak type epoxides, bisphenol A type epoxides, bisphenol F type epoxides, bisphenol S type epoxides, hydrogenated bisphenol A type epoxides, hydrogenated bisphenol F type epoxides, An epoxide, a triazine skeleton-containing epoxide, a fluorene skeleton-containing epoxide, a linear aliphatic epoxide, an alicyclic epoxide, a glycidylamine type epoxide, a triphenol methane type epoxide, an alkyl-modified triphenol methane type epoxide , Biphenyl-type epoxides, dicyclopentadiene skeleton-containing epoxides, naphthalene skeleton-containing epoxides, arylalkylene-type epoxides, tetraglycidyl xylenediamines, dimer acid-modified epoxides which are dimer acid- Dimer acid diglycidyl ester, and the like. JER828 "," jER834 "," jER807 "manufactured by Mitsubishi Chemical Corporation," ST-3000 "manufactured by Shinnitetsu Chemical Co., Ltd., and" YE-172-X75 &quot; manufactured by Shin-Nittsu Chemical Co., Ltd., and &quot; TETRAD-X &quot; manufactured by Mitsubishi Gas Chemical Co., Among them, at least one species selected from the group consisting of bisphenol A type epoxide, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy and alicyclic epoxide is preferable from the viewpoint of balance of heat-resistant adhesive property, moisture-absorbing solder heat resistance and low dielectric property Do.

Particularly, tetraglycidyldiamine

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

Has good compatibility with the polyimide. Further, by using this, the low-loss elastic modulus of the adhesive layer becomes easy, and the heat-resistant adhesive property and the low dielectric property become good.

When an epoxide is used as the crosslinking agent, various known curing agents for epoxide can be used in combination. The curing agent for epoxides may be used alone or in combination of two or more. The curing agent for epoxides may be selected from the group consisting of succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4- A mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, a mixture of tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, anhydrous nadic anhydride, methylnadonic anhydride, norbornane-2, 3- dicarboxylic anhydride, (DICY), an aromatic diamine (trade name: Lonzacure M-DEA, manufactured by Nippon Shokubai Co., Ltd.), and an anhydride-based curing agent such as anthraquinone dicarboxylic acid anhydride, 2,3-dicarboxylic acid anhydride, methylcyclohexadecarboxylic acid anhydride, Lonzacure M-DETDA, etc.), amine-based curing agents such as aliphatic amines, phenol novolak resins, cresol novolac resins, bisphenol A-type novolac resins, Modified phenol novolac resin, modified phenol novolak resin, phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compounds, maleic acid modified rosin and its hydride Rosin-based crosslinking agents and the like. Among these, a phenolic curing agent, particularly a phenazine hydroxyl group-containing phosphazene curing agent, is preferred. The amount of the curing agent to be used is not particularly limited, but is preferably about 0.1 to 120 mass%, and more preferably about 10 to 40 mass%, when the solid content of the adhesive is 100 mass%.

When a curing agent for epoxide and epoxide is used in combination as a crosslinking agent, a reaction catalyst can be used in combination. The reaction catalyst may be used alone or in combination of two or more. The reaction catalyst is 1,8-diazabicyclo [5. Tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol and tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole , Imidazoles such as 2-phenyl-4-methylimidazole and 2-heptadecylimidazole, imidazoles such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate. The amount of the reaction catalyst to be used is not particularly limited, but it is preferably about 0.01 to 5% by mass when the solid content of the adhesive is 100% by mass.

(Benzoxazine photo)

Benzoxazine was prepared by reacting 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H- (3,4-dihydro-3-methyl-2H-1,3-benzoxazine), and the like. The nitrogen of the oxazine ring may be bonded with a phenyl group, a methyl group, a cyclohexyl group or the like. Examples of commercially available products of benzoxazine include "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shigokufu Sangyo Co., Ltd., and "RLV-100" manufactured by Air Water .

(Bismaleimide)

The bismaleimide may be selected from the group consisting of 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'- (2, 2, 4-trimethyl) hexane, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane bismaleimide, Ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, and the like. A commercially available product of bismaleimide is "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like.

(Cyanate ester)

The cyanate ester can be prepared by reacting a 2-allylphenol cyanate ester, a 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,3,3,3,3-hexafluoropropane , Bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumyl phenol cyanate ester, 1,1 Bis (4-cyanatophenyl) ethane, 4,4'-bisphenol cyanate ester, and 2, 2-bis (4-cyanatophenyl) propane. A commercially available product of the cyanate ester is &quot; PRIMASET BTP-6020S (Lonza Japan) &quot;.

The upper limit of the content of the crosslinking agent relative to 100 parts by mass (in terms of solid content) of the polyimide in the adhesive is 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, And the lower limit is 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 relative to 100 parts by mass (in terms of solid content) of the polyimide is preferably about 5 to 900 parts by mass.

The upper limit of the content of the crosslinking agent in 100 mass% of the adhesive is 80, 70, 60, 50, 40, 30, 20, 10, 5 mass% and the lower limit is 70, 60, 50, 40, 30, 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 solvents>

As the organic solvent, various known organic solvents may be used singly or in combination of two or more kinds. Examples of the organic solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme and methyldiglime, Alicyclic solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol; aromatic solvents such as toluene; and the like.

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

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

<Flame Retardant>

In one embodiment, the adhesive includes a flame retardant. The flame retardants 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 (phosphorus-containing flame retardant))

Phosphorous flame retardants include polyphosphoric acid and phosphoric acid esters, and phosphazene derivatives not containing a phenolic hydroxyl group. Among these phosphazene derivatives, cyclic phosphazene derivatives are preferred in view of flame retardancy, heat resistance, bleed-out resistance, and the like. Commercially available products of cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., and Rabitol FP-300B manufactured by Fushimi Chemical Co., Ltd., and the like.

(Inorganic filler)

In one embodiment, examples of the inorganic filler include a silica filler, a phosphorous filler, a fluorine-based filler, and an inorganic ion exchanger filler. Commercially available products include FB-3SDC manufactured by Denka Co., Exolit OP935 manufactured by Clariant Chemicals Co., Ltd., KTL-500F manufactured by Kitamura Co., Ltd., and IXE manufactured by Toagosei Co.,

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

&Lt; Reactive alkoxysilyl compound &

In one embodiment, the adhesive has the formula: a group containing _{^{Z-Si (R 1) a}} (OR 2) 3 is _-a anhydride (Z in the formula reacts to the functional group, R ¹ is hydrogen or a carbon number A hydrocarbon group having 1 to 8 carbon atoms, R ² is a hydrocarbon group having 1 to 8 carbon atoms, and a is 0, 1 or 2). With the reactive alkoxysilyl compound, the melt viscosity of the adhesive layer of the present invention can be controlled while maintaining low dielectric properties. As a result, permeation of the cured layer generated from the substrate can be suppressed while increasing the interfacial adhesion (so-called anchor effect) between the adhesive layer and the substrate.

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

Compounds where Z contains an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, and the like. Examples of the compound containing Z in the epoxy group include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldi Ethoxy silane, and the like. Of these, compounds having Z in the amino group are preferred, since the effects of reactivity and flow control are good.

The upper limit of the content of the reactive alkoxysilyl compound relative to 100 parts by mass (in terms of solid content) of the polyimide in the adhesive is 5, 2.5, 1, 0.5, 0.1, 0.05 parts by mass and the lower limit is 4, 2.5, 1, 0.5 , 0.1, 0.05, 0.01 parts by mass, and the like. In one embodiment, the content of the reactive alkoxysilyl compound relative 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 include, as an additive, any one of the polyimide, the cross-linking agent, the organic solvent, the flame retardant, and the reactive alkoxysilyl compound.

Examples of the additive include a ring opening esterification catalyst, a dehydrating agent, a plasticizer, a lubricant, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a brightener, a colorant, a conductive agent, a releasing agent, a surface treatment agent, a viscosity modifier, a silica filler and a fluorine filler do.

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

In another embodiment, the content of the additive is, for example, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, and 0 parts by mass based on 100 parts by mass (in terms of solid content) of the polyimide.

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

[Film adhesive]

The present disclosure provides a film-based adhesive comprising a heated cured product of the adhesive. Examples of the method for producing the film-like adhesive include a step of applying the adhesive to an appropriate support, a step of curing by heating the organic solvent by volatilization, a step of peeling from the support, and the like. The thickness of the adhesive material is not particularly limited, but is preferably about 3 to 40 mu m. Examples of the support include the following.

[Adhesive layer]

The present disclosure provides an adhesive or an adhesive layer comprising the film-like adhesive. When the adhesive layer is produced, various known adhesives other than the adhesive may be used in combination with the adhesive. Similarly, various known film-like adhesive materials other than the film-like adhesive material may be used in combination with the film-like adhesive material.

[Adhesive sheet]

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

A plastic film is exemplified as the supporting film. The plastic may be selected from the group consisting of polyesters, polyimides, polyimide-silica hybrids, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethylmethacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile- (So-called liquid crystal polymer; Kuraray Co., Ltd., &quot; Beckstar &quot;) obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid and parahydroxybenzoic acid.

When the adhesive is applied to the support film, the application means may be employed. The thickness of the coating layer is not particularly limited, but the thickness after drying is preferably about 1 to 100 mu m, more preferably about 3 to 50 mu m. The adhesive layer of the adhesive sheet may be protected with various protective films.

[Copper with resin]

The present disclosure provides a resin-attached copper foil comprising the adhesive layer and the copper foil. Specifically, the resin-coated copper foil is obtained by applying the adhesive or the adhesive material on the film to the copper foil. Examples of the copper foil include a rolled copper foil and an electrolytic copper foil. The thickness is not particularly limited, but is preferably about 1 to 100 mu m, more preferably about 2 to 38 mu m. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). The rust-preventive treatment may be a plating treatment using a plating solution containing Ni, Zn, Sn or the like, or a so-called mirror-surface treatment such as a chromate treatment. As the application means, the above-described method is exemplified.

The adhesive layer of the resin-coated copper foil may be uncured or partially cured or fully cured under heating. The partially cured adhesive layer is in a state called a B stage. The thickness of the adhesive layer is not particularly limited, and is preferably about 0.5 to 30 mu m. Further, a copper foil may be further adhered to the adhesive surface of the resin-bonded copper foil to obtain a copper foil with a resin on both sides.

[Copper clad laminate]

The present disclosure provides a copper clad laminate comprising the resin-attached copper foil and the copper foil or the insulating sheet. Copper clad laminates are also referred to as CCL (Copper Clad Laminate). Specifically, the copper clad laminate is obtained by pressing the resin-coated copper foil on at least one surface or both surfaces of various known copper foils or insulating sheets under heating. The resin-bonded copper foil may be bonded to the other surface thereof. The number of copper foils with resin and insulating sheet in the copper clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. Prepreg is a sheet-like material that is impregnated with a resin such as glass cloth and cured to the B-stage (JIS C 5603). As the resin, an insulating resin such as a polyimide resin, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, or an aramid resin is used. The thickness of the prepreg is not particularly limited, and is preferably about 20 to 500 mu m. The heating and pressing conditions are not particularly limited, and are preferably about 150 to 280 DEG C (more preferably about 170 DEG C to 240 DEG C) and preferably about 0.5 to 20 MPa (more preferably about 1 to 8 MPa) .

[Printed circuit board]

The present disclosure provides a printed wiring board having a circuit pattern on a copper foil surface of the copper clad laminate. The patterning means for forming a circuit pattern on the copper foil surface of the copper clad laminate is exemplified by a subtractive method and a semiadditive method. The semi-additive method is 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. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. It is also possible to obtain a multilayer substrate by using the printed wiring board as a core substrate and laminating the same printed circuit board or another known printed circuit board or a printed circuit board thereon. For lamination, a known adhesive other than the above-mentioned adhesive may be used in combination with the adhesive. In addition, the number of layers in the multi-layer substrate is not particularly limited. In addition, a via hole may be inserted in each lamination and the inside may be plated. The line / space ratio of the circuit pattern is not particularly limited, but is preferably about 1 탆 / 1 탆 to 100 탆 / 100 탆. The height of the circuit pattern is not particularly limited, but is preferably about 1 to 50 mu m.

[Multilayer wiring board]

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

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

Step 2: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the substrate with the adhesive layer, and pressing and bonding under heating and pressing

The present invention also provides a method of manufacturing a multilayer wiring board.

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

In Step 1, the means for bringing the adhesive or film-like adhesive material into contact with the adherend is not particularly limited and may be various known coating means, a curtain coater, a roll coater, a laminator, ) And the like.

The heating temperature and the pressing time in Step 2 are not particularly limited, but (A) the adhesive or film-like adhesive of the present invention is brought into contact with at least one surface of the core substrate, and then heated to about 70 to 200 DEG C for about 1 to 10 minutes And then (b) heat treatment is further carried out at about 150 ° C to 250 ° C for about 10 minutes to 3 hours to advance the curing reaction of the crosslinking agent. The pressure is not particularly limited, but preferably about 0.5 to 20 MPa, more preferably about 1 to 8 MPa, through the steps (A) and (B).

Example

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. It should be understood, however, that the description of the preferred embodiments and the following examples are provided for illustrative purposes only and are not intended to be limiting of the present invention. Therefore, the scope of the present invention is not limited to the embodiments specifically described in this specification and the embodiments, but is limited only by the claims. In the following Examples and Comparative Examples, numerical values such as parts and% are based on mass unless otherwise specified.

&Lt; Preparation of polyimide &

Manufacturing example  One

To the reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introducing tube, 9,9'-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene acid dianhydride (Hereinafter abbreviated as &quot; BPF-PA &quot;, manufactured by JFE Chemical Co., hereinafter abbreviated as BPF-PA), 980.20 g of cyclohexanone, and 196.04 g of methylcyclohexane. Next, 236.60 g of a commercially available dimer diamine (trade name: PRIAMINE 1075, manufactured by Kuroda Japan K.K.) was dropped thereon and imidization reaction was carried out at 140 캜 for 12 hours to obtain a solution of polyimide (1-1) Volatile content 31.6%). The molar ratio of the acid component / amine component of the polyimide was 1.03.

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

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

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

BisDA-1000: Bis (4-methoxyphenyl) diphthalic acid dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Joint Corporation)

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

Example  One

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

EXAMPLES and COMPARATIVE EXAMPLES EXAMPLES EXAMPLES EXAMPLES 1 and 2 were carried out in the same manner as in Example 1 except that the composition of the adhesive was changed as shown in Table 2 to obtain an adhesive.

The organic solvent may also include an organic solvent used in producing the polyimide.

&Lt; Preparation of adhesive sheet &gt;

The resulting adhesive was applied to a polyimide film (trade name "Kapton 50EN", manufactured by Toray-DuPont Co., Ltd., film thickness 12.5 μm; thermal expansion coefficient 15 ppm / ° C.) Lt; 0 &gt; C for 3 minutes to obtain an adhesive sheet.

<Fabrication of copper clad laminate>

A copper foil with resin laminated on the roughening side of a commercially available electrolytic copper foil (trade name "F2-WS", made by Furukawa Circuit Foil Co., Ltd., thickness of 18 μm) was prepared.

Next, the copper foil with resin thus obtained was placed on a pressing support, and heat-pressed under the conditions of a pressure of 5 MPa, 200 캜 and 60 minutes via a support obtained from the copper material from above, thereby producing a copper clad laminate.

&Lt; Adhesion test &gt;

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

&Lt; 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 Sogo Kogyo Kogyo Co., Ltd.), and the mixture was heated at 30 占 폚 for 10 hours, 70 占 폚 for 10 hours, And then cured under the conditions of 120 占 폚 for 6 hours, 150 占 폚 for 6 hours, and 180 占 占 12 hours to obtain a resin for permittivity measurement and a cured product sample having a film thickness of about 300 占 퐉.

Next, the obtained dielectric constant measuring resin and cured product samples were measured for dielectric constant and dielectric tangent at 10 GHz in accordance with JIS C2565 using a commercially available permittivity measuring apparatus (cavity resonator type, manufactured by AiTi). The results are shown in the table.

Claims (14)

Aromatic tetracarboxylic acid anhydrides,
And diamines including dimer diamines
, And is a reactant of a monomer group containing a fluorenylene group

&Lt; / RTI &gt; The method according to claim 1,
When the diamine is a fluorene skeleton-containing diamine

(Wherein either one of R ¹ and R ² represents a group having an amino group and the other represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom, and either one of R ³ or R ⁴ has an amino group; And one of them represents a hydrogen atom, a hydroxy group, an alkyl group, or a halogen atom)
&Lt; RTI ID = 0.0 &gt; polyimide. &Lt; / RTI &gt; 3. The method according to claim 1 or 2,
Wherein the diamine comprises a diaminopolysiloxane. 4. The method according to any one of claims 1 to 3,
Wherein the molar ratio of the aromatic tetracarboxylic acid anhydride to the diamine (aromatic tetracarboxylic acid anhydride / diamine) is 1.0 to 1.5. An adhesive comprising the polyimide, the crosslinking agent and the organic solvent according to any one of claims 1 to 4. 6. The method of claim 5,
Wherein the crosslinking agent is contained in an amount of 5 to 900 parts by mass based on 100 parts by mass of the polyimide (in terms of solid content), and the organic solvent is contained in an amount of 150 to 900 parts by mass. A film-form adhesive comprising a heated 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 resin-coated copper foil comprising the adhesive layer and the copper foil according to claim 8. A copper clad laminate comprising the resin-attached copper foil and the copper foil or the insulating sheet according to claim 10. A printed wiring board having a circuit pattern on a copper foil surface of the copper clad laminate according to claim 11. The printed wiring board 1 or the printed circuit board 1,
An adhesive layer according to claim 8, and
A printed wiring board (2) or a printed circuit board (2). A process for producing a multilayer wiring board comprising the following steps 1 and 2.
Process 1: A process for manufacturing an adhesive layer-attached substrate by bringing the adhesive according to claim 5 or 6 or the film-like adhesive material according to claim 7 into contact with at least one surface of a printed wiring board (1) or a printed circuit board
Step 2: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the substrate with the adhesive layer, and pressing and bonding under heating and pressing