KR20160117368A - Adhesive layer on adhesive composition film, adhesive sheet, polymer attached copper foil, copper-clad laminate, flexible copper-clad laminate, printed wiring board, flexible printed wiring board, multilayer wiring board, printed circuit board, flexible printed circuit board - Google Patents

Abstract

Provided is an adhesive composition capable of forming an adhesive layer (a cured product) having excellent room temperature adhesiveness, moisture absorption solder heat resistance, and low dielectric characteristics. In addition, the composition comprises: a long-chain polyimide (A) including a monomer group () containing an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2) as a reaction component; a short-chain polyimide (B) including a monomer group () containing an aromatic tetracarboxylic acid anhydride (b1) and a dimer diamine (b2) as a reaction component; a thermosetting crosslinking agent (C); and an organic solvent (D). In addition, a weight average molecular weight (M_(A)) of component (A) is 24000 or more and less than 45000, and a weight average molecular weight (M_(B)) of component (B) is 7000 or more and less than 24000. Moreover, the adhesive composition is satisfied with conditions (1) and (2): 1.2 <= [M_(A)/ M_(B)] <= 3.5, and 1.5 <= [content (W_(A)) of component (A)/content (W_(B)) of component (B)] <= 9.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper clad laminate, a flexible copper clad laminate, a printed wiring board, a flexible printed wiring board, a multilayer wiring board, a printed circuit board, a flexible printed wiring board, a flexible printed wiring board, a multilayer wiring board, a printed circuit board, a flexible printed circuit board,

The present invention relates to an adhesive composition used in the production of a flexible printed circuit board and the like, a film-like adhesive comprising the adhesive composition, an adhesive composition thereof, and an adhesive layer (hardness hardened) A copper clad laminate, a flexible copper clad laminate, a printed wiring board, a flexible printed wiring board multilayer wiring board printed circuit board, and a flexible printed circuit board.

It is necessary to transmit and process a large amount of information at a low loss and at a high speed in a mobile communication device such as a cellular phone and a smart phone, a network related electronic device such as a base station device, a server router, and a large computer. The high frequency of the electric signal to be handled is progressing. However, since high-frequency electrical signals are easily attenuated, it is necessary to further reduce the transmission loss of the printed wiring board. Therefore, an adhesive composition generally used for a printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent (hereinafter, also referred to as low dielectric property).

In addition, solder heat resistance is required at a reflow temperature of about 260 캜 as solder materials used for mounting components on printed wiring boards are made lead-free. In addition, before the reflow process, the printed wiring board is pre-dried at a temperature of 100 to 120 ° C in order to suppress foaming and swelling caused by moisture absorption. However, in order to improve the production efficiency, the solder reflow process is being carried out without pre-drying. Therefore, the adhesive used for the printed wiring board is required to exhibit soldering heat resistance not only at room temperature but also in a hygroscopic state.

For example, in Patent Document 1, a film-form polyimide adhesive having a predetermined glass transition temperature, tensile breaking strength and tensile modulus of elasticity is used as the adhesive composition having excellent room temperature adhesiveness and moisture- However, the low-dielectric property in the GHz band is insufficient.

<Prior Art Literature>

[Patent Document 1] JP-A-7-197007

An object of the present invention is to provide an adhesive composition capable of forming an adhesive layer (cured product) excellent in room temperature adhesiveness, moisture absorption solder heat resistance and low dielectric property.

As a result of intensive studies, the present inventors have found that an adhesive composition capable of solving the above problems can be obtained by additionally adding a crosslinking agent to a combination of a long polyimide having a molecular chain and a short polyimide so as to have predetermined conditions.

That is, the present invention relates to an adhesive composition having the following constitution and an invention related to the specific technical features thereof.

1. A thermoplastic resin composition comprising a long-chain polyimide (A) having as a reaction component a monomer group (?) Comprising an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2)

Chain polyimide (B) having as a reaction component a monomer group (?) Comprising an aromatic tetracarboxylic acid anhydride (b1) and a dimer diamine (b2)

The thermosetting cross-linking agents (C),

Containing an organic solvent (D)

Meanwhile,

It is less than (A) 24000 and less than 45000 weight average molecular weight _{(M (A))} is more than 24,000 in the component and (B) a weight average molecular weight of component (M _(B)) is more than 7,000,

Meanwhile,

Wherein the adhesive composition satisfies the following conditions (1) and (2).

1.1? [M _(A) / M _(B) ]? 3.7

1.5? (Content of component (A) (W _(A) ) / content of component (B) (W _(B) )? 9.5

2. The first adhesive composition, wherein one or both of the components (a1) and (b1) are represented by the following formula:

(3)

　

(Wherein X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-X ¹ -OCO- (Wherein X ¹ represents - (CH ₂ ) _l - (l = 1 to 20) or -H ₂ C-HC (-OC (═O) -CH ₃ ) -CH ₂ -).

3. The adhesive composition according to the first or second aspect, wherein the component (a) further comprises alicyclic diamine (a3) and / or diaminopolysiloxane (a4).

4. The adhesive composition according to any one of claims 1 to 3, wherein the component (?) Further comprises an alicyclic diamine (b3) and / or a diaminopolysiloxane (b4).

5. The adhesive composition according to any one of items 1 to 4, wherein the component (C) comprises at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound and a cyanate ester compound.

6. The adhesive composition of claim 5, wherein the epoxy compound comprises a diamine of the following structure.

[Chemical Formula 4]

　

(Wherein Y represents a phenyl group or a cyclocynyl group).

7. The adhesive composition according to any one of items 1 to 6, wherein the content of the component (C) is 1 to 150 parts by weight based on 100 parts by weight of the total of the components (A) and (B).

8. A film-based adhesive comprising the adhesive composition of any one of claims 1 to 7.

9. An adhesive layer comprising the adhesive composition of any one of claims 1 to 7 or the filmy adhesive of the above item 8.

10. An adhesive sheet comprising the adhesive layer and the substrate sheet as constituent elements.

11. Resin-bonded copper foil (RCC) comprising the adhesive layer and the copper foil as a component.

12. A copper clad laminate (CCL) comprising the resin-attached copper foil (RCC) of item 11 above and a prepreg sheet as a component.

13. A flexible copper clad laminate (FCCL) comprising the resin-attached copper foil (RCC) and the polyimide film of item 11 above as constituent elements.

14. A printed wiring board (PWB) formed by forming a copper foil circuit pattern of the copper clad laminate (CCL) of item 12 above.

15. A flexible printed wiring board (FPWB) formed by forming a copper foil circuit pattern of the flexible copper clad laminate (FCCL) of item 13 above.

16. A multilayer wiring board (MLB) comprising the printed wiring board (PWB) of item 14 and / or the flexible printed wiring board (FPWB) of 15 as constituent elements.

17. A printed circuit board (PCB) comprising a semiconductor component mounted on a printed wiring board (PWB) of the item 14 or a circuit of the multilayer wiring board (MLB) of the item 16.

18. A flexible printed circuit board (FPCB) comprising a semiconductor component mounted on a circuit of the flexible printed wiring board (FPWB) of the item 15 above.

According to the adhesive composition of the present invention, an adhesive layer (cured product) excellent in room temperature adhesiveness, moisture absorption solder heat resistance and low dielectric property can be formed.

The film-like adhesive obtained from the adhesive composition of the present invention forms an adhesive layer (cured product) excellent in room-temperature adhesiveness, moisture-absorbing solder heat resistance and low dielectric properties. The adhesive is suitable, for example, as a die bonding sheet.

The adhesive layer of the present invention is excellent in room-temperature adhesiveness, moisture-absorbing soldering heat resistance and low dielectric properties, and constitutes a base sheet (except for a copper foil) or a copper-clad laminated adhesive sheet or a copper foil with a resin. The adhesive sheet is useful as an auxiliary material for producing, for example, a copper clad laminate, a flexible copper clad laminate, a printed wiring board, a flexible printed wiring multi-layer wiring board, a printed circuit board and a flexible printed circuit board. The adhesive sheet can be used as a semiconductor carrier member (carrier tape, carrier sheet, etc.).

The resin-attached copper foil of the present invention and the copper-clad laminate and the flexible copper-clad laminate obtained therefrom are useful as starting materials for flexible copper-clad laminate, printed wiring board, multilayer wiring board and printed circuit board and enable low dielectric loss tangent.

The printed wiring board, the flexible printed wiring board multi-layer wiring board, the printed circuit board and the flexible printed circuit board according to the present invention can be applied to a mobile communication apparatus typified by a smart phone or a mobile phone, a network related electronic apparatus such as a base station apparatus, a server router, It is preferable as a flexible printed circuit board provided for use.

1 is a GPC chart (actual data) of the polyimide (A-1) of Production Example 1 and the polyimide (B-4) of Production Example 7, and it can be understood that the molecular weight distribution is different.

A predetermined polyimide (B) (hereinafter also referred to as a component (B)) A thermosetting cross-linking agent (C) (hereinafter, also referred to as a component (A) (Hereinafter also referred to as component (C)) and an organic solvent (hereinafter also referred to as component (D)).

 The component (A) is a monomer group (α) comprising an aromatic tetracarboxylic acid anhydride (a1) (hereinafter also referred to as a component (a1)) and a dimer diamine (hereinafter also referred to as a component (a2) (Hereinafter also referred to as (?) Component) as a reaction component, and is characterized by being a relative molecular weight relative to the component (B).

 The component (B) is a monomer group (β) comprising an aromatic tetracarboxylic acid anhydride (b1) (hereinafter also referred to as a component (b1)) and a dimer diamine (hereinafter referred to also as a component (b2) (Hereinafter also referred to as (?) Component) as a reaction component, and has a lower molecular weight than that of the component (A).

 The component (a1) and the component (b1) may be the same or different, and all known various aromatic tetracarboxylic acid anhydrides may be used. it is preferable that one or both of the component (a1) and the component (b1) is represented by the following formula.

 [Chemical Formula 5]

　

(Wherein X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-X ¹ -OCO- (Wherein X ¹ represents - (CH ₂ ) _l - (l = 1 to 20) or -H ₂ C-HC (-OC (═O) -CH ₃ ) -CH ₂ -).

Specific examples of the aromatic tetracarboxylic acid anhydride include pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride Water, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,2,3,4-benzene Tetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic anhydride, Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 '- benzophenone tetracarboxylic acid anhydride, 2,3,3', 4'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 2 , 2-bis (3 3 ', 4,4'-tetracarboxyphenyl) tetrafluoropropane dianhydride Water, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- -Dicarboxyphenyl) propane dianhydride, cyclopentanetetracarboxylic acid anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentyl acetic anhydride and 4,4'- [Propane-2,2-diyl bis (1,4-phenyleneoxy)] diphthalic anhydride, and the like. Among them, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'- [propane-2-2-ylbis (1,4-phenyleneoxy)] diphthalic anhydride and 4,4'-oxydiphthalic anhydride are preferable.

 The component (a2) and the component (b2) may be the same or different, and all known diamine diamines may be used without particular limitation.

The dimer diamine is a compound derived from dimer acid which is an aliphatic unsaturated fatty acid such as oleic acid (see JP-A-9-12712). The non-limiting structure is as follows. M + n = 6 to 17 in each structural formula, p + q = 8 to 19, and the broken line means a carbon-carbon single bond or a carbon-carbon double bond.

[Chemical Formula 6]

　

(7)

　

[Chemical Formula 8]

　

[Figure 9]

　

　

[Chemical formula 10]

　

(11)

　

Examples of commercially available products of the above dimer diamines include PRAMINE1075 and PRIAMINE1074 (all manufactured by Kuroda Japan Co., Ltd.) such as BASAMAIN 551 (BASF Japan Co., Ltd.), Vasamin 552 (Cosenox Japan Co., Etc.), and combinations of two or more kinds can be combined.

 The ratio of the component (a1) to the component (a2) is not particularly limited, but it is preferable that the ratio of the component (a1) to the component (a2) [mol of component (a1) / mole of component (a2)] = 90 to 120%, preferably 95 to 115%.

 The ratio of the component (b1) to the component (b2) is not particularly limited. However, the ratio of the component (b1) to the component (b2) (Mol of component (b1) / mol of component (b2)] is about 90 to 120%, preferably about 95 to 115%.

 The component (a) may further comprise an alicyclic diamine (a3) (hereinafter also referred to as component (a3)) and / or a diaminopolysiloxane (hereinafter also referred to as component (a4)). (b3) (hereinafter, also referred to as a component (b3)) and / or a diaminopolysiloxane (b4) (hereinafter also referred to as a component (b4)). The components (a3) and (b3) may be the same or different, and the components (a4) and (b4) may be the same or different.

 Examples of the component (a3) and the component (b3) include, for example, diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, 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 , 1,3-bisaminomethylcyclohexane, isophoronediamine, and the like, and two or more kinds of them may be combined.

 The component (a4) and the component (b4) may be, for example, α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω- (4-aminobutyl) polydimethylsiloxane,?,? - bis (5-aminobenzyl) polydimethylsiloxane,?,? - bis [3- 3- (4-aminophenyl) propyl] polydimethylsiloxane, and the like.

 The use ratio of the component (a3) and the component (a4) is not particularly limited, but it is preferable that the ratio of the component (a3) to the component (a4) (the total molar amount of the component (a3) and the component (a4) / the total molar amount of the total diamine component) is about 0 to 70%, preferably about 0.5 to 50%. The ratio of the component (a3) and the component (a4) is not particularly limited, and is generally about 10 / 0-6 / 4 in terms of the former / the latter molar ratio.

 The ratio of the component (b3) and the component (b4) is not particularly limited, but it is preferable that the ratio of the component (b3) to the component (b4) [the total molar amount of the component (b3) and the component (b4) / the total molar amount of the total diamine component] is about 0 to 70%, preferably about 0.5 to 50%. The ratio of the component (b3) and the component (b4) is not particularly limited, and is generally about 10 / 0-6 / 4 in terms of the former / latter molar ratio.

 The component (a) and the component (?) may be used in combination with another diamine (hereinafter also referred to as component (a5) or component (b5)). Specific examples thereof include bisaminophenox such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (4-aminophenoxy) Phenyl phenyl propane; Diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; Diaminodiphenyl sulfides such as 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide and 4,4'-diaminodiphenylsulfide; Diaminodiphenylsulfones such as 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone and 4,4'-diaminodiphenylsulfone; Diaminobenzophenones such as 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone and 3,4'-diaminobenzophenone; Diaminodiphenylmethanes such as 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and 3,4'-diaminodiphenylmethane; Diaminophenylpropane such as 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane and 2- (3-aminophenyl) -2- Ryu; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3 , Diaminophenylhexafluoro such as 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane Propane; Di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- ) -1-phenylethane; Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bisaminophenoxybenzenes such as benzophenone and aminophenoxy) benzene; Benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, Bisaminobenzoylbenzenes such as benzene; Benzene, 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, bisaminomethylbenzenes such as? -dimethylbenzyl) benzene and 1,4-bis (4-amino-?,? - dimethylbenzyl) benzene; Benzene, 1,3-bis (3-amino- alpha, alpha -trifluoromethylbenzyl) benzene, 1,3- Bisaminotrifluoromethylbenzylbenzenes such as 3-amino- [alpha], [alpha] -trifluoromethylbenzyl) benzene and 1,4-bis (4-amino- alpha, alpha -trifluoromethylbenzyl) benzene; Bis (3-aminophenoxy) benzene, 2,6-bis (3-aminophenoxy) pyridine, 4,4'- (4-aminophenoxy) phenyl; Aminophenoxy phenyl ketones such as bis [4- (3-aminophenoxy) phenyl] ketone and bis [4- (4-aminophenoxy) phenyl] ketone; Aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl] sulfide and bis [4- (4-aminophenoxy) phenyl] sulfide; Aminophenoxyphenyl sulfones such as bis [4- (3-aminophenoxy) phenyl] sulfone and bis [4- (4-aminophenoxy) phenyl] sulfone; Aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; Bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Aminophenoxyphenyl propanes such as fluoropropane and 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1, 1,3,3,3-hexafluoropropane; Other examples include 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- ] Benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4- Benzene] benzene, 1,4-bis [4- (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 4,4'- Bis [4- (4-amino- alpha, alpha -dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- Phenyl sulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] phenyl sulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, Mino-4,4'-biphenoxybenzophenone, 3,3'-diamino-4- 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis (3-aminophenoxy) Spirobiindane 6,6'-bis (4-aminophenoxy) 3,3,3'3'-tetramethyl-1,1'-spirobiindane 1,3-bis (3-aminopropyl) (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) silane, Ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- Bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene bis (2-aminoethoxy) ethane, Glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1, Diaminohexane, 1,8-diaminoheptane, 1,7-diaminoheptane, 1,7-diaminoheptane, 1,7-diaminoheptane, 1,8- And can combine two or more different types. Such an amount to be used is not particularly limited, but is usually less than 75 mol% when the total diamine component is taken as 100 mol%.

 The component (A) and the component (B) can be prepared by various known methods. (A) is at least one member selected from the group consisting of (a1) and (a2) and optionally (a3), (a4) and (a5) (Preferably 80 to 100 ° C) for about 0.1 to 2 hours (preferably 0.1 to 0.5 hours). The imidization reaction, that is, the dehydration ring-closing reaction, is further carried out at a temperature of about 80 to 250 ° C, preferably 100 to 200 ° C, for about 0.5 to 50 hours (preferably 1 to 20 hours) . The component (B) can be produced in the same manner as the component (A).

In the imidization reaction, various known reaction catalysts, dehydrating agents and the following component (D) can be used. 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, and combinations of two or more species It is also good. As the dehydrating agent, for example, an aliphatic acid anhydride such as acetic anhydride and an aromatic acid anhydride such as anhydrous benzoic acid and the like may be used, or two or more kinds may be used in combination.

 The imide ring-closing ratio of the component (A) and the component (B) is not particularly limited, but is usually 70% or more, preferably 85 to 100%. Herein, the term "imide ring closing ratio" means the content of cyclic imide bonds in the components (A) and (B) (hereinafter the same), for example, by various spectroscopic means such as NMR and IR analysis You can decide.

The adhesive composition of the present invention has a weight average molecular weight (M _(A) ) of the component (A) and a weight average molecular weight (M _(A) ) of the component (A) in the balance of the adhesiveness at room temperature, moisture absorption soldering heat resistance, _(B) ) are all limited. In the present specification, "weight average molecular weight" refers to the polystyrene reduced value by gel permeation chromatography (the same shall apply hereinafter). The ranges of M _(A) and M _(B) are as follows:

usually;

M _(A) : 24000 or more and less than 45000

M _(B) : 7000 or more and less than 24000

Preferably;

M _(A) : 24000 to less than 44000

M _(B) : 8000 or more and less than 21000

Particularly preferably;

M _(A) : 24000 or more and less than 43000

M _(B) : 9000 or more and less than 21000

The difference (M _(A) -M _(B) ) between the M _(A) and the M _(B) is not particularly limited, but is generally about 33,000 or less from the viewpoint of a balance between room temperature adhesiveness, heat absorption solder heat resistance, Preferably about 30000 or less, more preferably about 29000 or less.

The component _(A) is preferably a combination of two or more kinds of polyamides different from each other in M _(A) , and a combination of two or more kinds of polyamides in which the component _(B) is different from M _(B) . In this case, both M _(A) and M _(B) are represented by arithmetic mean values (M _{(A) μ} and M _{(B) μ} ). In this case, the range of M _{(A) μ} is that of M _(A) , and the range of M _{(B) μ is regarded as that} of M _(B ).

 [Equation 1]

_{M (A) μ = [(} M (A1) + M (A2) + ... M (An))] / n '

(Where n is a natural number of 1 or more).

 &Quot; (2) &quot;

M _{( B1)} + M _(B2) + ... M _(Bn) )] / n '

(Where n 'is a natural number of 1 or more).

The upper limit of n 'in both formulas, that is, the number of polyimides to be bonded is not particularly limited, but is usually about 10 in view of productivity.

The adhesive composition of the present invention is characterized in that the ratio of M _(A) to M _(B ) is limited to the following condition (1) from the viewpoint of balance of room temperature adhesiveness, moisture absorption soldering heat resistance and low dielectric property, (Hereinafter referred to as W _(A) ) and the content of the component (B) (hereinafter referred to as W _(B) ) is limited to the following condition (2).

usually;

(1) 1.1? [M _(A) / M _(B) ]? 3.7

(2) 1.5? [W _(A) / W _(B) ]? 9.5

Preferably;

(1) 1.2? [M _(A) / M _(B) ]? 3.5

(2) 1.8? [W _(A) / W _(B) ]? 8.8

Particularly preferably;

(1) 1.4? [M _(A) / M _(B) ]? 3.2

(2) 2.0? W _(A) / W _(B) ? 8.3

When at least two or more polyamides are used as the component (A), W _(A) is calculated as follows.

&Quot; (3) &quot;

W _(A) = W _(A1) + W _(A2) + ... W _(An)

When at least two or more polyamides are used as the component (B), W _(B) is calculated as follows.

&Quot; (4) &quot;

W _(B) = W _(B1) + W _(B2) + ... W _(Bn)

 The other physical properties of the component (A) and the component (B) are softening points. The softening point is a measurement value obtained using a commercially available measuring instrument ([ARES-2 KSTD-FCO-STD] manufactured by Rheometric Scientific). Concretely, the temperature at which the decrease of the stiffness starts to decrease in the viscoelastic profile of each of the component (A) and the component (B) is softened. The value of the softening point is not particularly limited, but is generally as follows from the viewpoint of balance between room temperature adhesiveness, moisture absorption solder heat resistance and low dielectric properties.

Sp _(A) : about 50 deg. C or more and less than 220 deg. C, preferably about 60 deg. C or more and less than 200 deg. C, more preferably about 80 deg. C or more and less than 180 deg.

Sp _(B) : about 50 ° C or more and less than 200 ° C, preferably about 60 ° C or more and less than 180 ° C, more preferably about 70 ° C or more and less than 150 ° C or so

The reason why the adhesive composition of the present invention satisfies the above conditions (1) and (2) is not clear, but it is presumed that the adhesive layer composed of the adhesive composition (A) (C) component forms a dense crosslinked (net) structure. On the other hand, (I) the reaction product of the component (A) and the component (C) having relatively long molecular chains act elastically, I think it might be to harmonize.

 As the component (C), various known ones can be used without particular limitation, provided that they function as a crosslinking agent for polyimide. Specifically, at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound and a cyanate ester compound is preferable.

Examples of the epoxy compound include phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, hydrogen An epoxy compound containing an addition bisphenol F, a stilbene epoxy compound, a triazine skeleton-containing epoxy compound, a fluorene skeleton-containing epoxy compound, a linear aliphatic epoxy compound, an alicyclic epoxy compound, a glycidylamine type epoxy compound, An epoxy compound, an alkyl modified triphenolmethane type epoxy compound, a biphenyl type epoxy compound, a dicyclopentadiene skeleton containing epoxy compound, a naphthalene skeleton containing epoxy compound, an arylalkylene type epoxy compound, tetraglycidyl xylylene diamine, Dimer acid And and the like made of modified epoxy compounds, dimer acid diglycidyl ester, it may be a combination of two or more thereof. Examples of commercially available products include "jER828" and "jER834" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Shinil Chemical Co., YD-172-X75 "manufactured by Shin-il Chemical Co., Ltd.," TETRAD-X "manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among these, the adhesive properties at room temperature, moisture absorption solder heat resistance, At least one selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a hydrogenated bisphenol A type epoxy compound and an alicyclic epoxy compound is preferable from the viewpoint of balance of dielectric properties.

Particularly, the diamine of the following structure is preferable because it lowers the melt viscosity of the adhesive composition and the cured product of the present invention, and also improves the heat-resistant adhesiveness and low-dielectric property of the cured product. Further, the diamine is preferable in view of good compatibility with the component (A) and the component (B), and the cured product becomes transparent. Examples of commercially available diamines include "TETRAD-X" and "TETRAD-C" manufactured by Mitsubishi Gas Chemical Co.,

 [Chemical Formula 12]

　

(Wherein Y represents a phenyl group or a cyclocynyl group).

When an epoxy compound is used as the thermosetting crosslinking agent, various known curing agents for epoxy compounds can be used in combination. Specific examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, trimellic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride or A mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, a mixture of tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nasic anhydride, methylnadic anhydride, norborane-2,3-dicarboxylic acid Acid anhydride-based curing agents such as anhydride, methylnorbornane-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl anhydride succinic acid, and octenyl succinic acid anhydride; Amine curing agents such as dicyandiamide (DICY), aromatic diamines (trade names "Lonzacure M-DEA" and "Lonzacure M-DETDA" all manufactured by Longe Japan Co., Ltd.) and aliphatic amines; Phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, triazine-modified phenol novolac resin, phenol hydroxyl group-containing hydrogenated phenol (such as SPH-100 from Otsuka Chemical Co., Ltd.) A rosin-based curing agent such as a curing agent-circulating hosogen-based compound, and a maleic acid-modified rosin or its hydride; and two or more kinds of these may be used in combination. Among them, a phenol-based curing agent, particularly a phenolic hydroxyl group-containing hosogen-based curing agent, is preferred. The amount of the curing agent to be used is not particularly limited, but is generally about 0.1 to 120% by weight, preferably about 10 to 40% by weight, based on 100% by weight of the solid content of the adhesive composition of the present invention.

A catalyst for promoting the reaction between the epoxy compound and the crosslinking agent may be used. Specific examples thereof include 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol Tertiary amines; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; Organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine and phenylphosphine; Tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate, and the like, or a combination of two or more of them. The amount of the catalyst to be used is not particularly limited, but is generally about 0.01 to 5% by weight when the solid content of the adhesive composition of the present invention is 100% by weight.

Examples of the benzoxazine compound include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) (1-methylethylidene) bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine), and combinations of two or more species. The nitrogen of the oxazine ring is bonded to a phenyl group, a methyl group, a cyclohexyl group, or the like. Examples of commercially available products include "benzooxane F-a type" and "benzoxazine P-d type" manufactured by Sanko Chemical Industry Co., Ltd., and "RLV-100" manufactured by Airworth.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5 -Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane , 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide and the like, or a combination of two or more species may be used. Examples of commercially available products include BAF-BMI manufactured by JFE Kagaku Co., Ltd.

Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanophenol) -1,1,1,3, 3-hexafluoropropane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatphenyl) Bis (4-cyanatophenyl) ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis (4-cyanatphenyl) propane. The above may be combined. Commercial products include, for example, "PRIMASET BTP-6020S (manufactured by Lonsa Japan Co., Ltd.) ".

 The amount of the component (C) to be used is not particularly limited, but it is generally about 1 to 150 parts by weight, preferably about 3 to 100 parts by weight per 100 parts by weight (in terms of solid content) of the components (A) , And more preferably 3 to 75 parts by weight.

 As the component (D), those known as reaction solvents and diluting solvents for polyimide may be used without particular limitation. Specific examples thereof include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltrigrams, Alicyclic solvents such as cyclohexanone and methylcyclohexane; alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol; and aromatic solvents such as toluene. Two or more kinds of these solvents may be used in combination. The amount of the solvent to be used is not particularly limited, but the solid content of the adhesive composition according to the present invention generally ranges from 10 to 60% by weight.

The adhesive composition according to the present invention may further contain additives such as the above-mentioned opening esterification catalyst and dehydration, plasticizer, weathering inhibitor, antioxidant, heat stabilizer, lubricant, antistatic agent, bleaching agent, colorant, A phosphorus flame retardant, a flame retardant coating, a silica coating, and a fluorine filler.

The film-like adhesive of the present invention is an article made of the adhesive composition of the present invention. The article includes a so-called bonding sheet (BS), which is useful as an adhesive for laminating a printed wiring board. The film-like adhesive of the present invention can be obtained, for example, by applying the adhesive on a lower support to heat the component, volatilizing the component (D) and curing the component, and then peeling the support from the support. The curing condition is not particularly limited. However, in order to advance the curing reaction of the component (C) (thermosetting cross-linking agent) after heating to about 70 to 200 ° C and curing reaction for about 1 to 10 minutes, Deg.] C for 10 minutes to 3 hours. The film-like adhesive obtained by two steps of this reaction has a shrinkage of shrinkage, and the adhesion to the substrate becomes good. Further, bubbles due to water as a by-product in the dehydrated ring closure reaction can be easily suppressed. The coating method is not particularly limited, and examples thereof include a curtain coater, a roll coater, and a laminator.

The adhesive layer according to the present invention is a cured layer of the adhesive composition or film-like adhesive according to the invention. The thickness of the cured layer is not particularly limited and can be appropriately adjusted according to the use. For example, when the adhesive composition of the present invention is provided on an adhesive sheet described later, it is usually about 1 to 100 mu m, preferably about 3 to 50 mu m. When the adhesive composition of the present invention is applied to a resin-coated copper foil, the thickness of the cured product is usually about 0.5 to 30 mu m, preferably about 1 to 10 mu m. The adhesive layer may be one of a partially cured state (B stage) and a fully cured state (C stage) under heating in an uncured state (A stage). The thickness of the adhesive layer is not particularly limited and is generally about 0.5 to 30 mu m. The low-dielectric property of the adhesive layer is not particularly limited, but generally, the dielectric constant at a frequency of 10 GHz is about 2.2 to 3.0, and the dielectric loss tangent is about 0.001 to 0.008.

The adhesive sheet of the present invention is a product containing an adhesive layer and a support as constituent elements according to the present invention, and includes a so-called cover layer. As the support, for example, a polyester, a polyimide, a polyimide-silica hybrid, a polyethylene, a polypropylene, a polyethylene terephthalate, a polyethylene naphthalate, a polymethyl methacrylate resin, a polystyrene resin, a polycarbonate resin, (E.g., liquid crystal polymer; KURARAYE "Beckstar &quot;) obtained from phenol, butadiene-styrene resin, ethylene terephthalate or phenol, phthalate, hydroxynaphthoic acid and parahydroxybenzoic acid) Among them, a polyimide film, particularly a polyimide-silica hybrid film, is preferable from the viewpoints of heat resistance and dimensional stability, etc. The polyimide-silica hybrid film may be any of various well- , Preferably, the block-type polyimide-silica hybrid film obtained by thermosetting an alkoxy group-containing silane-modified block-type polyamic acid is preferable. As the block-type polyimide-silica hybrid film, for example, 179638. The adhesive sheet is suitable, for example, as a cover layer film, and can be used for other carrier film carrier tapes, etc. Also, the adhesive composition according to the present invention can be applied to the support The thickness of the coating layer is not particularly limited, but it may be within a range of usually about 1 to 100 μm, preferably about 3 to 50 μm after drying. The adhesive layer of the adhesive sheet is protected by various protective films.

The Resin Coated Copper (RCC) of the present invention is an article comprising the adhesive layer of the present invention and a copper foil as constituent elements. As the copper foil, various known ones can be used without particular limitation. Specifically, for example, a rolled copper foil or an electrolytic copper foil can be mentioned. The thickness is not particularly limited, but is generally about 1 to 100 mu m, preferably about 2 to 38 mu m. The copper foil may also be subjected to various surface treatments (roughening, or rust prevention). Examples of the rust prevention treatment include a so-called mirror-surface treatment such as a plating treatment and a chromate treatment using a plating solution containing Ni, Zn, Sn or the like. The coating means is the same as described above.

The CCL (Copper Clad Laminate) of the present invention is an article comprising the resin-coated copper foil of the present invention as one element. Specifically, the resin-coated copper foil of the present invention is pressed on at least one surface or both surfaces of various known insulating sheets under heating. Further, in the case of a single-sided cross-section, a different one from the resin-bonded copper foil of the present invention may be bonded to the other side. Further, the number of copper foil and the insulating sheet attached to the copper clad laminate is not particularly limited. The insulating sheet is preferably a prepreg. (JIS C5603) in which a reinforcing material such as glass fiber or the like is impregnated with a resin and cured to the B stage (JIS C5603). The resin is generally a polyimide resin, a phenol resin, an epoxy compound, a polyester resin liquid crystal polymer, An insulating resin such as a resin is used. The thickness of the prepreg is not particularly limited and is generally about 20 to 500 탆. The heating and pressing conditions are not particularly limited, but are generally about 150 to 280 DEG C (preferably about 170 DEG C to 240 DEG C) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

The flexible copper clad laminate (FCCL) of the present invention is an article comprising the resin-coated copper foil of the present invention as one element. Concretely, the resin-coated copper foil of the present invention is pressed on at least one side or both sides of various known insulating films under heating. Further, in the case of a single-sided cross-section, a different one from the resin-bonded copper foil of the present invention may be bonded to the other side. Further, the number of copper foil and the insulating sheet in the flexible copper clad laminate is not particularly limited. As the insulating sheet, a polyimide film or a liquid crystal polymer film is generally used. The thickness of the film is not particularly limited, and is generally about 20 to 500 mu m. The conditions for hot pressing are not particularly limited and are generally about 150 to 300 캜 (preferably about 170 캜 to 240 캜) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

The printed wiring board (PWB) of the present invention is an article formed by forming at least one copper foil circuit pattern of the copper clad laminate (CCL) of the present invention or the flexible copper clad laminate (FCCL) of the present invention. As the patterning means, for example, a semi-additive method can be mentioned. Specifically, for example, there is a method of patterning a copper foil surface of a copper-clad laminate of the present invention with a resist film and then performing electrolytic copper plating to remove the resist and etch it with an alkaline solution. The circuit pattern layer of the printed circuit board is not particularly limited.

The flexible printed wiring board (FPWB) of the present invention is an article forming at least one copper foil circuit pattern of the flexible copper clad laminate (FCCL) of the present invention. As the patterning means, for example, a semi-additive method can be mentioned. Specifically, for example, there is a method of patterning a copper foil surface of a flexible copper-clad laminate of the present invention with a resist film and then performing electrolytic copper plating to remove the resist and etch it with an alkaline solution. The circuit pattern layer of the printed circuit board is not particularly limited.

The multi-layer board (MLB) of the present invention is an article comprising the printed wiring board (PWB) and / or the flexible printed wiring board (FPWB) of the present invention as constituent elements. Concretely, the above-mentioned printed wiring board is repeatedly laminated on its end face or both sides with a resin-bonded copper foil of the present invention by bonding, thermosetting, via processing, plating and circuit pattern formation. When laminated, the adhesive layer according to the present invention can be applied. Instead of the resin-coated copper foil of the present invention, a commercially available interlayer insulating material may be used and laminated in the same process.

The printed circuit board (PCB) of the present invention is an article formed by mounting a semiconductor component on a circuit of a printed wiring board (PWB) or a multilayer wiring board (MLB) of the present invention. Examples of the semiconductor component include a silicon chip formed with a minute circuit on one surface or both surfaces (the same applies hereinafter). The mounting is usually performed by soldering, and solder materials include solder paste, solder balls and the like (hereinafter the same).

The flexible printed circuit board (FPCB) of the present invention is an article formed by mounting a semiconductor component on a circuit of a flexible printed wiring board (flexible PWB) or a multilayer wiring board of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the scope of the present invention is not limited thereto. Further, in each of the examples, parts and percentages are by weight unless otherwise specified. The number average molecular weight is a value obtained by using a commercially available measuring instrument ("high speed GPC HLC-8220" manufactured by TOSOH).

&Lt; Preparation of component (A) >

Production Example 1

A commercial aromatic tetracarboxylic acid anhydride (trade name: "BTDA-PF" manufactured by Ebonic Japan Co., Ltd .; 3 ', 4,4'-benzophenonetetra (product name)) was added to a reaction vessel equipped with a stirrer, Carboxylic acid anhydride), 768.00 g of cyclohexanone and 153.60 g of methylcyclohexane were introduced and heated to 60 占 폚. Then, 20.81 g of commercially available polydimethylsiloxane (trade name: KF-8010, manufactured by Shin-Etsu Chemical Co., Ltd.) and 242.60 g of dimer diamine (trade name: PRIAMINE1075 manufactured by Kuroda Japan K.K.) (Non-volatile matter content of 30.1%) of a polyimide (A-1) having a softening point of 80 캜 and a weight average molecular weight of about 25,000 was obtained by imidization reaction. The molar ratio of the acid component / amine component was 1.05.

Production Example 2

210.00 g of commercial aromatic tetracarboxylic acid anhydride (trade name "BTDA-PF" manufactured by Ebonic Japan; 3 ', 4,4'-benzophenonetetracarboxylic dianhydride) in the same reaction vessel as in Production Example 1, 1000.80 g of cyclohexanone and 201.60 g of methylcyclohexane were introduced and heated to 60 캜. Next, 341.67 g of PRIAMINE 1075 was dropped thereon, and imidization reaction was carried out at 140 캜 for 10 hours to obtain a polyimide A-2 solution (nonvolatile matter content of 30.5%) having a softening point of 80 캜 and a weight average molecular weight of about 38,000. The molar ratio of the acid component / amine component was 1.03.

Production Example 3

(4,4 '- [propane 2,2-diylbis (1,4-phenyleneoxy) propane] was added to the same reaction vessel as in Production Example 1, using a commercial aromatic tetracarboxylic acid anhydride (trade name: BISDA1000, manufactured by Ebonic Japan Co., ] Diphthalic anhydride), 780.78 g of cyclohexanone and 156.16 g of methylcyclohexane were introduced and heated to 60 ° C. Next, 211.73 g of PRIAMINE 1075 was added dropwise, followed by imidization reaction at 140 캜 for 10 hours to obtain a polyimide A-3 solution (non-volatile matter content of 31 2.0%) having a softening point of 90 캜 and a weight average molecular weight of about 42,000. The molar ratio of the acid component / amine component was 1.03.

&Lt; Preparation of component (B) >

Production Example 4

160.00 g of BTDA-PF, 768.00 g of cyclohexanone and 153.60 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Thereafter, 18.83 g of KF-8010 and 219.59 g of PRIAMINE 1075 were added dropwise and imidized at 140 ° C. for 10 hours to obtain a polyimide B-1 solution (nonvolatile content 30.7%) having a softening point of 60 ° C. and a weight average molecular weight of about 10,000. The molar ratio of the acid component / amine component was 1.16.

Production Example 5

160.00 g of BTDA-PF, 768.00 g of cyclohexanone and 153.60 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Next, 18.92 g of KF-8010 and 220.54 g of PRIAMINE 1075 were dropped thereon and imidized at 140 ° C. for 10 hours to obtain a polyimide B-2 solution (nonvolatile matter content 30.4%) having a softening point of 60 ° C. and a weight average molecular weight of about 13,000. The molar ratio of the acid component / amine component was 1.16.

Production Example 6

160.00 g of BTDA-PF, 768.00 g of cyclohexanone and 153.60 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Then, 19.00 g of KF-8010 and 221.50 g of PRIAMINE 1075 were added dropwise and imidized at 140 DEG C for 10 hours to obtain a polyimide B-3 solution (nonvolatile matter content 30.8%) having a softening point of 60 DEG C and a weight average molecular weight of about 15,000. The molar ratio of the acid component / amine component was 1.15.

Production Example 7

210.00 g of BTDA-PF, 976.50 g of cyclohexanone and 195.30 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Next, 322.86 g of PRIAMINE 1075 was added dropwise and imidized at 140 ° C. for 10 hours to obtain a polyimide B-4 solution (non-volatile matter content of 30.2%) having a softening point of 80 ° C. and a weight average molecular weight of about 18,000. The molar ratio of the acid component / amine component was 1.09.

Production Example 8

300.00 g of BISDA 1000, 960.00 g of cyclohexanone and 120.00 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Then, 285.82 g of PRIAMINE 1075 was added dropwise, followed by imidization reaction at 140 캜 for 10 hours to obtain a polyimide B-5 solution (non-volatile content 33 0.3%) having a softening point of 90 캜 and a weight average molecular weight of about 20,000. The molar ratio of the acid component / amine component was 1.09.

&Lt; Production of polyimide other than components (A) and (B)

Comparative Preparation Example 1

200.00 g of BTDA-PF, 960.00 g of cyclohexanone and 192.00 g of methylcyclohexane were introduced into the same reaction vessel as in Production Example 1 and heated to 60 占 폚. Subsequently, 520.18 g of KF-8010 was gradually added over 1 hour and imidized at 140 DEG C for 12 hours to obtain a solution (non-volatile matter content of 38.0%) of the acid anhydride group-terminated polyimide (H). The molar ratio of the acid component / amine component of the polyimide resin was 1.05. The weight average molecular weight of the component (a) was about 30,000 and the softening point was 20 ° C.

&Lt; Preparation of adhesive composition >

Example 1

N, N, N ', N'-tetraglycidyl xylylenediamine (manufactured by Nippon Polyurethane Industry Co., Ltd.) as the component (C), 100.00 g of the polyimide A-1 solution (solid content 30.1 g), polyimide B- 2.39 g of Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-X") and 6.23 g of toluene as component (D) were mixed and stirred well to obtain an adhesive composition having a nonvolatile content of 30.0%.

Examples 2 to 12

An adhesive composition was obtained in the same manner as in Example 1 except that the component (A), the component (B), the component (C), the component (D), and the kind and amount of additives were changed to those shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (A) Component (A-1) (A-1) (A-1) (A-1) (A-1) (A-1) Mw _(A) 25000 25000 25000 25000 25000 25000 Sp _(A) 80 80 80 80 80 80 Component (B) (B-4) (B-4) (B-4) (B-3) (B-3) (B-3) Mw _(B) 18000 18000 18000 15000 15000 15000 Sp _{( B )} 80 80 80 80 80 60 (C) Component TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X (C) Component (g) 2.39 1.79 2.01 1.82 2.40 1.79 Toluene (g) 6.24 4.66 5.37 4.75 7.32 4.99 NV (%) 30.0 30.0 30.0 30.0 30.0 30.0 (A) Component (g) 100.00 100.00 100.00 100.00 100.00 100.00 (A) Solid content (%) 30.1% 30.1% 30.1% 30.1% 30.1% 30.1% (B) Component (g) 49.83 11.96 25.91 13.95 50.01 11.73 (B) Solid content (%) 30.2% 30.2% 30.2% 30.2% 30.8% 30.8% (1): 1.1 _? Mw _{( A)} / Mw _(B)? 3.7 1.4 1.4 1.4 1.7 1.7 1.7 (2): 1.5 _? W _{( A)} / W _(B)? 9.5 2.0 8.3 3.8 7.1 2.0 8.3

Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 (A) Component (A-2) (A-2) (A-3) (A-3) (A-3) (A-3) Mw _(A) 38000 38000 42000 42000 42000 42000 Sp _(A) 80 80 90 90 90 90 Component (B) (B-3) (B-3) (B-2) (B-2) (B-2) (B-3) Mw _(B) 15000 15000 13000 13000 13000 15000 Sp _{( B )} 60 60 60 60 60 60 (C) Component TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X (C) Component (g) 2.41 1.83 2.47 1.84 1.92 2.07 Toluene (g) 8.61 6.42 9.54 7.94 7.99 8.98 NV (%) 30.0 30.0 30.0 30.0 30.0 30.0 (A) Component (g) 100.00 100.00 100.00 100.00 100.00 100.00 (A) Solid content (%) 30.5% 30.5% 31.0% 31.0% 31.0% 31.0% (B) Component (g) 48.70 12.87 51.33 12.24 17.34 26.17 (B) Solid content (%) 30.8% 30.8% 30.4% 30.4% 30.4% 30.8% (1): 1.1 _? Mw _{( A)} / Mw _(B)? 3.7 2.5 2.5 3.2 3.2 3.2 2.8 (2): 1.5 _? W _{( A)} / W _(B)? 9.5 2.0 7.7 2.0 8.3 5.9 3.8

Example 13

(Solid content: 10.75 g) of polyimide (A-1) solution, 41.61 g (solid content: 12.90 g) of polyimide (A-3) solution, 32.28 g (solid content: , 2.85 g of TETRAD-X as the component (C), and 11.67 g of toluene as the component (D) were mixed and stirred well to obtain an adhesive composition having a nonvolatile content of 30.0%.

Example 14

(Solid content: 6.99 g) of polyimide (A-1), 41.61 g (solid content: 12.90 g) of polyimide (A-3) solution, 20.98 g (solid content: 2.65 g of TETRAD-X as component (C), and 10.25 g of toluene as component (D) were mixed and stirred well to obtain an adhesive composition having a nonvolatile content of 30.0%.

Example 15

(Solid content: 16.13 g) of polyimide (A-1), 41.61 g (solid content: 12.90 g) of polyimide (A-3) solution, 53.39 g (solid content: 3.13 g of TETRAD-X as component (C), and 9.31 g of toluene as component (D) were mixed and stirred well to obtain an adhesive composition having a nonvolatile content of 30.0%.

Example 16

(Solids content: 7.45 g) of polyimide (A-1), 41.61 g (solid content: 12.90 g) of polyimide (A- , 2.67 g of TETRAD-X as the component (C), and 7.58 g of toluene as the component (D) were mixed and stirred well to obtain an adhesive composition having a nonvolatile content of 30.0%.

Example 17

(Solid content: 4.39 g) of polyimide (A-3) solution (solid content: 43.90 g), polyimide (B-5) solution (19.77 g, solid content: 6.58 g) 2.91 g of TETRAD-X as component (C), and 13.58 g of toluene as component (D) were mixed and stirred well to obtain an adhesive composition having a non-volatile content of 30.0%.

Example 13 Example 14 Example 15 Example 16 Example 17 (A) Component (A-1) + (A-3) (A-1) + (A-3) (A-1) + (A-3) (A-1) + (A-3) (A-3) Mw _{(A) μ} 36900 36900 36900 36900 42000 Sp _(A) 86 86 86 86 90 Component (B) (B-5) (B-5) (B-4) (B-3) (B-5) + (B-2) Mw _{(B) μ} 20000 20000 18000 15000 17200 Sp _{( B )} 90 90 80 80 70 (C) Component TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X (C) Component (g) 2.85 2.65 3.13 2.67 2.91 Toluene (g) 11.67 10.25 9.31 7.58 13.58 NV (%) 30.0 30.0 30.0 30.0 30.0 (A) Component (g) (Total) 141.61 141.61 141.61 141.61 141.61 (A) Solid content (%) 30.4% 30.4% 30.4% 30.4% 31.0% (B) Component (g) (Total) 32.28 20.98 53.39 24.2 34.21 (B) Solid content (%) 33.3% 33.3% 30.2% 30.8% 32.1% (1): 1.1 _? Mw _{( A)} / Mw _(B)? 3.7 1.8 1.8 2.1 2.5 2.4 (2): 1.5 _? W _{( A)} / W _(B)? 9.5 4.0 6.2 2.7 5.8 4.0

Comparative Examples 1 to 8

An adhesive composition was obtained in the same manner as in Example 1 except that the component (A), the component (B), the component (C), the component (D), and the kind and amount of additives were changed to those shown in Table 4.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 (A) Component (A-1) (A-1) (A-1) (A-1) (A-2) (A-2) (A-3) (A-3) Mw _(A) 25000 25000 25000 25000 38000 38000 42000 42000 Sp _(A) 80 80 80 80 80 80 90 90 Component (B) (B-5) (B-5) (B-3) (B-3) (B-3) (B-3) (B-2) (B-2) Mw _(B) 20000 20000 15000 15000 15000 15000 13000 13000 Sp _(B) 90 90 80 80 80 80 60 60 (C) Component TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X (C) Component (g) 3.19 1.75 3.99 1.76 3.21 1.78 3.32 1.79 Toluene (g) 18.00 5.54 13.78 4.81 11.43 6.13 12.46 7.77 NV (%) 30.0 30.0 30.0 30.0 30.0 30.0 30.0 30.0 (A) Component (g) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 (A) Solid content (%) 30.1% 30.1% 30.1% 30.1% 30.5% 30.5% 31.0% 31.0% (B) Component (g) 90.39 9.04 146.59 10.00 97.4 9.74 104.37 9.18 (B) Solid content (%) 33.3% 33.3% 30.8% 30.8% 30.8% 30.8% 30.4% 30.4% (1): 1.1 _? Mw _{( A)} / Mw _(B)? 3.7 1.3 1.3 1.7 1.7 2.5 2.5 3.2 3.2 (2): 1.5 _? W _{( A)} / W _(B)? 9.5 1.0 10.0 0.7 9.8 1.0 10.2 1.0 11.1

Comparative Examples 9-15

An adhesive composition was obtained in the same manner as in Example 1 except that the component (A), the component (B), the component (C), the component (D) and the kind and amount of the additives were changed to those shown in Table 5.

Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 (A) Component (A-2) (A-3) (A-2) (A-2) (A-2) (A-2) (A-1) Mw _(A) 38000 42000 38000 38000 38000 38000 25000 Sp _(A) 80 90 80 80 80 80 80 Component (B) (B-1) (B-1) (B-1) (B-1) (B-1) (B-1) (A-1) Mw _(B) 10000 10000 10000 10000 10000 10000 25000 Sp _(B) 60 60 60 60 60 60 80 (C) Component TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X TETRAD-X (C) Component (g) 1.81 1.92 2.04 2.43 3.23 1.78 1.91 Toluene (g) 6.26 8.10 7.03 8.38 11.55 5.92 4.88 NV (%) 30.0 30.0 30.0 30.0 30.0 30.0 30.0 (A) Component (g) 100.00 100.00 100.00 100.00 100.00 100.00 100.00 (A) Solid content (%) 30.5% 31.0% 30.5% 30.5% 30.5% 30.5% 30.1% (B) Component (g) 11.92 17.17 25.83 50.01 99.35 9.93 20.00 (B) Solid content (%) 30.7% 30.7% 30.7% 30.7% 30.7% 30.7% 30.1% (1): 1.1 _? Mw _{( A)} / Mw _(B)? 3.7 3.8 4.2 3.8 3.8 3.8 3.8 1.0 (2): 1.5 _? W _{( A)} / W _(B)? 9.5 8.3 5.9 3.8 2.0 1.0 10.0 5.0

Comparative Example 16

An adhesive composition was obtained in the same manner as in Example 1, except that the components (a), (C), (D), and the kind and amount of additives were changed to those shown in Table 6.

Comparative Example 16 Polyimide (Ah) M _{W (a)} 30000 (C) Component TETRAD-X Toluene (g) 31.22 NV (%) 30.0

&Lt; Measurement of dielectric constant and dielectric tangent &

The adhesive composition of Example 1 was applied onto a naproton PTFE tape TOMBO No. 1. 9001 (Nichios Corporation), dried at room temperature for 12 hours, and then cured at 200 占 폚 for 1 hour to obtain a sheet of a cured product having a thickness of 50 占 퐉.

Then, a dielectric constant and a dielectric loss tangent of 10 GHz were measured using a commercial dielectric constant measuring apparatus (cavity resonator type, manufactured by AiTi) according to JIS C2565 for the cured sheet. The results are shown in Table 7.

A sheet of a cured product was similarly prepared for the adhesive compositions of other examples and comparative examples, and dielectric constant and dielectric tangent were measured. The results are shown in Table 7.

&Lt; Preparation of adhesive sheet &

The adhesive composition of Example 1 was applied onto a naproton PTFE tape TOMBO No. 1. 9001 (Nichios Corporation) and dried at 180 ° C for 5 minutes to obtain an adhesive sheet having a thickness of 20 μm.

&Lt; Production of copper foil with resin &

The adhesive composition of Example 1 was coated on the mirror surface of an electrolytic copper foil having a thickness of 18 占 퐉 (trade name "F2-WS 'Furukawa Electric Co., Ltd., width 25.4 cm) with a gap coater so that the thickness after drying was 5 占 퐉, And then cut into a predetermined length to obtain a resin-attached copper foil.

&Lt; Fabrication of copper clad laminate &

Subsequently, an epoxy prepreg (trade name: 5100, manufactured by Teraoka Co., Ltd.) having a thickness of 80 mu m was laminated on the bonding surface of the resin-coated copper foil, and the resin-coated copper foil was superimposed thereon. To produce a copper clad laminate.

&Lt; Evaluation of adhesiveness at room temperature &

The peel strength (N / cm) according to JIS C 6481 (test method for copper clad laminate for printed wiring board) for the copper-clad laminate was evaluated. The results are shown in Table 7.

&Lt; Evaluation of moisture-absorbing soldering heat resistance &

The copper clad laminate was allowed to stand in a constant temperature chamber at 23 ° C and 50% R for 4 days, and then the copper foil was placed on the solder bath at 288 ° C with the copper foil down. O shows no change in appearance, X indicates foam, and expansion. The results are shown in Table 7.

A copper-clad laminate was similarly prepared for the adhesive compositions of other examples and comparative examples to evaluate initial adhesion and room temperature adhesiveness. The results are shown in Table 7.

permittivity
(10 GHz) Dielectric tangent
(10 GHz) Adhesion at room temperature
Peel strength
(N / cm) Absorption
pewter
Heat resistance Example 1 2.50 0.0045 10.0 O Example 2 2.55 0.0040 9.0 O Example 3 2.58 0.0043 9.5 O Example 4 2.65 0.0048 8.5 O Example 5 2.55 0.0048 9.0 O Example 6 2.60 0.0045 9.0 O Example 7 2.50 0.0035 9.5 O Example 8 2.55 0.0030 10.0 O Example 9 2.50 0.0040 9.0 O Example 10 2.50 0.0030 10.0 O Example 11 2.50 0.0032 10.5 O Example 12 2.50 0.0035 9.0 O Example 13 2.50 0.0035 10.0 O Example 14 2.50 0.0035 9.5 O Example 15 2.50 0.0035 8.5 O Example 16 2.50 0.0045 9.5 O Example 17 2.50 0.0040 9.5 O Comparative Example 1 2.61 0.0057 5.0 O Comparative Example 2 2.67 0.0055 8.4 X Comparative Example 3 2.62 0.0058 5.3 X Comparative Example 4 5.58 0.0055 8.0 X Comparative Example 5 2.62 0.0045 6.0 O Comparative Example 6 2.58 0.0040 11.6 X Comparative Example 7 2.63 0.0050 6.6 X Comparative Example 8 2.63 0.0045 10.2 X Comparative Example 9 2.40 0.0033 9.0 X Comparative Example 10 2.40 0.0033 9.0 X Comparative Example 11 2.62 0.0045 6.0 O Comparative Example 12 2.50 0.0050 6.0 O Comparative Example 13 2.55 0.0045 5.5 O Comparative Example 14 2.50 0.0035 9.0 X Comparative Example 15 2.55 0.0045 8.0 X Comparative Example 16 2.85 0.011 12.0 X

&Lt; Production of printed wiring board &

Copper foils were dipped in a ferric chloride aqueous solution having a concentration of 40% on both sides of the copper clad laminate according to Example 1 to form a copper circuit with an etching line / space of 0.2 (mm) / 0.2 (mm) to obtain a printed wiring board.

&Lt; Preparation of multilayer wiring board &

Using the obtained printed wiring board as a core material, the resin-coated copper foil of Example 1 was pressed on both sides thereof under the conditions of a pressure of 4.5 MPa, 200 占 폚 and 30 minutes. Subsequently, the untreated copper foil in the outer layer was immersed in a ferric chloride aqueous solution having a concentration of 40% to form a copper circuit with an etching line / space of 0.2 (mm) / 0.2 (mm), thereby obtaining a multilayer wiring board having four circuit pattern layers.

A printed wiring board and a multilayer wiring board were obtained in the same manner as in the other examples of the adhesive composition.

Claims (18)

A long-chain polyimide (A) having as a reaction component a monomer group (?) Containing an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2)
Chain polyimide (B) having as a reaction component a monomer group (?) Comprising an aromatic tetracarboxylic acid anhydride (b1) and a dimer diamine (b2)
The thermosetting cross-linking agents (C),
Containing an organic solvent (D)
Meanwhile,
It is less than (A) 24000 and less than 45000 weight average molecular weight _{(M (A))} is more than 24,000 in the component and (B) a weight average molecular weight of component (M _(B)) is more than 7,000,
Meanwhile,
Wherein the adhesive composition satisfies the following conditions (1) and (2).
(1) 1.1? [M _(A) / M _(B) ]? 3.7
(2) 1.5 ≦ content of component (A) (W _(A) ) / content of component (B) (W _(B) ) ≦ 9.5
The adhesive composition according to claim 1, wherein one or both of the component (a1) and the component (b1) is represented by the following formula.
[Chemical Formula 1]

(Wherein X is a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-X ¹ -OCO- (Wherein X ¹ represents - (CH ₂ ) _l - (l = 1 to 20) or -H ₂ C-HC (-OC (═O) -CH ₃ ) -CH ₂ -).
The adhesive composition according to claim 1 or 2, wherein the component (?) Further comprises an alicyclic diamine (a3) and / or a diaminopolysiloxane (a4).
The adhesive composition according to any one of claims 1 to 3, wherein the component (?) Further comprises an alicyclic diamine (b3) and / or a diaminopolysiloxane (b4).
The adhesive composition according to any one of claims 1 to 4, wherein the component (C) is at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound and a cyanate ester compound .
The adhesive composition according to claim 5, wherein the epoxy compound comprises a diamine of the following structure.
(2)

(Wherein Y represents a phenyl group or a cyclocynyl group).
The adhesive composition according to any one of claims 1 to 6, wherein the content of the component (C) is 1 to 150 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
A film-like adhesive comprising the adhesive composition according to any one of claims 1 to 7.
An adhesive layer comprising the adhesive composition according to any one of claims 1 to 7 or the film adhesive according to claim 8.
An adhesive sheet comprising the adhesive layer according to claim 9 and a substrate sheet as constituent elements.
A resin-attached copper foil (RCC) comprising the adhesive layer according to claim 9 and a copper foil as a component.
A copper clad laminate (CCL) comprising the resin-attached copper foil (RCC) according to claim 11 and a prepreg sheet as constituent elements.
A flexible copper clad laminate (FCCL) comprising the resin-attached copper foil (RCC) according to claim 11 and a polyimide film as a component.
A printed wiring board (PWB) formed by forming a copper foil circuit pattern of a copper clad laminate (CCL) according to claim 12.
A flexible printed wiring board (FPWB) formed by forming a copper foil circuit pattern of a flexible copper clad laminate (FCCL) according to claim 13.
A multilayer wiring board (MLB) comprising a printed wiring board (PWB) according to claim 14 and / or a flexible printed wiring board (FPWB) according to claim 15 as constituent elements,
A printed circuit board (PCB) comprising a semiconductor component mounted on a circuit of a printed wiring board (PWB) according to claim 14 or a circuit of the multilayer wiring board (MLB) according to claim 16.
A flexible printed circuit board (FPCB) comprising a semiconductor component mounted on a circuit of a flexible printed wiring board (FPWB) according to claim 15.

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