TWI690578B - Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, flexible copper-clad laminate, printed circuit board, flexible printed circuit board, multilayer circuit board , Printed circuit boards and flexible printed circuit boards - Google Patents

Abstract

The problem to be solved by the present invention is to provide an adhesive composition capable of forming an adhesive layer (hardened material), which has excellent room temperature adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties.

The solution of the present invention is an adhesive composition, which is characterized by comprising: a long-chain polyimide (A), which contains a single monomer containing an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2) The body group (α) as the reaction component; the short-chain polyimide (B), which reacts with the monomer group (β) containing the aromatic tetracarboxylic anhydride (b1) and the dimer diamine (b2) Component; thermosetting crosslinking agent (C); and, organic solvent (D); and, (A) component weight average molecular weight (M _(A) ) is 24,000 or more and less than 45000, (B) component weight average molecular weight (M _(B) ) is more than 7000 and less than 24000, and the following conditions (1) and (2) are satisfied: (1) 1.1≦[M _(A) /M _(B) ]≦3.7; (2)1.5≦ [Content of (A) component (W _(A) )/(B) content of component (W _(B) )]≦9.5.

Description

Adhesive composition, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, flexible copper-clad laminate, printed circuit board, flexible printed circuit board, multilayer circuit board , Printed circuit boards and flexible printed circuit boards

The invention relates to an adhesive composition, a film-shaped adhesive material, an adhesive layer (hardened material), and an adhesive sheet, a copper foil with resin, a copper-clad laminate, a flexible copper-clad laminate, a printed circuit board, Flexible printed circuit board, multilayer circuit board, printed circuit board, and flexible printed circuit board, the adhesive composition is used to manufacture a flexible printed circuit board, the film-shaped adhesive material is composed of the adhesive composition, The adhesive layer is composed of the adhesive composition and the film-like adhesive material, the adhesive sheet contains the adhesive layer as a constituent element, and the resin-coated copper foil contains the adhesive layer as a constituent element.

In mobile communication devices such as mobile phones or smart phones or their base station devices, network-related electronic devices such as servers/routers, large computers, etc., it is necessary to transmit/process large-capacity messages with low loss and high speed, and The electrical signals processed in the printed circuit boards of these products have also been high-frequency. However, high-frequency electrical signals are easily attenuated, so it is necessary to further reduce the transmission loss in the printed wiring board. Therefore, the requirements are generally used for printing The adhesive composition of the printed circuit board is of low dielectric constant and low dielectric loss tangent (hereinafter also referred to as low dielectric characteristics).

In addition, in order to respond to lead-free solder materials used when mounting components, solder heat resistance at a reflow temperature of about 260°C is required for printed wiring boards. In addition, before the reflow step, in order to suppress blistering or expansion due to moisture absorption, the printed wiring board is mostly pre-dried at a temperature of 100 to 120°C. However, recently, in order to improve production efficiency, the number of cases in which the reflow step is carried out without pre-drying is gradually increasing. Therefore, in addition to the room temperature adhesiveness, the adhesive used for the printed wiring board is required to exhibit solder heat resistance in a hygroscopic state.

As an adhesive composition excellent in room temperature adhesiveness and hygroscopic solder heat resistance and also having low dielectric properties, for example, Patent Document 1 describes a film-like polyimide-based adhesive material having a specific glass transition temperature, Tensile breaking strength and tensile modulus of elasticity, but the film-like polyimide-based adhesive material has insufficient low dielectric properties in the GHz band.

[Prior Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 7-197007

The main problem of the present invention is to provide an adhesive composition capable of forming an adhesive layer (hardened material) which is excellent in room temperature adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties.

The present invention has been devoted to research, and as a result, it has been found that an adhesive composition capable of solving the aforementioned problems can be obtained by combining a polyimide with a relatively long molecular chain and a short poly with a specific condition The imine is further blended with a crosslinking agent.

That is, the present invention relates to an adhesive composition composed of the following composition and related inventions. The related invention has the adhesive composition as a special technical feature.

1. An adhesive composition, characterized in that it contains: a long-chain polyimide (A) composed of a monomer group containing an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2) ( α) as a reaction component; short-chain polyimide (B), which has a monomer group (β) containing an aromatic tetracarboxylic anhydride (b1) and a dimer diamine (b2) as a reaction component; thermal hardening Sexual crosslinking agent (C); and, organic solvent (D); and, (A) component weight average molecular weight (M _(A) ) is 24,000 or more and less than 45000, (B) component weight average molecular weight (M _{(B )} ) Is more than 7000 and less than 24000, and meet the following conditions (1) and (2): (1) 1.1≦[M _(A) /M _(B) ]≦3.7; (2)1.5≦[(A) The content of the component (W _(A) )/(B) The content of the component (W _(B) )]≦9.5.

上述式中，X表示單鍵、-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-或-COO-X¹-OCO-(X¹表示-(CH₂)_l-(l=1~20)或是-H₂C-HC(-O-C(=O)-CH₃)-CH₂-)。 2. The adhesive composition according to the aforementioned item 1, wherein either or both of the component (a1) and the component (b1) are represented by the following general formula:

In the above formula, X represents 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 -(X ¹ means -(CH ₂ ) _l -(l=1~20) or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -).

3. The adhesive composition according to the above item 1 or item 2, wherein the component (α) further contains an alicyclic diamine (a3) and/or a diaminopolysiloxane (a4).

4. The adhesive composition according to any one of items 1 to 3 above, wherein the (β) component further contains an alicyclic diamine (b3) and/or a diaminopolysiloxane ( b4).

化合物、雙馬來醯胺化合物及氰酸酯化合物。 5. The adhesive composition according to any one of items 1 to 4 above, wherein the component (C) contains at least one selected from the group consisting of: epoxy compound, benzo

Compounds, bismaleamide compounds and cyanate compounds.

上述式中，Y表示苯基或環己烯基。 6. The adhesive composition according to item 5 above, wherein the epoxy compound contains a diamine having the following structure,

In the above formula, Y represents phenyl or cyclohexenyl.

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

8. A film-like adhesive material comprising the adhesive composition according to any one of the above items 1 to 7.

9. An adhesive layer comprising the adhesive composition according to any one of items 1 to 7 or the film-like adhesive material according to item 8 above.

10. An adhesive sheet comprising, as its constituent elements, the adhesive layer and the substrate sheet as described in item 9 above.

11. A copper foil (RCC) with resin as its constituent elements, comprising: the adhesive layer and the copper foil as described in item 9 above.

12. A copper-clad laminate (CCL) comprising, as its constituent elements, the copper foil with resin (RCC) as described in item 11 above and a prepreg sheet.

13. A flexible copper-clad laminate (FCCL) comprising, as its constituent elements, the copper foil with resin (RCC) as described in item 11 above and a polyimide film.

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

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

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

17. A printed circuit board (PCB) in which semiconductor parts are built on the circuit of the printed wiring board (PWB) described in the aforementioned item 14 or the multilayer wiring board (MLB) described in the aforementioned item 16 Made.

18. A flexible printed circuit board (FPCB) formed by mounting semiconductor components on a circuit of a flexible printed circuit board (FPWB) as described in the aforementioned item 15.

According to the adhesive composition of the present invention, an adhesive layer (hardened material) can be formed, which is excellent in room-temperature adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties.

The film-like adhesive material obtained from the adhesive composition of the present invention can form an adhesive layer (hardened material), which is excellent in room temperature adhesiveness, hygroscopic solder heat resistance, and low dielectric properties. This adhesive material is suitable as, for example, a die bonding sheet.

The adhesive layer of the present invention is excellent in room temperature adhesiveness, hygroscopic solder heat resistance and low dielectric properties, and can be formed by laminating various substrate sheets (except copper foil) or copper foil to form an adhesive sheet or attached Resin copper foil. The adhesive sheet is useful as an auxiliary material for manufacturing, for example, copper-clad laminates, flexible copper-clad laminates, printed wiring boards, flexible printed wiring boards, multilayer wiring boards, printed circuit boards And flexible printed circuit boards. In addition, the adhesive sheet can also be used as a member (carrier tape, carrier sheet, etc.) for transporting semiconductors.

The copper foil with resin of the present invention, the copper-clad laminate and the flexible copper-clad laminate obtained using the same are used as flexible copper-clad laminates, printed wiring boards, multilayer wiring boards and printed circuit boards. The starting material is useful and enables these to be tangent to low dielectric loss.

The printed wiring board, the flexible printed wiring board, the multilayer wiring board, the printed circuit board and the flexible printed circuit board of the present invention are suitable as flexible printed circuit boards for the following purposes: using smart phones or mobile The telephone is a representative mobile communication device or its base station device, server/router and other network-related electronic devices, large computers, etc.

Figure 1 is a graph of colloidal permeation chromatography (GPC) (measured data) of the polyimide (A-1) of Manufacturing Example 1 and the polyimide (B-4) of Manufacturing Example 7 and it can be understood that the molecular weight distribution is different Situation.

The adhesive composition of the present invention includes: specific polyimide (A) (hereinafter also referred to as (A) component), specific polyimide (B) (hereinafter also referred to as (B) component), and thermosetting Sexual crosslinking agent (C) (hereinafter also referred to as (C) component) and organic solvent (D) (hereinafter also referred to as (D) component).

(A) The component is a polyimide which contains aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as (a1) component) and dimer diamine (a2) (hereinafter also referred to as (a2) The monomer group (α) of the component) (hereinafter also referred to as (α) component) is used as a reaction component, and the (A) component is characterized by a relatively high molecular weight relative to the (B) component.

Component (B) is a polyimide, which contains aromatic tetracarboxylic anhydride (b1) (hereinafter also referred to as (b1) component) and dimer diamine (b2) (hereinafter also referred to as (b2) The monomer group (β) of the component) (hereinafter also referred to as (β) component) is a reaction component, and the (B) component is characterized by a relatively low molecular weight compared to the (A) component.

The component (a1) and the component (b1) may be the same or different, and various well-known aromatic tetracarboxylic anhydrides can be used. Either or both of (a1) component and (b1) component are preferably represented by the following general formula.

In the above formula, X represents 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 -(X ¹ means -(CH ₂ ) _l -(l=1~20) or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -).

Specific examples of the aforementioned aromatic tetracarboxylic anhydride include pyromellitic dianhydride, 4,4'-oxybis(phthalic anhydride), 3,3',4,4'-diphenyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,2,3, 4-Benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-diphenyl ketone tetracarboxylic acid Dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ash tetracarboxylic dianhydride, 2,2-bis(3,3 ',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) lanthanide dianhydride, 2,2-bis(2,3 -Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) propane dianhydride, cyclopentane tetracarboxylic anhydride, butane-1,2,3,4-tetracarboxylic acid, 2,3,5-Tricarboxycyclopentylacetic anhydride, and 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride) Etc.; and more than two types can be combined. Among them, from the viewpoint of the balance of room temperature adhesiveness, hygroscopic solder heat resistance, and low dielectric properties, it is preferably at least one selected from the group consisting of: 3,3',4,4' -Diphenyl ketone tetracarboxylic dianhydride, 4,4'-[propan-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride), and 4,4 '-Oxybis (phthalic anhydride).

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

The dimer diamine is a compound derived from a dimer of unsaturated fatty acid such as oleic acid, that is, a dimer acid (refer to Japanese Patent Laid-Open No. 9-12712, etc.). The non-limiting structural formula is shown below. In each structural formula, m+n=6~17, p+q=8~19, and the dotted line means carbon-carbon single bond or carbon-carbon double bond.

Examples of the commercially available products of the dimer diamine include Versamine 551 (manufactured by BASF Corporation of Japan), Versamine 552 (manufactured by Cognis Japan Ltd., hydride of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (both Croda Japan KK)); etc.; and more than two types can be combined.

The use ratio of the component (a1) and the component (a2) is not particularly limited. In order to achieve the number average molecular weight of the component (A) described later and to optimize the balance between room temperature adhesiveness, moisture absorption solder heat resistance, and low dielectric properties, As long as it is within the following range: [(mol of component (a1)/mole of component (a2)] = about 90 to 120%, preferably about 95 to 115%.

The use ratio of (b1) component and (b2) component is also not particularly limited, in order to achieve the number average molecular weight of (B) component described later and to optimize the balance of room temperature adhesiveness, hygroscopic solder heat resistance and low dielectric properties, As long as it is within the following range: [(b1) component mole/(b2) component mole] = about 90 to 120%, preferably about 95 to 115%.

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

(a3) Component and (b3) component, any one of them can be exemplified by diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl -Diaminodicyclohexylmethane, 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-bis(aminomethyl)cyclohexane, isophorone diamine, etc.; and 2 or more combinations.

(a4) component and (b4) component, any one of them can be exemplified by: α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-amine Propylpropyl) polydimethylsiloxane, α,ω-bis (4-aminobutyl) polydimethylsiloxane, α,ω-bis (5-aminopentyl) polydimethyl Siloxane, α,ω-bis[3-(2-aminophenyl)propyl] polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl] Polydimethylsiloxane, etc.; and more than two types can be combined.

The use ratio of the component (a3) and the component (a4) is not particularly limited, and in order to achieve the number average molecular weight of the component (A) described later and to optimize the balance of room temperature adhesiveness, moisture absorption solder heat resistance, and low dielectric properties, As long as it is within the following range: [Total moles of (a3) component and (a4) component/Total moles of all diamine components] becomes about 0 to 70%, preferably about 0.5 to 50%. In addition, the use ratio of the component (a3) and the component (a4) is not particularly limited, but the molar ratio of the former/the latter is generally about 10/0 to 6/4.

The use ratio of the component (b3) and the component (b4) is not particularly limited. In order to achieve the number average molecular weight of the component (B) described later, the normal temperature is used The balance of adhesiveness, heat resistance of hygroscopic solder, and low dielectric properties may be properly adjusted as long as it is within the following range: [Total moles of (b3) and (b4) components/Total moles of all diamine components ] Becomes about 0 to 70%, preferably about 0.5 to 50%. In addition, the use ratio of the component (b3) and the component (b4) is not particularly limited, but the molar ratio of the former/the latter is generally about 10/0 to 6/4.

The (α) component and the (β) component can be obtained by combining other diamines (hereinafter also referred to as (a5) component and (b5) component). Specifically, for example, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Bis(aminophenoxyphenyl)propanes such as propane; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Diaminodiphenyl ethers such as phenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3'-diaminodiphenyl sulfide, 3,4'-diamino Diphenyl sulfide, 4,4'-diamino diphenyl sulfide and other diamino diphenyl sulfides; 3,3'-diamino diphenyl sulfone, 3,4'-diamine Diphenyl diphenyl sulfone, 4,4'-diamino diphenyl diphenyl benzene, etc.; 3,3'-diamino diphenyl ketone, 4,4'-diamino di Diphenyl diphenyl ketones such as phenyl ketone, 3,4'-diamino diphenyl ketone; 3,3'-diamino diphenyl methane, 4,4'-diamino diphenyl Diaminodiphenylmethanes such as methane, 3,4'-diaminodiphenylmethane; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminobenzene )) propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane and other bis(aminophenyl)propanes; 2,2-bis(3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-( 3-aminobenzene Yl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane and other bis(aminophenyl)hexafluoropropanes; 1,1-bis(3- Aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4- Aminophenyl)-1-phenylethane and other bis(aminophenyl)phenylethanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and other bis(aminophenoxy)benzenes ; 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl) Bis(aminobenzyl)benzenes such as benzene, 1,4-bis(4-aminobenzyl)benzene; 1,3-bis(3-amino-α,α-dimethylbenzene Methyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl ) Bis(aminodimethylbenzyl)benzenes such as benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene; 1,3-bis(3-amine -Α,α-bis(trifluoromethyl)benzyl)benzene, 1,3-bis(4-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,4 -Bis(3-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,4-bis(4-amino-α,α-bis(trifluoromethyl)benzyl ) Benzene and other bis (amino bis (trifluoromethyl) benzyl) benzenes; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminobenzene Oxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl and other aminophenoxybiphenyls; Aminophenoxyphenyl ketones such as bis[4-(3-aminophenoxy)phenyl] ketone, bis[4-(4-aminophenoxy)phenyl] ketone; bis[4- (3-aminophenoxy)phenyl] sulfide, bis[4-(4-aminophenoxy)phenyl] sulfide and other aminophenoxyphenyl sulfides; bis[4-( 3-aminophenoxy)phenyl] benzene, bis[4-(4-aminophenoxy)benzene Amino] phenoxy phenyl phenanthrene; bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether, etc. Aminophenoxyphenyl ethers; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)benzene Group]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3, Aminophenoxyphenylpropanes such as 3-hexafluoropropane; others, 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4- (4-Aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4 -Aminophenoxy)benzyl]benzene, 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis [4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethyl Benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4- Aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl ketone , 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfone, 4,4'-bis[4-(4-amino Phenoxy)phenoxy]diphenyl sulfone, 3,3'-diamino-4,4'-diphenoxydiphenyl ketone, 3,3'-diamino-4,4'- Diphenoxy diphenyl ketone, 3,3'-diamino-4-phenoxy diphenyl ketone, 3,3'-diamino-4-biphenoxy diphenyl ketone, 6 ,6'-bis(3-aminophenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, 6,6'-bis(4-amino (Phenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobisindan, 1,3-bis(3-aminopropyl)tetramethyldisilaxane, 1,3-bis(4-aminobutyl)tetramethyldisilaxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-amine Propyl) ether, bis[(2-aminomethoxy)ethyl] ether, bis[2-(2-aminoethoxy)ethyl] ether, bis[2-(3-aminopropyl) Oxy)ethyl] ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(amine Methoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl) ether, Diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diamino Butane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diamino Nonane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc.; and two or more kinds can be combined. The use amount of these diamines is not particularly limited. When all diamine components are set to 100 mol%, it is generally less than 75 mol%.

(A) component and (B) component can be manufactured by various well-known methods. Taking component (A) as an example, generally, at a temperature of about 60 to 120°C (preferably 80 to 100°C), the components (a1) and (a2) are selected from (a3) as needed At least one of the group consisting of (a4) component and (a5) component is subjected to polymerization addition reaction for about 0.1 to 2 hours (preferably 0.1 to 0.5 hours). Then, as long as it is further at a temperature of about 80 to 250°C, preferably 100 to 200°C, the obtained polymer adduct is subjected to an amide imidization reaction, that is, a dehydration ring-closure reaction for about 0.5 to 50 hours (preferably 1 ~20 hours). The component (B) can also be produced by the same method as the component (A).

In the amide imidization reaction, various well-known reaction catalysts, dehydrating agents, and (D) components described later can be used. Examples of reaction catalysts include: Aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic tertiary amines such as pyridine, picoline, isoquinoline, etc.; and more than two types can be combined . Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic acid anhydride, and two or more types can be combined.

The ring closure rate of the amide imide of the component (A) and the component (B) is not particularly limited, but in general, both are 70% or more, preferably 85 to 100%. "Amidimine ring closure rate" means the content of the cyclic amideimide bond in the (A) component and (B) component (the same below) and can be obtained by, for example, nuclear magnetic resonance (NMR) or infrared (IR) spectroscopy It is determined by various spectroscopic means such as analysis.

The adhesive composition of the present invention is characterized by the balance of the weight-average molecular weight (M _(A) ) of the component (A) from the viewpoint of achieving a balance between room temperature adhesiveness, hygroscopic solder heat resistance, and low dielectric properties. (B) The weight average molecular weight of the component (M _(B) ) is limited. In addition, in this specification, "weight average molecular weight" means the value converted to polystyrene measured by the colloidal permeation chromatography method (the same below). The ranges of M _(A) and M _(B) are as follows.

Generally

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

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

Preferably

M _(A) : more than 24000 and less than 44000

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

Tejia is

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

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

The difference between M _(A) and M _(B) (M _(A) -M _(B) ) is not particularly limited, from the viewpoint of the balance of room temperature adhesiveness, hygroscopic solder heat resistance, and low dielectric properties It is generally about 33,000 or less, preferably about 30,000 or less, and more preferably about 29000 or less.

(A) component may be a combination of two or more polyimides of different M _(A) , and (B) component may also be a polyimide of two or more different M _(B) Composed of amines. At this time, both M _(A) and M _(B) are expressed as arithmetic average values (M _(A)μ , M _(B)μ ). At this time, the range of M _{(A) μ} is regarded as the aforementioned range of M _(A) , and the range of M _{(B) µ} is regarded as the aforementioned range of M _(B) (the same applies hereinafter).

M _(A)μ = [(M _(A1) +M _(A2) +...M _(An) )]/n' (In the above formula, n'is a natural number of 1 or more.)

M _(B)μ = [(M _(B1) +M _(B2) +...M _(Bn) )]/n' (In the above formula, n'is a natural number of 1 or more.)

In the above two formulas, the upper limit of n', that is, the number of polyimides combined, is not particularly limited, and considering productivity, it is generally about 10.

The adhesive composition of the present invention is also characterized in that the ratio of M _(A) and M _(B) is limited to the following from the viewpoint of achieving a balance between room temperature adhesiveness, hygroscopic solder heat resistance, and low dielectric properties. In the above condition (1), the ratio of the content of (A) component (hereinafter referred to as W _(A) ) and the content of (B) component (hereinafter referred to as W _(B) ) is limited to the following condition (2) in.

Generally

(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

Tejia is

(1)1.4≦[M _(A) /M _(B) ]≦3.2

(2)2.0≦[W _(A) /W _(B) ]≦8.3

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

W _(A) =W _(A1) +W _(A2) +…W _(An)

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

W _(B) =W _(B1) +W _(B2) +…W _(Bn)

Examples of the other physical properties of the component (A) and the component (B) include softening points. The softening point is a measured value obtained using a commercially available measuring device ("ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific). Specifically, in the viscoelastic curve of each of the component (A) and the component (B), the temperature at which the rigidity modulus starts to decrease is regarded as the softening point. The value of the softening point is not particularly limited, and it is generally as follows from the viewpoint of the balance between room-temperature adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties.

Sp _(A) : 50°C or more and less than about 220°C, preferably 60°C or more and less than about 200°C, more preferably 80°C or more and less than about 180°C Sp _(B) : 50°C or more and less than 200°C About 60°C or more and less than about 180°C, more preferably 70°C or more and less than 150°C

The reason why the adhesive composition of the present invention can exert the desired effect by satisfying the aforementioned conditions (1) and (2) is presumed to be due to the following reason: In the adhesive layer composed of the adhesive composition In (a), the relatively short molecular chain (B) component and (C) component form a dense cross-linked (mesh) structure, on the other hand, (b) the relatively long molecular chain (A) component and (C ) The reactant of the component acts as an elastomer and moderately roughens the mesh structure.

化合物、雙馬來醯胺化合物及氰酸酯化合物。 As the component (C), as long as it can exhibit performance as a crosslinking agent for polyimide, various known components can be used without particular limitation. Specifically, for example, it is preferably at least one selected from the group consisting of: epoxy compound, benzo

Compounds, bismaleamide compounds and cyanate compounds.

Examples of the epoxy compound include phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A epoxy compounds, bisphenol F epoxy compounds, and bisphenol S epoxy compounds. 、Hydrogenated bisphenol A epoxy compound, hydrogenated bisphenol F epoxy compound, diphenylethylene epoxy compound, epoxy compound with three skeletons, epoxy compound with stilbene skeleton, linear aliphatic epoxy Compound, alicyclic ring Oxygen compounds, epoxypropylamine type epoxy compounds, triphenol phenol methane type epoxy compounds, alkyl modified triphenol methane type epoxy compounds, biphenyl type epoxy compounds, epoxy containing dicyclopentadiene skeleton Compounds, epoxy compounds containing a naphthalene skeleton, aryl alkylene type epoxy compounds, tetraglycidoxypropyl xylenediamine, modified epoxy compounds modified with dimer acids Polymer acid diglycidyl ester; etc.; and two or more kinds can be combined. Examples of commercially available products include "jER828" or "jER834" and "jER807" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; Daicel Chemical Industry Co., Ltd. "CELLOXIDE 2021P" manufactured by Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among them, from the viewpoint of the balance between room temperature adhesiveness, moisture absorption solder heat resistance, and low dielectric properties, it is preferably at least one selected from the group consisting of: bisphenol A type epoxy compound, bis Phenol F-type epoxy compound, hydrogenated bisphenol A-type epoxy compound, and alicyclic epoxy compound.

In particular, the diamine having the following structure can reduce the melt viscosity of the adhesive composition and the cured product of the present invention, and can improve the heat-resistant adhesiveness and low dielectric properties of the cured product, which is preferable. In addition, the diamine has good compatibility with the component (A) and the component (B) and can make the cured product transparent, which is also preferable. Examples of commercially available products of this diamine include "TETRAD-X" or "TETRAD-C" manufactured by Mitsubishi Gas Chemical Co., Ltd.

In the above formula, Y represents phenyl or cyclohexenyl.

When an epoxy compound is used as a thermosetting crosslinking agent, various known curing agents for epoxy compounds can be used in combination. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride Formic anhydride, 4-methyl-hexahydrophthalic anhydride, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl -Tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methyl alcohol Anhydride-based hardeners such as dicyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamine (DICY), aromatic diamine (trade name "LonzacureM-DEA", " LonzacureM-DETDA", etc. are all manufactured by Lonza Japan Ltd.), aliphatic amines and other amine hardeners; phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, three modified phenol novolak resin , Phenolic hydroxyl-containing phosphazenes (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.) and other phenolic hardeners, cyclic phosphazene compounds; maleic acid-modified rosin or its hydride Rosin-based cross-linking agent, etc.; and more than two types can be combined. Among them, phenolic hardeners are preferred, and phenolic hydroxyl groups are particularly preferred Based phosphazene hardener. The use amount of these hardeners is not particularly limited. Generally speaking, when the solid content of the adhesive composition of the present invention is 100% by weight, it is about 0.1 to 120% by weight, preferably 10 to 40% by weight %about.

A catalyst for promoting the reaction of the aforementioned epoxy compound with its cross-linking agent can also be used. Specifically, for example, 1,8-diaza-bicyclo[5.4.0]undecane-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamino Tertiary amines such as ethanol and ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, etc. Imidazoles; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphines; tetraphenylphosphonium tetraphenylphosphonium (tetraphenyl phosphonium tetraphenylborate), tetraphenyl Tetraphenylborate, such as boric acid 2-ethyl-4-methylimidazole, tetraphenylboronic acid N-methylmorpholine, etc.; and two or more types can be combined. In addition, the amount of the reaction catalyst used is not particularly limited. Generally speaking, when the solid content of the adhesive composition of the present invention is 100% by weight, it is about 0.01 to 5% by weight.

化合物，可列舉例如：6,6-(1-甲基亞乙基)雙(3,4-二氫-3-苯基-2H-1,3-苯并

)、6,6-(1-甲基亞乙基)雙(3,4-二氫-3-甲基-2H-1,3-苯并

)等；且可將2種以上組合。再者，在環的氮上可鍵結有苯基、甲基、環己基等。又，作為市售品，可列舉例如四國化成工業股份有限公司製造的 「Benzoxazine F-a型」或「Benzoxazine P-d型」、AIR WATER INC.製造的「RLV-100」等。 As the aforementioned benzo

Compounds include, for example: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzo

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

) Etc.; and more than two types can be combined. Furthermore, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the ring. In addition, examples of commercially available products include "Benzoxazine Fa type" or "Benzoxazine Pd type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by AIR WATER INC., and the like.

Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, meta-phenylene bismaleimide, and bisphenol A diphenyl ether bismaleimide. Laimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-benzidine Bis-maleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenyl bismaleimide, etc.; and more than two types can be combined. In addition, examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Corporation.

Examples of the cyanate compound include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanophenol)-1,1,1 , 3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-ginseng (4-cyanic acid Phenyl)ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2 -Bis(4-cyanophenyl)propane, etc.; and two or more kinds can be combined. In addition, examples of commercially available products include "PRIMASET BTP-6020S (manufactured by Lonza Japan Ltd.)" and the like.

(C) The use amount of the component is not particularly limited. Generally speaking, it is about 1 to 150 parts by weight relative to the total amount of 100 parts by weight of the (A) component and (B) component (calculated as solid content). It is preferably about 3 to 100 parts by weight, and more preferably 3 to 75 parts by weight.

As the component (D), various well-known solvents can be used without particular limitation as the reaction solvent or dilution solvent of polyimide. Specifically, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyl Aprotic polar solutions such as triethylene glycol dimethyl ether and methyl diglyme; or, alicyclic solvents such as cyclohexanone and methylcyclohexane; methanol, ethanol, propanol, benzyl alcohol, methyl alcohol Alcohol solvents such as phenol; aromatic solvents such as toluene; etc.; and two or more kinds can be combined. In addition, the amount of the organic solvent used is not particularly limited, but it is generally in the range of about 10 to 60% by weight of the solid content of the adhesive composition of the present invention.

In the adhesive composition of the present invention, the aforementioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, slip agent, antistatic agent, whitening agent may be blended as needed , Colorants, conductive agents, release agents, surface treatment agents, viscosity regulators, phosphorus flame retardants, flame retardant fillers, silica fillers, fluorine fillers and other additives, fillers.

The film-shaped adhesive material of the present invention is an article composed of the adhesive composition of the present invention. This article includes a so-called bonding sheet (BS), which is useful as an adhesive material for laminating printed wiring boards. The film-like adhesive material of the present invention can be obtained, for example, by applying the adhesive to a support described later, heating it to volatilize the component (D), hardening it, and then peeling it from the support. The curing conditions are not particularly limited. First, it is generally heated to about 70 to 200° C. and takes about 1 to 10 minutes to undergo a curing reaction, and then further heat treatment is performed to make the component (C) (thermosetting crosslinking agent) Hardening reaction The heat treatment is usually about 150~250℃, about 10 minutes~3 hours. By carrying out the two-stage reaction in this way, the obtained sheet-shaped adhesive material shrinks more slowly and has good adhesion to the substrate. Also, in the aforementioned dehydration ring-closing reaction reaction, it becomes easy to suppress foaming caused by water as a by-product. In addition, the coating means is not particularly limited, and examples thereof include a curtain coater, a roll coater, and a laminator.

The adhesive layer of the present invention is a hardened layer of the adhesive composition or film-like adhesive material of the present invention. The thickness of the hardened layer is not particularly limited, and can be appropriately adjusted according to the application. For example, when the adhesive composition of the present invention is provided for an adhesive sheet described later, it is generally about 1 to 100 μm, preferably about 3 to 50 μm. In addition, when the adhesive composition of the present invention is provided for a copper foil with resin, the film thickness of the cured product is generally about 0.5 to 30 μm, preferably about 1 to 10 μm. In addition, the adhesive layer may be any of an uncured state (stage A), a partially cured state under heating (stage B), and a completely cured state under heating (stage C). The thickness of the adhesive layer is not particularly limited, but is generally about 0.5 to 30 μm. The low dielectric property of the adhesive layer is not particularly limited. Generally speaking, 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 an article, and as its constituent elements, it includes the adhesive layer and the support of the present invention, and includes a so-called coverlay. Examples of the support include the following plastic films: polyester, polyimide, polyimide-silica mixture, polyethylene, polypropylene, polyethylene terephthalate, and polynaphthalene Ethylene formate, Polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate or phenol, phthalic acid, hydroxynaphthoic acid, etc. Aromatic polyester resin obtained from p-hydroxybenzoic acid (so-called liquid crystal polymer, "Vecstar" manufactured by KURARAY CO., LTD., etc.), etc. Among them, from the viewpoint of heat resistance and dimensional stability, a polyimide film is preferred, and a polyimide-silica mixture film is particularly preferred. As the polyimide-silica mixture film, various known polyimide-silica mixture films can be used without particular limitation, and it is preferably a modified block copolymer type modified from alkoxysilane-containing A block copolymerized polyimide-silica mixture film obtained by thermally curing polyamic acid. As the block copolymerization type polyimide-silica mixture film, for example, the block copolymerization type polyimide-silica mixture film described in Japanese Patent Laid-Open No. 2014-179638 is preferable. This adhesive sheet is suitable as a protective film, for example, and can also be used as a carrier film or a carrier tape. In addition, when applying the adhesive composition of the present invention to the support, the aforementioned coating means can be used. The thickness of the coating layer is also not particularly limited, as long as it is within the following range: generally, the thickness after drying becomes about 1 to 100 μm, preferably about 3 to 50 μm. In addition, the application means may be the aforementioned application means. In addition, various protective films can be used to protect the adhesive layer of the adhesive sheet.

The resin-coated copper foil (RCC: Resin Coated Copper) of the present invention is an article that includes the adhesive layer of the present invention and a copper foil as its constituent elements. As the copper foil, various known copper foils can be used without particular limitation. Specifically, for example, rolled copper foil or electric Solution copper foil. In addition, the thickness is not particularly limited, but is generally about 1 to 100 μm, preferably about 2 to 38 μm. In addition, the copper foil may be a copper foil subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the anti-rust treatment include so-called mirror treatment such as plating treatment using a plating solution containing nickel, zinc, tin, and the like, or chromate treatment. In addition, as the coating means, the aforementioned coating means may be used.

The copper-clad laminate (CCL: Copper Clad Laminate) of the present invention is an article that uses the copper foil with resin of the present invention as one of the elements. Specifically, it is an article obtained by press-bonding the copper foil with resin of the present invention on at least one side or both sides of various well-known insulating sheets under heating. In the case of one side, a different one from the resin-coated copper foil of the present invention may be pressed on the other side. In addition, the number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited. In addition, the insulating sheet is preferably a prepreg. A prepreg refers to a sheet-like material, which is obtained by impregnating a reinforcing material such as glass cloth with a resin and hardening it up to the B stage (Japanese Industrial Standard (JIS) C5603). As the resin, a polymer is generally used. Insulating resins such as amide imide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, polyaromatic amide resin. In addition, the thickness of the prepreg is not particularly limited, but is generally about 20 to 500 μm. The heating and pressing conditions are not particularly limited, but are generally about 150 to 280°C (preferably about 170°C to 240°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 that uses the copper foil with resin of the present invention as one of the elements. Specifically, it is an article obtained by press-bonding the copper foil with resin of the present invention on at least one side or both sides of various well-known insulating films under heating. In addition, in the case of one side, a different one from the resin-coated copper foil of the present invention may be pressed on the other side. In addition, the number of resin-coated copper foils and insulating sheets in the flexible copper-clad laminate is not particularly limited. In addition, as the insulating sheet, a polyimide film or a liquid crystal polymer film is generally used. In addition, the thickness of the film is not particularly limited, but is generally about 20 to 500 μm. The heating and pressing conditions are not particularly limited, but are generally about 150 to 300°C (preferably about 170°C to 240°C) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

The printed wiring board (PWB: Printed Wiring Board) of the present invention is an article in which a circuit pattern is formed on the copper-clad laminate (CCL) of the present invention or the flexible copper-clad laminate (FCCL) of the present invention Made from at least one copper foil. As a patterning means, for example, a semi-additive method can be mentioned. Specifically, the following method may be mentioned: On the copper foil surface of the copper-clad laminate of the present invention, a resist film is patterned, then electrolytic copper plating is performed to remove the resist, and then etching is performed with an alkaline solution. In addition, the circuit pattern layer in this printed wiring board is not particularly limited.

The flexible printed wiring board (FPWB: Flexible Printed Wiring Board) of the present invention is an article in which a circuit pattern is formed on the flexible copper-clad laminate of the present invention (FCCL) on at least one copper foil. As a patterning means, for example, a semi-additive method can be mentioned. Specifically, the following method may be mentioned: On the copper foil surface of the flexible copper-clad laminate of the present invention, a resist film is patterned, and then electrolytic copper plating is performed to remove the resist, and then use an alkaline solution Perform etching. In addition, the circuit pattern layer in this printed wiring board is not particularly limited.

The multilayer wiring board (MLB: Multi-Layer Board) of the present invention is an article, and its constituent elements include the printed wiring board (PWB) and/or flexible printed wiring board (FPWB) of the present invention. Specifically, the following articles can be cited: using the printed wiring board as a core material, and using one or both sides of the resin-coated copper foil of the present invention, lamination, thermosetting, through-hole processing, and plating are repeated Cover and form a circuit pattern to build up. When laminating, the adhesive layer of the present invention can be applied. Alternatively, a commercially available interlayer insulating material may be used instead of the resin-coated copper foil of the present invention, and the lamination may be performed in the same procedure.

The printed circuit board (PCB: Print Circuit Board) of the present invention is an article that is formed by mounting semiconductor components on the printed circuit board (PWB) or multilayer circuit board (MLB) circuit of the present invention. Examples of semiconductor components include silicon wafers in which fine circuits are formed on one or both surfaces (the same applies hereinafter). Generally, the mounting is performed by soldering, and examples of soldering materials include solder paste and solder ball.

The flexible printed circuit board (FPCB: Flexible Print Circuit Board) of the present invention is an article, which The semiconductor component is constructed on the circuit of the flexible printed circuit board (Flexible PWB) or multilayer circuit board of the present invention.

[Example]

The present invention will be specifically described below through examples and comparative examples, but the scope of the present invention is not limited to these examples and comparative examples. In addition, in each case, unless otherwise noted, parts and% are based on weight. In addition, the number average molecular weight is a value obtained using a commercially available measuring machine ("High Speed GPC HLC-8220", manufactured by Tosoh Corporation).

<Manufacture (A) component>

(Production Example 1)

160.00g of commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", Evonik Japan Co., Ltd.) was put in a reaction vessel equipped with a stirrer, water separator, thermometer and nitrogen introduction tube Co., Ltd.) manufactured 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride), 768.00g of cyclohexanone, and 153.60g of methylcyclohexane, and heated to 60 ℃ until. Then, 20.81g of commercially available polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 242.60g of dimer diamine (trade name "PRIAMINE 1075") were added dropwise. Croda Japan Co., Ltd.), and then spent 10 hours at 140 ℃ to carry out the amide imidization reaction, thereby obtaining a solution of a polyimide (A-1) having a softening point of about 80 ℃ and a weight average molecular weight of about 25,000 ( Non-volatile content 30.1%). In addition, the molar ratio of the acid component/amine component was 1.05.

(Production Example 2)

In the same reaction vessel as in Production Example 1, 210.00 g of commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", 3, 3', 4, manufactured by Evonik Japan Co., Ltd., 4'-diphenyl ketone tetracarboxylic dianhydride), 1000.80 g of cyclohexanone, and 201.60 g of methylcyclohexane, and heated up to 60°C. Then, 341.67 g of PRIAMINE 1075 was added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a solution of polyimide (A-2) having a softening point of approximately 80° C. and a weight average molecular weight of approximately 38,000. (30.5% of non-volatile components). In addition, the molar ratio of the acid component/amine component was 1.03.

(Production Example 3)

In the same reaction vessel as in Production Example 1, 210.00 g of commercially available aromatic tetracarboxylic dianhydride (trade name "BISDA1000", 4,4'-[propyl-2 manufactured by Evonik Japan Co., Ltd. ,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride)), 780.78g of cyclohexanone, and 156.16g of methylcyclohexane, and heated to 60 ℃ until. Subsequently, 211.73 g of PRIAMINE 1075 was added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a solution of polyimide (A-3) having a softening point of approximately 90° C. and a weight average molecular weight of approximately 42,000. (Non-volatile content 31.0%). In addition, the molar ratio of the acid component/amine component was 1.03.

<Manufacture (B) component>

(Production Example 4)

In the same reaction vessel as in Production Example 1, 160 g of BTDA-PF, 768.00 g of cyclohexanone, and 153.60 g of methyl ring were put in Hexane, and heated to 60 ℃. Then, 18.83g of KF-8010 and 219.59g of PRIAMINE1075 were added dropwise, and then the amide imidization reaction was carried out at 140°C for 10 hours, thereby obtaining a polyimide having a softening point of about 60°C and a weight average molecular weight of about 10,000. (B-1) solution (30.7% of non-volatile components). In addition, the molar ratio of the acid component/amine component was 1.16.

(Production Example 5)

In the same reaction vessel as in Production Example 1, 160 g of BTDA-PF, 768.00 g of cyclohexanone, and 153.60 g of methylcyclohexane were charged and heated to 60°C. Then, 18.92 g of KF-8010 and 220.54 g of PRIAMINE 1075 were added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a polyimide having a softening point of about 60° C. and a weight average molecular weight of about 13,000. (B-2) solution (30.4% of non-volatile content). In addition, the molar ratio of the acid component/amine component was 1.16.

(Production Example 6)

In the same reaction vessel as in Production Example 1, 160 g of BTDA-PF, 768.00 g of cyclohexanone, and 153.60 g of methylcyclohexane were charged and heated to 60°C. Then, 19.00 g of KF-8010 and 221.50 g of PRIAMINE 1075 were added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a polyimide having a softening point of about 60° C. and a weight average molecular weight of about 15,000. (B-3) solution (non-volatile content 30.8%). In addition, the molar ratio of the acid component/amine component was 1.15.

(Production Example 7)

In the same reaction vessel as in Production Example 1, 210.00 g of BTDA-PF, 976.50 g of cyclohexanone, and 195.30 g of methylcyclohexane were charged and heated to 60°C. Subsequently, 322.86 g of PRIAMINE 1075 was added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a solution of polyimide (B-4) having a softening point of approximately 80° C. and a weight average molecular weight of approximately 18,000. (Non-volatile content 30.2%). In addition, the molar ratio of the acid component/amine component is 1.09.

(Production Example 8)

In the same reaction vessel as in Production Example 1, 300.00 g of BISDA1000, 960.00 g of cyclohexanone, and 120.00 g of methylcyclohexane were charged and heated up to 60°C. Then, 285.82 g of PRIAMINE 1075 was added dropwise, and then the amide imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a solution of a polyimide (B-5) having a softening point of approximately 90° C. and a weight average molecular weight of approximately 20,000. (Non-volatile content 33.3%). In addition, the molar ratio of the acid component/amine component is 1.09.

<Manufacture of polyimide other than (A) component and (B) component>

(Comparative manufacturing example 1)

In the same reaction vessel as in Production Example 1, 200.00 g of BTDA-PF, 960.00 g of cyclohexanone, and 192.00 g of methylcyclohexane were charged and heated to 60°C. Then, it took 1 hour to slowly drop 520.18 g of KF-8010, and then spent 12 hours at 140° C. to carry out the imidization reaction, thereby obtaining a solution of the acid anhydride group-terminated polyimide (a) Liquid (non-volatile content 38.0%). In addition, the molar ratio of the acid component/amine component of this polyimide resin was 1.05. In addition, the weight average molecular weight of the component (a) is about 30,000, and the softening point is 20°C.

<Formulation of adhesive composition>

(Example 1)

A solution of 100.00 g (solid content 30.1 g) of polyimide (A-1), 49.51 g (solid content 14.95 g) of polyimide (B-4) solution, and (C) component 2.39 g of N,N,N',N'-tetraepoxypropylxylenediamine (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "TETRAD-X") and 6.23g of toluene as the component (D), Stir uniformly to obtain a 30.0% non-volatile adhesive composition.

(Examples 2-12)

(A) component, (B) component, (C) component, (D) component and additive and usage amount are changed as shown in Tables 1 and 2 except that it is carried out in the same manner as in Example 1 to obtain an adhesive Composition.

(Example 13)

Mix 100.00g (solid content 30.1g) of polyimide (A-1) solution, 41.61g (solid content 12.90g) of polyimide (A-3) solution, 32.28g (solid content 10.75g ) A solution of polyimide (B-5), TETRAD-X 2.85g as the (C) component and 11.67g toluene as the (D) component, and uniformly stirred to obtain a nonvolatile component 30.0 % Adhesive composition.

(Example 14)

A solution of 100.00 g (solid content 30.1 g) of polyimide (A-1), 41.61 g (solid content 12.90 g) of polyimide (A-3) solution, 20.98 g (solid content 6.99 g) ) A solution of polyimide (B-5), TETRAD-X 2.65g as the (C) component and 10.25g toluene as the (D) component, and uniformly stirred to obtain a nonvolatile component 30.0 % Adhesive composition.

(Example 15)

Mix 100.00g (solid content 30.1g) of polyimide (A-1) solution, 41.61g (solid content 12.90g) of polyimide (A-3) solution, 53.39g (solid content 16.13g ) A solution of polyimide (B-4), 3.13g of TETRAD-X as the (C) component and 9.31g of toluene as the (D) component, and uniformly stirred to obtain a nonvolatile component 30.0 % Adhesive composition.

(Example 16)

A solution of 100.00 g (solid content 30.1 g) of polyimide (A-1), 41.61 g (solid content 12.90 g) of polyimide (A-3) solution, 24.20 g (solid content 7.45 g) ) A solution of polyimide (B-3), 2.67g of TETRAD-X as component (C) and 7.58g of toluene as (D) component, and uniformly stirred to obtain a nonvolatile component 30.0 % Adhesive composition.

(Example 17)

A solution of polyimide (A-3) of 141.61 g (solid component 43.90 g), a solution of polyimide (B-5) of 19.77 g (solid component 6.58 g), 14.44 g (4.39 g of solid component) ) Solution of polyimide (B-2), 2.91g of TETRAD-X as component (C) and 13.58g of toluene as (D) component, and uniformly stirred to obtain a nonvolatile component 30.0 % Adhesive composition.

[table 3]

(Comparative Examples 1~8)

The components (A), (B), (C), (D) and the additives and their amounts were changed as shown in Table 4, and the same procedure as in Example 1 was carried out to obtain an adhesive composition.

(Comparative Examples 9~15)

The (A) component, (B) component, (C) component, (D) component, and additive were changed as shown in Table 5, and it carried out similarly to Example 1, and obtained the adhesive composition.

(Comparative Example 16)

The component (a), the component (C), the component (D) and the additives and the amounts were changed as shown in Table 6, and the same procedure as in Example 1 was carried out to obtain an adhesive composition.

<Determination of dielectric constant and dielectric loss tangent>

The adhesive composition of Example 1 was coated on NAFLON PTFE tape TOMBO No. 9001 (manufactured by NICHIAS Corporation), dried at room temperature for 12 hours, and then cured at 200°C 1 hour, thereby obtaining a cured product sheet with a film thickness of 50 μm.

Then, according to JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET INC.) was used to measure the dielectric constant and dielectric loss tangent at 10 GHz. The results are shown in Table 7.

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

<Making Adhesive Sheet>

The adhesive composition of Example 1 was coated on NAFLON PTFE tape TOMBO No. 9001 (manufactured by NICHIAS Corporation), and dried at 180° C. for 5 minutes, thereby obtaining an adhesive sheet with a film thickness of 20 μm.

<Making copper foil with resin>

Using a gap coater, the adhesive composition of Example 1 was applied to an 18-μm-thick electrolytic copper foil (trade name “F2-WS”) so that the film thickness after drying became 5 μm. Manufactured by Furukawa Electric Industry Co., Ltd. (roll shape with a width of 25.4 cm), then dried at 200°C for 3 minutes, and then cut to a specific length to obtain a copper foil with resin.

<Making copper clad laminates>

Then, the epoxy prepreg (trade name "5100" manufactured by Teraoka Manufacturing Co., Ltd.) after 80 μm was laminated on the adhesive surface of the resin-coated copper foil, and the resin-coated copper foil was further added. After being laminated on it, heat-pressing was carried out under the conditions of a pressure of 4.5 MPa, 200° C. and 30 minutes, thereby producing a copper-clad laminate.

<Evaluation of room temperature adhesiveness>

For this copper-clad laminate, the peel strength (N/cm) was evaluated in accordance with JIS C 6481 (Test method for copper-clad laminate for printed wiring boards). The results are shown in Table 7.

<Evaluation of heat resistance of hygroscopic solder>

The copper-clad laminate was placed in a constant temperature room at 23°C and 50% relative humidity (RH) for 4 days. Afterwards, the copper foil was turned down and floated in a solder bath at 288°C. bubble. ○ indicates no change in appearance, and × indicates that blistering and swelling are observed. The results are shown in Table 7.

For the adhesive compositions of other examples and comparative examples, copper-clad laminates were also produced in the same manner, and the heat resistance of the hygroscopic solder and the room temperature adhesiveness were evaluated. The results are shown in Table 7.

[Table 7]

<Making Printed Circuit Board>

Etching was performed by immersing the double-sided copper foil of the copper-clad laminate of Example 1 into a 40% concentration aqueous solution of ferric chloride to form a line width/pitch=0.2(mm)/0.2(mm) Copper circuit, thereby obtaining a printed circuit board.

<Making multilayer circuit board>

The obtained printed wiring board was used as a core material, and the copper foil with resin of Example 1 was laminated on its both sides, and then pressed together at a pressure of 4.5 MPa, 200° C., and 30 minutes. Then, by immersing the unprocessed copper foil of the outer layer in a 40% concentration aqueous solution of ferric chloride to perform etching, a copper circuit with a line width/pitch=0.2(mm)/0.2(mm) was formed by This results in a multilayer wiring board with 4 circuit pattern layers.

The adhesive composition of other embodiments is also carried out in the same manner to obtain printed wiring boards and multilayer wiring boards.

Claims (18)

An adhesive composition characterized by comprising: a long-chain polyimide (A), a monomer group (α) comprising an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2) As a reaction component; short-chain polyimide (B), which uses a monomer group (β) containing aromatic tetracarboxylic anhydride (b1) and dimer diamine (b2) as a reaction component; thermosetting crosslinking Agent (C); and, organic solvent (D); and, (A) component weight average molecular weight M _(A) is 24000 and less than 45000, (B) component weight average molecular weight M _(B) is 7000 or more and Less than 24000, and satisfy the following conditions (1) and (2): (1) 1.1≦[M _(A) /M _(B) ]≦3.7; (2)1.5≦[(A) component content W _{(A )} /(B) The content of component W _(B) ]≦9.5. The adhesive composition according to claim 1, wherein either or both of the component (a1) and the component (b1) are represented by the following general formula:

In the above formula, X represents 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 -, where X ¹ represents -(CH ₂ ) _l -, l=1~20 or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -. The adhesive composition according to claim 1 or 2, wherein the component (α) further contains an alicyclic diamine (a3) and/or a diaminopolysiloxane (a4). The adhesive composition according to claim 1 or 2, wherein the (β) component further contains an alicyclic diamine (b3) and/or a diaminopolysiloxane (b4). The adhesive composition according to claim 1 or 2, wherein the component (C) contains at least one selected from the group consisting of epoxy compounds, benzo

Compounds, bismaleamide compounds and cyanate compounds. The adhesive composition according to claim 5, wherein the epoxy compound contains a diamine having the following structure:

In the above formula, Y represents phenyl or cyclohexenyl. The adhesive composition according to claim 1 or 2, wherein the content of the component (C) is 1 to 150 parts by weight relative to 100 parts by weight of the total amount of the components (A) and (B). A film-like adhesive material composed of the adhesive composition according to any one of claims 1 to 7. An adhesive layer composed of the adhesive composition according to any one of claims 1 to 7 or the film-like adhesive material according to claim 8. An adhesive sheet comprising the adhesive layer and the substrate sheet as described in claim 9 as its constituent elements. A copper foil with a resin comprising the adhesive layer as described in claim 9 and copper foil as its constituent elements. A copper-clad laminate comprising the copper foil with resin as described in claim 11 and a prepreg sheet as its constituent elements. A flexible copper-clad laminate comprising the copper foil with resin as described in claim 11 and a polyimide film as its constituent elements. A printed wiring board formed by forming a circuit pattern on the copper foil of the copper-clad laminate according to claim 12. A flexible printed wiring board formed by forming a circuit pattern on the copper foil of the flexible copper-clad laminate according to claim 13. A multilayer wiring board comprising the printed wiring board described in claim 14 and/or the flexible printed wiring board described in claim 15 as its constituent elements. A printed circuit board which constructs semiconductor parts on the printed wiring board as described in claim 14 or as described in claim 16 Made of multi-layer circuit boards. A flexible printed circuit board is constructed by mounting semiconductor components on the circuit of the flexible printed circuit board according to claim 15.

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