TWI754668B - Copper clad laminate for flexible printed circuit board and flexible printed circuit board - Google Patents

Abstract

The problem to be solved by the present invention is to provide a copper clad laminate, Even when the low-roughness copper foil with Rz of 1.5 μm or less is used, excellent adhesiveness (peel strength (N/m) of copper foil) can be exhibited by the adhesive layer of the film.

The solution of the present invention is a copper-clad laminate for a flexible printed circuit board, comprising: (1) copper foil, the 10-point average roughness (Rz) of the adhesive surface of which is 0.1-1.5 μm; (2) adhesive layer, which is a thermosetting product of an adhesive (2') with a thickness of 2 to 5 μm, and the adhesive (2') contains the reactant of the reactive component (α), that is, the acid anhydride group-terminated polyimide (A), A crosslinking agent (B), and an organic solvent (C), the reaction component (α) contains an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2); and, (3) an insulating film, which is at 100 The thermal expansion coefficient at ℃~200℃ is 4~30ppm/℃.

Description

Copper clad laminate for flexible printed circuit board and flexible printed circuit board

The present disclosure relates to a copper-clad laminate for a flexible printed circuit board and a flexible printed circuit board.

In recent years, the demand for flexible printed wiring boards (FPWBs) has increased with the diversification of electronic devices including smartphones, such as miniaturization and high density.

Flexible Copper Clad Laminate (FCCL: Flexible Copper Clad Laminate) (hereinafter also referred to as Copper Clad Laminate), which is a material of FPCB, is a single side of a flexible insulating film that is laminated with copper foil through an adhesive layer. or a double-sided structure. As the insulating film, a polyimide film having high heat resistance and high reliability is often used. A resist layer is formed on this copper-clad laminate, and the steps of exposure, development, etching, and stripping of the resist layer are performed, thereby obtaining an FPBC with a circuit formed thereon.

In order to protect the conductive circuit or insulation, an adhesive is used for the FPCB, and the adhesive is used to bond the insulating film and the copper foil. As the adhesive used in the manufacture of FPCB, adhesives containing epoxy resin and cross-linking agent have been the mainstream in the past. For example, in Patent Document 1, a carboxyl group-containing acrylonitrile butadiene rubber/epoxy resin adhesive has been proposed. Moreover, in patent document 2, the glycidyl group containing elastomer/epoxy resin adhesive agent is proposed. In addition, in Patent Document 3, a carboxyl group-containing vinyl acrylic elastomer/epoxy resin adhesive has been proposed. Moreover, in patent document 4, the polyester amide resin/epoxy resin adhesive which has an acid value has been proposed. Moreover, in patent document 5, the polyester urethane resin/epoxy resin adhesive which has an acid value is proposed. Moreover, in patent document 6, a nylon/epoxy resin adhesive is proposed. In Patent Document 7, a polyurethane resin/epoxy resin-based adhesive is proposed which uses a phenol novolak resin having a specific structure as an epoxy hardener. [Prior Art Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open No. 6-049427 Patent Document 2: Japanese Patent Laid-Open No. 2001-354936 Patent Document 3: Japanese Patent Laid-Open No. 7-235767 Patent Document 4: Japanese Patent Laid-Open No. 2006-152015 5: Japanese Patent Laid-Open No. 2005-244139 Patent Document 6: Japanese Patent Laid-Open No. 2000-188451 Patent Document 7: Japanese Patent Laid-Open No. 2011-190424

However, as the miniaturization and densification of electronic devices such as smart phones are further advanced, the fine pitch or thinning of the circuit of the FPCB is also further advanced. Therefore, in the copper clad laminate that is the material of the FPCB, in order to facilitate the finer pitch, copper foil with low roughness (for example, 10-point average roughness (Rz) of 1.5 μm or less) is used, or insulation is required. The layer is the thinning of the adhesive layer (eg, 5 μm or less). However, as the adhesive layer is made thinner, the adhesiveness with the low-roughness copper foil decreases. Therefore, there is a need for a technique that can adhere as low a roughness copper foil as possible to a base film with an adhesive layer of the film. In this regard, the adhesives of Patent Documents 1 to 7 and the thickness of the adhesive layer assumed to be thick in use are 20 to 30 μm, and the roughness of the copper foil is also not mentioned.

The problem to be solved by the present invention is to provide a novel copper-clad laminate, which can exhibit excellent adhesiveness ( peel strength (N/m) of copper foil, and low dielectric constant and dielectric loss tangent.

As a result of research by the present inventors, it was found that a copper clad laminate composed of a specific structure can solve the aforementioned problems.

式(1)中，X表示單鍵、-SO₂ -、-CO-、-O-、-O-C₆ H₄ -C(CH₃ )₂ -C₆ H₄ -O-、或-COO-Y-OCO-，Y表示-(CH₂ )_l -、或-H₂ C-HC(-O-C(=O)-CH₃ )-CH₂ -，且l表示1～20。 (項目3) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述反應成分(α)包含二胺基聚矽氧烷(a3)。 (項目4) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述交聯劑(B)包含選自由聚苯醚樹脂、環氧樹脂、苯并噁嗪樹脂、雙馬來醯亞胺樹脂及氰酸酯樹脂所組成之群組中的至少一種。 (項目5) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述黏著劑(2’)進一步包含阻燃劑(D)。 (項目6) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述黏著劑(2’)進一步包含反應性烷氧基矽烷基化合物(E)。 (項目7) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述反應性烷氧基矽烷基化合物(E)是由通式Q-Si(R¹ )_a (OR² )_3-a 表示，並且，式中，Q表示包含能夠與酸酐反應的官能基之基團，R¹ 表示氫或碳數1～8的烴基，R² 表示碳數1～8的烴基，a表示0、1或2。 (項目8) 如上述項目中任一項所述之可撓性印刷線路板用覆銅積層板，其中，前述絕緣薄膜(3)是聚醯亞胺薄膜。 (項目9) 一種可撓性印刷線路板，其在上述項目中任一項所述之可撓性印刷線路板用覆銅積層板的銅箔面上具有電路圖案層。According to the present disclosure, the following items are provided. (Item 1) A copper-clad laminate for a flexible printed wiring board, comprising: (1) a copper foil, the 10-point average roughness (Rz) of the adhesive surface of which is 0.1 to 1.5 μm; (2) an adhesive layer, It is a thermosetting product of an adhesive (2') with a thickness of 2 to 5 μm, and the adhesive (2') contains a reactant of the reactive component (α), that is, an acid anhydride group-terminated polyimide (A), cross-linking agent (B), and organic solvent (C), the reaction component (α) contains aromatic tetracarboxylic anhydride (a1) and dimer diamine (a2); and, (3) insulating film, which is at 100 ° C ~ The thermal expansion coefficient at 200°C is 4 to 30 ppm/°C. (Item 2) The copper-clad laminate for a flexible printed wiring board according to the above item, wherein the aromatic tetracarboxylic anhydride (a1) is represented by the following general formula (1):

In formula (1), X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, or -COO-Y -OCO-, Y represents -(CH ₂ ) ₁ -, or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -, and 1 represents 1-20. (Item 3) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the reaction component (α) contains a diamine polysiloxane (a3). (Item 4) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the crosslinking agent (B) contains a polyphenylene ether resin, an epoxy resin, a benzoxan At least one of the group consisting of oxazine resin, bismaleimide resin and cyanate resin. (Item 5) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the adhesive (2') further contains a flame retardant (D). (Item 6) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the adhesive (2') further contains a reactive alkoxysilyl compound (E). (Item 7) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the reactive alkoxysilyl compound (E) is composed of the general formula Q-Si(R ¹ ) _a (OR ² ) _3-a represents, and, in the formula, Q represents a group containing a functional group capable of reacting with an acid anhydride, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents a group having 1 to 8 carbon atoms. The hydrocarbon group of 8, a represents 0, 1 or 2. (Item 8) The copper-clad laminate for a flexible printed wiring board according to any one of the above items, wherein the insulating film (3) is a polyimide film. (Item 9) A flexible printed wiring board having a circuit pattern layer on the copper foil surface of the copper-clad laminate for a flexible printed wiring board according to any one of the above items.

The copper-clad laminate of the present embodiment is formed by adhering a low-roughness copper foil and an insulating film with an adhesive layer of a film. The composition and thickness of the layer and the thermal expansion coefficient of the insulating film can exhibit excellent properties such as high peel strength, good heat resistance, and no warpage of the copper foil.

The copper clad laminate of this embodiment and the flexible printed wiring board obtained by using the copper clad laminate are suitable for the manufacture of fine-pitch, multi-layer wiring boards such as display drivers, camera modules, and 3D touch sensor substrates. , which are installed in mobile communication equipment represented by smart phones or mobile phones.

(1. Copper-clad laminates for flexible printed wiring boards)

The copper-clad laminate of the present embodiment is an article comprising at least (1) a copper foil with a specific surface roughness (hereinafter also referred to as copper foil (1)), and (2) an adhesive layer with a specific thickness (hereinafter also referred to as "copper foil"). An insulating film (hereinafter also referred to as an insulating film (3)) having a specific thermal expansion coefficient for the adhesive layers (2)) and (3) serves as a constituent element. The copper clad laminate can be single-sided as shown in Figure 1, or double-sided as shown in Figure 2.

(Copper foil (1)) Examples of the upper limit of the 10-point average roughness (Rz) of the surface in contact with the adhesive layer (2) in the copper foil (1) include 1.5, 1.4, 1.3, 1.2, 1.1 , 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.2 μm, etc.; examples of the lower limit include: 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.2 μm Wait. The upper limit value and the lower limit value of the 10-point average roughness (Rz) of the surface in contact with the adhesive layer (2) in the copper foil (1) are not limited to the above-mentioned values. The range of the 10-point average roughness (Rz) of the surface in contact with the adhesive layer (2) in the copper foil (1) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the 10-point average roughness (Rz) of the surface in contact with the adhesive layer (2) in the copper foil (1) is preferably It is 0.1-1.5 micrometers, More preferably, it is 0.2-1.1 micrometers. As an example of the copper foil which has the said 10-point average roughness (Rz), a rolled copper foil, an electrolytic copper foil, etc. are mentioned. In addition, in the present disclosure, Rz is expressed in millimeters as a difference between the average value of the elevations of the peaks from the highest to the fifth highest in the portion obtained by extracting only the reference length from the cross-sectional curve, and the The difference between the average values of the elevations of the troughs up to the 5th deepest.

The copper foil (1) may be a copper foil whose one side or both sides have been subjected to surface treatments such as roughening treatment and anti-rust treatment. Examples of the anti-rust treatment include plating treatment using a plating solution containing nickel, zinc, tin, and the like, so-called mirror treatment such as chromate treatment, and the like.

The thickness of the copper foil (1) is not particularly limited. Examples of the upper limit of the thickness of the copper foil (1) include 100, 90, 80, 70, 60, 50, 40, 38, 30, 20, 10, 5, 2, 1 μm, etc.; and examples of the lower limit include : 90, 80, 70, 60, 50, 40, 38, 30, 20, 10, 5, 2, 1 μm, etc. The range of the thickness of the copper foil (1) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, it is preferably about 1 to 100 μm, more preferably about 2 to 38 μm.

(Adhesive layer (2)) The adhesive layer (2) is a thermosetting product of a specific adhesive (2') (hereinafter also referred to as the adhesive (2')).

The adhesive (2') is a composition comprising: a specific acid anhydride group-terminated polyimide (A) (hereinafter also referred to as (A) component), a crosslinking agent (B) (hereinafter also referred to as ( B) component), and organic solvent (C) (henceforth (C) component is also called).

(Acid anhydride group-terminated polyimide (A)) The component (A) is a reactant of the reaction component (α) (hereinafter also referred to as the component (α)) containing an aromatic tetracarboxylic anhydride ( a1) (hereinafter also referred to as (a1) component) and dimer diamine (a2) (hereinafter also referred to as (a2) component). Furthermore, since the acid anhydride group-terminated polyimide provided according to the present disclosure has low water absorption, the copper clad laminate of the present embodiment is also low in water absorption.

式(1)中，X表示單鍵、-SO₂ -、-CO-、-O-、-O-C₆ H₄ -C(CH₃ )₂ -C₆ H₄ -O-、或-COO-Y-OCO-，Y表示-(CH₂ )_l -、或-H₂ C-HC(-O-C(=O)-CH₃ )-CH₂ -，且l表示1～20。(a1)成分，可將2種以上合併使用。(Aromatic tetracarboxylic anhydride (a1)) As the component (a1), various known aromatic tetracarboxylic anhydrides can be used without particular limitation. In one embodiment, an aromatic tetracarboxylic anhydride represented by the following general formula (1) is preferred from the viewpoint of solvent solubility, flexibility, adhesiveness, and heat resistance:

In formula (1), X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, or -COO-Y -OCO-, Y represents -(CH ₂ ) ₁ -, or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -, and 1 represents 1-20. (a1) A component can be used in combination of 2 or more types.

Examples of the component (a1) include pyromellitic dianhydride, 4,4'-oxybis(phthalic anhydride), and 3,3',4,4'-diphenylketone tetracarboxylic dianhydride , 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1,2,3,4-benzenetetramethyl Acid 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 dianhydride, 2, 3,3',4'-diphenylether tetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,3',4,4 '-Tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)stilbene dianhydride, 2,2-bis(2,3-dicarboxyphenyl) ) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanedianhydride, and 4,4'-[prop-2,2-diylbis(1,4-phenyleneoxy) )] bis (phthalic anhydride) and the like.

以下表示氫化二聚物二胺的一例。

(a2)成分，可將2種以上合併使用。(dimer diamine (a2)) Dimer diamine is a compound derived from a dimer of an unsaturated fatty acid such as oleic acid, that is, a dimer acid (refer to Japanese Patent Laid-Open No. 9-12712, etc.), And various well-known components can be used without particular restriction. The non-limiting structural formula of the dimer diamine is shown below (in each structural formula, m+n=6-17, p+q=8-19, and the dotted line part means a carbon-carbon single bond or a carbon-carbon double bond).

An example of the hydrogenated dimer diamine is shown below.

(a2) A component can be used in combination of 2 or more types.

Examples of commercial products of the component (a2) include Versamine 551 (manufactured by BASF Co., Ltd., Japan), Versamine 552 (manufactured by Corning Co., Ltd., hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (all from Japan) Manufactured by Koluoda Co., Ltd.), etc.

(Diaminopolysiloxane (a3)) In the component (α), for the purpose of imparting flexibility to the adhesive layer (2), various well-known diaminopolysiloxanes (a3) may be contained (hereinafter also referred to as called (a3) component). (a3) A component can be used in combination of 2 or more types. (a3) Examples of the component include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Alkane, α,ω-bis(4-aminobutyl)dimethiconol, α,ω-bis(5-aminopentyl)dimethylsiloxane, α,ω-bis[ 3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane, etc.

(Diamines (a4) other than (a2) components to (a3) components) In the (α) component, if necessary, diamines other than (a2) to (a3) components (hereinafter also referred to as (a4) Ingredient). (a4) A component can be used in combination of 2 or more types. (a4) Examples of the component include alicyclic diamines, bis(aminophenoxyphenyl)propane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, Diaminodiphenyl sulfone, diaminodiphenyl ketone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, Bis(aminophenoxy)benzene, bis(aminobenzyl)benzene, bis(aminodimethyl)benzene, bis(aminobis(trifluoromethyl)benzyl)benzene, amino Phenoxybiphenyl, bis(aminophenoxy)aryl, aminophenoxyphenone, aminophenoxyphenyl sulfide, aminophenoxyphenyl, aminophenoxy Phenyl ether, aminophenoxyphenyl hexafluoropropane, alkanediamine, etc. Examples of alicyclic diamines include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, and 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, isophoronediamine, etc. Examples include bis(amines such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane) 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, etc. Amino diphenyl ethers; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide , 4,4'-diaminodiphenyl sulfide and other diamino diphenyl sulfides; 3,3'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide , 4,4'-diaminodiphenyl ketone and other diamino diphenyl ketones; 3,3'-diamino diphenyl ketone, 4,4'-diamino diphenyl ketone, 3 ,4'-Diaminodiphenylketone and other diaminodiphenylketones; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane and other diaminodiphenylmethanes; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2 -(3-aminophenyl)-2-(4-aminophenyl)propane and other diaminophenylpropanes; 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-aminophenyl) -2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane and other diaminophenyl 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 diaminophenylphenylethanes; 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)benzene, 1,4- Bis(aminobenzyl)benzenes such as bis(4-aminobenzyl)benzene; 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1 ,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4 -Bis(4-amino-α,α-dimethylbenzyl)benzene and other bis(aminodimethyl)benzenes; 1,3-bis(3-amino-α,α-bis(tri) Fluoromethyl)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(aminobis() Trifluoromethyl)benzyl)benzenes; 4,4'-bis(3-aminophenoxy)biphenyl, 4,4' - Bis(4-aminophenoxy)biphenyl and other aminophenoxybiphenyls; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-amine bis(aminophenoxy) aryls such as bis(aminophenoxy) pyridine; bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy) Phenyl] ketone and other aminophenoxy phenyl ketones; bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl] Aminophenoxyphenyl sulfides such as thioethers; bis[4-(3-aminophenoxy)phenyl]zine, bis[4-(4-aminophenoxy)phenyl]zyl, etc. Aminophenoxyphenyl group; bis[4-(3-aminophenoxy)phenyl] ether, bis[4-(4-aminophenoxy)phenyl] ether and other aminophenoxy 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4 -(4-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and other aminophenoxyphenyl hexafluoropropanes; ethylenediamine, 1,3- Diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminoheptane Alkanediamines such as aminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc. 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-dimethylbenzyl]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]diphenylketone, 4,4'-bis[4-(4-amine base-α,α-dimethylbenzyl)phenoxy]diphenylsulfanium, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsine, 3 ,3'-Diamino-4,4'-diphenoxy diphenyl ketone, 3,3'-diamino-4,4'-dibenzyloxy diphenyl ketone, 3,3' -Diamino-4-phenoxydiphenyl 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-aminophenoxy)-3,3,3',3' -Tetramethyl-1,1'-spirobisindan, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis (4-aminobutyl)tetramethyldisiloxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[( 2-Aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1 ,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy] Ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-amine propyl) ether, triethylene glycol bis(3-aminopropyl) ether, and the like.

In order to express higher adhesiveness, heat resistance, and dielectric properties, the component (A) may be a combination of a plurality of components (A) having different types and ratios of the components (a1) to (a4).

(Content, ratio) The molar ratio of the acid component (a1) to the amine component (a2), (a3) and (a4) [(a1)/[(a2)+(a3) +(a4)]], which is not particularly limited. Examples of the upper limit of the molar ratio include 1.5, 1.4, 1.3, 1.2, 1.1, and the like, and examples of the lower limit include 1.4, 1.3, 1.2, 1.1, 1, and the like. The upper limit and lower limit of the molar ratio are not limited to the above-mentioned values. The range of the above-mentioned molar ratio can be appropriately set (for example, by combining the above-mentioned upper limit and lower limit). In one embodiment, it is preferably about 1 to 1.5, more preferably about 1 to 1.2, in terms of the balance between the tackiness and the heat-resistant tackiness.

The ratio of the dimer diamine (a2) in the amine component is not particularly limited. Examples of the upper limit of the component (a2) in 100 mol% of amine components include 100, 90, 80, 70, 60, 50, 40, 30, 20, 15 mol%, etc.; examples of the lower limit include : 95, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10 mol%, etc. The upper limit and lower limit of the component (a2) are not limited to the above-mentioned values. The range of the component (a2) in the 100 mol% amine component can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the (a2) component is preferably 10 to 100 mol in 100 mol % of the amine component, from the viewpoint of the balance of adhesion, heat-resistant adhesion, flow controllability, and low dielectric properties. %, more preferably about 30 to 100 mol%.

The ratio of the diamine polysiloxane (a3) in the amine component is not particularly limited. Examples of the upper limit of the component (a3) in 100 mol% of amine components include: 50, 40, 30, 20, 10, 5 mol%, etc.; examples of the lower limit include: 45, 40, 30, 20 , 10, 5, 0 mol%, etc. The upper limit and lower limit of the component (a3) are not limited to the above-mentioned values. The range of the component (a3) in 100 mol% of the amine component can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the (a3) component is preferably 0 to 50 mol in 100 mol % of the amine component from the viewpoint of the balance of adhesiveness, heat-resistant adhesiveness, flow controllability, and low dielectric properties. %, more preferably about 0 to 5 mol%.

The ratio of the diamine (a4) other than (a2) component - (a3) component in an amine component is not specifically limited. Examples of the upper limit of the component (a4) in 100 mol% of amine components include 90, 80, 70, 60, 50, 40, 30, 20, 10, 5 mol%, etc.; and examples of the lower limit include : 85, 80, 70, 60, 50, 40, 30, 20, 10, 5, 0 mol%, etc. The upper limit value and lower limit value of the component (a4) are not limited to the above-mentioned values. The range of the (a4) component in the 100 mol% amine component can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the (a4) component is preferably 0 to 90 mol in 100 mol % of the amine component from the viewpoint of the balance of adhesiveness, heat-resistant adhesiveness, flow controllability, and low dielectric properties. %, more preferably about 0 to 70 mol%.

The content of the component (A) in the adhesive (2') is not particularly limited. Examples of the upper limit of the content of the component (A) in 100 mass % (in terms of solid content) in the adhesive (2') include 95, 94.99, 94.95, 90, 80, 70, 60, 55 mass %, etc.; Examples of the lower limit include 94.99, 94.95, 90, 80, 70, 60, 55, 50 mass %, and the like. The upper limit and lower limit of the content of the component (A) in 100% by mass (in terms of solid content) in the adhesive (2') are not limited to the above-mentioned values. The range of the content of the component (A) in 100% by mass (in terms of solid content) in the adhesive (2') can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the content of component (A) in 100% by mass (in terms of solid content) in the adhesive (2') is preferably about 50 to 95% by mass, more preferably about 50 to 94.99% by mass, More preferably, it is about 80 to 95 mass %, and particularly preferably about 80 to 94.95 mass %.

(Manufacturing method of (A) component) (A) component can be manufactured by various well-known methods. An example of the production method of the component (A) includes a method including the following steps: Usually, at a temperature of about 60 to 120°C (preferably about 80 to 100°C), the components (a1) and (a2) The component and, if necessary, the component (a3) and/or the component (a4) are subjected to a polymerization addition reaction for about 0.1 to 2 hours (preferably 0.1 to 0.5 hours); then, further at about 80 to 250°C, preferably At a temperature of 100 to 200° C., the obtained polymer adduct is subjected to an imidization reaction (dehydration ring-closure reaction) for about 0.5 to 50 hours (preferably about 1 to 20 hours). In addition, at the time of each reaction, an appropriate organic solvent (preferably an aprotic solvent) among the organic solvents (C) described later can be used.

In the imidization reaction, various known catalysts can be used. Examples of catalysts include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline, etc. ; and can be used in combination of two or more.

In the imidization reaction, various known dehydrating agents can be used. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides such as benzoic anhydride, and the like, and two or more kinds can be used in combination.

(Physical properties of (A) component) The imide ring closure rate of (A) component is not particularly limited. (A) Examples of the upper limit of the imide ring closure ratio of the component include 100, 90, 80, 75%, etc., and examples of the lower limit include 95, 90, 80, 75, 70%, and the like. The upper limit value and the lower limit value of the imide ring closure ratio of the component (A) are not limited to the above-mentioned values. The range of the imide ring closure ratio of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the ring closure rate of the imide of the component (A) is preferably 70% or more, more preferably 85 to 100%. Here, the "imide ring closure rate" means the content of the cyclic imide bond in the component (A), and can be determined by various spectroscopic means such as nuclear magnetic resonance (NMR) and infrared (IR) spectroscopic analysis. .

The number-average molecular weight (Mn) of the component (A) (a value in terms of polystyrene measured by colloid permeation chromatography. The same applies hereinafter) is not particularly limited. (A) Examples of the upper limit of the number-average molecular weight of the component include 50,000, 45,000, 40,000, 35,000, 30,000, 25,000, 20,000, 15,000, 10,000, 6,000, etc.; 30000, 25000, 20000, 15000, 10000, 6000, 5000, etc. The upper limit and lower limit of the number average molecular weight of the component (A) are not limited to the above-mentioned values. The range of the number-average molecular weight of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the number average molecular weight of the component (A) is preferably about 5,000 to 50,000 in terms of the balance of adhesiveness, heat-resistant adhesiveness, flow controllability, and low dielectric properties.

The weight average molecular weight (Mw) of the component (A) (the value in terms of polystyrene measured by colloid permeation chromatography. The same applies hereinafter) is not particularly limited. Examples of the upper limit of the weight average molecular weight (Mw) of the component (A) include 150,000, 125,000, 100,000, 75,000, 50,000, 25,000, 15,000, and the like; examples of the lower limit include 125,000, 100,000, 75,000, 50,000, and 25,000. , 15000, 10000, etc. The range of the weight-average molecular weight of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the weight average molecular weight of the component (A) is preferably about 10,000 to 150,000 in terms of the balance of adhesion, heat-resistant adhesion, flow controllability, and low dielectric properties.

The molecular weight distribution (Mw/Mn) of the component (A) is not particularly limited. Examples of the upper limit of the molecular weight distribution (Mw/Mn) of the component (A) include 3.0, 2.5, 2.0, 1.6, and the like, and examples of the lower limit include 2.5, 2.0, 1.6, 1.5, and the like. The range of the molecular weight distribution of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the molecular weight distribution (Mw/Mn) of the component (A) is preferably about 1.5 to 3.0.

The softening point of the component (A) is not particularly limited. (A) Examples of the upper limit of the softening point of the component include 160, 150, 125, 100, 75, 50, 35°C, etc.; and examples of the lower limit include 150, 125, 100, 75, 50, 35°C Wait. The upper limit and lower limit of the softening point of the component (A) are not limited to the above-mentioned values. The range of the softening point of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the softening point of the component (A) is preferably about 30 to 160°C. In the present disclosure, the softening point is a viscoelasticity curve measured by using a commercially available measuring instrument (for example, "DSC6200" manufactured by Seiko Instruments Co., Ltd., "ARES-2KSTD-FCO-STD" manufactured by Rheometric Scientific Corporation). The temperature at which the stiffness modulus begins to decrease in the graph.

The terminal acid anhydride group concentration of the component (A) is not particularly limited. Examples of the upper limit of the terminal acid anhydride group concentration of the component (A) include 20,000, 17,500, 15,000, 12,500, 10,000, 7,500, 5,500eq/g, etc.; , 5500, 5000eq/g, etc. The upper limit and lower limit of the terminal acid anhydride group concentration of the component (A) are not limited to the above-mentioned values. The range of the terminal acid anhydride group concentration of the component (A) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, it is preferably about 5,000 to 20,000 eq/g.

(Crosslinking agent (B)) As the component (B), various known crosslinking agents can be used without particular limitation as long as it is a crosslinking agent for polyimide. Among them, in terms of heat resistance and adhesion, polyphenylene ether resin, epoxy resin, benzoxazine resin, bismaleimide resin and cyanate resin are preferred; among them, in terms of dielectric properties, more Preferred are epoxy resins and/or cyanate ester resins.

上述式中，Z¹ 表示碳數1～3的伸烷基或單鍵，m表示0～20，n表示0～20，m與n的合計值表示1～30。As the polyphenylene ether resin, various known polyphenylene ether resins can be used without particular limitation. Specifically, a polyphenylene ether resin represented by the following general formula is preferred:

In the above formula, Z ¹ represents an alkylene group having 1 to 3 carbon atoms or a single bond, m represents 0 to 20, n represents 0 to 20, and the total value of m and n represents 1 to 30.

The properties of the polyphenylene ether resin are not particularly limited, but from the viewpoints of adhesion and low dielectric properties, the terminal hydroxyl group concentration is preferably about 900 to 2500 μmol/g, and the number average molecular weight is about 800 to 2000.

Examples of epoxy resins include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, Hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, diphenylvinyl type epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing pentane skeleton, linear aliphatic epoxy resin Resin, alicyclic epoxy resin, glycidylamine type epoxy resin, trisphenol methane type epoxy resin, alkyl modified trisphenol methane type epoxy resin, biphenyl type epoxy resin, containing dicyclopentane Epoxy compounds with olefinic skeleton, epoxy resins containing naphthalene skeleton, arylalkylene epoxy resins, tetraglycidyl xylenediamine, modified epoxy resins obtained by modifying these epoxy resins with dimer acid Epoxy resin, diglycidyl dimer acid, etc.; and two or more kinds can be used in combination. Further, examples of commercially available products include "jER828", "jER834", "jER807", and "jER630" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; "CELLOXIDE 2021P" manufactured by Lu Chemical Industry Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.; "EXA-7250" manufactured by DIC Co., Ltd., etc.

上述式中，Z² 表示伸苯基。Among the epoxy resins, tetraglycidylxylenediamine having the following structure is preferable from the viewpoints of adhesiveness, heat-resistant adhesiveness and flow control properties, for example, a product made by Mitsubishi Gas Chemical Co., Ltd. can be used. Commercial products such as "Tetrad-X".

In the above formula, Z ² represents a phenylene group.

Various known hardeners can be combined with the epoxy resin. Examples of the curing agent include various polyphenylene ether resins, benzoxazine resins, bismaleimide resins and cyanate resins, succinic anhydride, phthalic anhydride, maleic anhydride, partial trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Mixtures of hydrogen phthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, Norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexenedicarboxylic anhydride, 3-dodecenylsuccinic anhydride, octenylsuccinic anhydride, etc. Acid anhydride-based hardeners; dicyandiamine (DICY), aromatic diamines (trade names "LonzacureM-DEA", "LonzacureM-DETDA", etc., all manufactured by Lonza Japan Co., Ltd.), amine-based hardeners such as aliphatic amines phenolic hardeners; phenolic hardeners such as phenol novolac resin, cresol novolac resin, bisphenol A novolac resin, triazine modified phenol novolac resin; phosphazene containing phenolic hydroxyl group (manufactured by Otsuka Chemical Co., Ltd. Cyclic phosphazene-based compounds such as trade name "SPH-100", etc.); rosin-based cross-linking agents such as maleic acid-modified rosin or its hydride; 6,6-(1-methylethylene) Bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylene)bis(3,4-dihydro-3- Benzoxazines such as methyl-2H-1,3-benzoxazine) (trade names "Benzoxazine Fa type" and "Benzoxazine Pd type" manufactured by Shikoku Chemical Industry Co., Ltd.; "Benzoxazine Pd type" manufactured by AIR WATER RLV-100", etc.); 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'-diphenyl Bismaleimides such as bismaleimide ("BAF-BMI" manufactured by JFE Chemical Co., Ltd., etc.); 2-allylphenol cyanate, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanatophenol)-1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-Phenylphenolcyanate, 1,1,1-Cham(4-cyanatophenyl)ethane, 4-cumylphenolcyanate, 1,1-bis(4-cyanato) Cyanate esters such as phenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-bis(4-cyanatophenyl)propane (Lonza Japan Co., Ltd. "PRIMASET BTP-6020S", "PRIMASET PT-30", etc. manufactured by Co., Ltd.), etc.; and two or more types can be used in combination. Among them, a cyanate ester compound is preferable. The usage-amount of the said hardening|curing agent is not specifically limited. In one embodiment, about 0.1-120 mass % is preferable in 100 mass % of solid content of the adhesive of this embodiment, More preferably, it is about 2-40 mass %.

Examples of benzoxazine resins include 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc.; and two or more kinds can be used in combination. In addition, a substituent (for example, a phenyl group, a methyl group, a cyclohexyl group, etc.) may be bonded to the nitrogen of the oxazine ring. In addition, examples of commercial products include "Benzoxazine F-a type" or "Benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., "RLV-100" manufactured by AIR WATER, and the like.

Examples of the bismaleimide resin include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide Imide, 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'-diphenyl bismaleimide, etc.; and two or more kinds can be used in combination. Moreover, as an example of a commercial item, "BAF-BMI" by JFE Chemical Co., Ltd. etc. is mentioned.

Examples of cyanate resins include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanatophenol)-1,1,1, 3,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-para(4-cyanato) phenyl)ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2- Bis(4-cyanatophenyl)propane, etc.; and two or more kinds can be used in combination. Further, examples of commercial products include "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)", "PRIMASET PT-30 (manufactured by Lonza Japan Co., Ltd.)", "CYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd.)" company)” etc.

(Curing catalyst) A curing catalyst can be combined with the component (B). Examples of the curing catalyst include 1,8-diaza-bicyclo[5.4.0]undec-7-ene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylamine Tertiary amines such as aminoethanol, ginseng (dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4 -Imidazoles such as methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine Organic phosphines such as phosphine, phenyl phosphine; tetraphenyl borate, etc; Methyl ethyl ketone peroxide, cyclohexanone peroxide, lauryl peroxide, di(tertiary butyl) peroxide, tertiary butyl peroxybenzoate, cumyl hydroperoxide, cumyl hydroperoxide, Radical initiators such as dicumyl peroxide, etc.; and two or more kinds can be used in combination. In addition, the usage-amount of this catalyst is not specifically limited, Usually, it is about 0.01-5 mass % when the solid content of the adhesive (2') is 100 mass %.

The content of the component (B) in the adhesive (2') is not particularly limited. Examples of the upper limit of the content of the component (B) in 100% by mass (in terms of solid content) in the adhesive (2') include 30, 25, 20, 15, 10, and 5% by mass; examples of the lower limit are: 25, 20, 15, 10, 5, 3 mass % etc. are mentioned. The upper limit and lower limit of the content of the component (B) in 100 mass % (in terms of solid content) in the adhesive (2') are not limited to the above-mentioned values. The range of the content of the component (B) in 100% by mass (in terms of solid content) in the adhesive (2') can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the range of the content of the component (B) in 100% by mass (in terms of solid content) in the adhesive (2') is preferably about 3 to 30% by mass, more preferably 5 to 20% by mass about.

(Organic solvent (C)) As (C) component, various well-known organic solvents can be used without a restriction|limiting in particular. Examples of the organic solvent include amide solvents such as N-methyl-2-pyrrolidone and N,N-dimethylacetamide; lactone solvents such as γ-butyrolactone; ketone solvents such as methyl ethyl ketone; Glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether and other ether solvents; cyclohexanone, methyl cyclohexane and other alicyclic solvents; methanol, ethanol, propanol, benzyl alcohol , alcohol solvents such as cresol; aromatic solvents such as toluene, xylene, etc.; and two or more kinds can be used in combination.

The content of the component (C) in the adhesive (2') is not particularly limited. Examples of the upper limit of the content of the component (C) in 100% by mass (in terms of solid content) in the adhesive (2') include 20, 15, 10, 5, and 3% by mass, and examples of the lower limit include : 15, 10, 5, 3, 2 mass %, etc. The upper limit and lower limit of the content of the component (C) in 100 mass % (in terms of solid content) in the adhesive (2') are not limited to the above-mentioned values. The range of the content of the component (C) in 100 mass % (in terms of solid content) in the adhesive (2') can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the range of the content of the component (C) in 100% by mass (in terms of solid content) in the adhesive (2') is preferably about 3 to 30% by mass, more preferably 2 to 20% by mass about 5 to 20 mass %, more preferably about 3 to 15 mass %.

(Flame Retardant (D)) The adhesive (2') may contain a flame retardant (D) (hereinafter also referred to as (D) component) as needed. Examples of the flame retardant (D) include phosphorus-based flame retardants, inorganic fillers, and the like. The flame retardant can be used in combination of two or more.

Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain a phenolic hydroxyl group. Phosphorus-based flame retardants can be used in combination of two or more. Among the phosphazene derivatives, from the viewpoints of flame retardancy, heat resistance, bleeding resistance, and the like, cyclic phosphazene derivatives are preferred. Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., RABITLE FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd., and the like.

Examples of inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, inorganic ion exchanger fillers, and the like. Inorganic fillers can be used in combination of two or more. Examples of commercially available products include FB-3SDC manufactured by Denka Co., Ltd., Exolit OP935 manufactured by Clariant Chemical Co., Ltd., KTL-500F manufactured by Kitamura Co., Ltd., and IXE manufactured by Toagosei Corporation.

The content of the component (D) in the adhesive (2') is not particularly limited. Examples of the upper limit of the content of the component (D) in 100% by mass (in terms of solid content) in the adhesive (2') include 30, 20, 10, 5, 1, and 0.2% by mass; examples of the lower limit are: 25, 20, 10, 5, 1, 0.1 mass % etc. are mentioned. The upper limit and lower limit of the content of the component (D) in 100% by mass (in terms of solid content) in the adhesive (2') are not limited to the above-mentioned values. The range of the content of the component (D) in 100 mass % (in terms of solid content) in the adhesive (2') can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). In one embodiment, the range of the content of the component (D) in 100% by mass (in terms of solid content) in the adhesive (2') is preferably about 0.1 to 30% by mass, more preferably 1 to 10% by mass about.

(Reactive alkoxysilyl compound (E)) The adhesive (2') may contain a reactive alkoxysilyl compound (E) (hereinafter also referred to as (E) component) as needed. (E) A component can maintain the low dielectric property of the adhesive layer of this embodiment, and can adjust the melt viscosity. As a result, it becomes possible to improve the interfacial adhesion between the adhesive layer and the base material (the so-called anchor effect), and to suppress the bleeding of the hardened layer generated from the base material end (hereinafter, sometimes referred to as This operation is called "flow control").

There is no restriction|limiting in particular as (E) component, Various well-known components can be used. Specifically, it is preferably represented by the general formula Q-Si(R ¹ ) _a (OR ² ) _3-a (in the aforementioned formula, Q represents a group containing a functional group capable of reacting with an acid anhydride, and R ¹ represents hydrogen or carbon A hydrocarbon group of 1 to 8, R ² represents a hydrocarbon group of 1 to 8 carbon atoms, and a represents a component represented by 0, 1 or 2). As a reactive functional group contained in Q, an amine group, an epoxy group, and a thiol group are mentioned; Preferably it is a primary amine group.

Examples of compounds in which Q is an amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane, etc.

Examples of compounds in which Q is an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, etc.

Examples of compounds in which Q is a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. -Mercaptopropylmethyldiethoxysilane, etc.

Moreover, content of (E) component is not specifically limited, either. Examples of the upper limit of the content of (E) component in 100 parts by mass (in terms of solid content) (A) component include 5.5, 5, 4, 3, 2, 1, 0.5, 0.2 parts by mass, etc.; Examples include 5, 4, 3, 2, 1, 0.5, 0.1 parts by mass, and the like. The upper limit value and the lower limit value of the content of (E) component in 100 parts by mass (in terms of solid content) of (A) component are not limited to the above-mentioned values. The range of content of (E) component in 100 mass parts (solid content conversion) (A) component can be set suitably (for example, it selects from the said upper limit and lower limit). In one embodiment, the content of the (E) component in 100 parts by mass (in terms of solid content) of the (A) component is preferably about 0.1 to 5.5 parts by mass, more preferably about 0.1 to 3 parts by mass.

The adhesive (2') is prepared by mixing (A) component, (B) component, and (C) component, and optionally (D) component, (E) component and/or additives by various known means. become.

(Additives) The adhesive (2') may contain formulations other than the components (A) to (E) as additives as needed. Examples of additives include ring-opening esterification catalysts or dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, dehydrating agents Molding agent, surface treatment agent, viscosity modifier, phosphorus flame retardant, flame retardant filler, silica filler, and fluorine filler, etc. In one embodiment, the example of the additive content is less than 40 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass with respect to 100 parts by mass (in terms of solid content) of the adhesive (2') part, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc; parts by mass, less than 200 parts by mass, less than 100 parts by mass, less than 50 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass copies etc.

The adhesive (2') is applied to the insulating film (3), which will be described later, and hardened by heat to form the adhesive layer (2). The hardening conditions will be described later.

Examples of the upper limit of the thickness of the adhesive layer (2) include 5, 4, 3, 2.5 μm, and the like, and examples of the lower limit include 4.5, 4, 3, 2.5, 2 μm, and the like. The upper limit value and the lower limit value of the thickness of the adhesive layer (2) are not limited to the above-mentioned values, and the range of the thickness of the adhesive layer (2) can be appropriately set (for example, selected from the above-mentioned upper limit value and lower limit value). The thickness of the adhesive layer (2) is not particularly limited, but in one embodiment, it is the gist of the present invention that the copper foil (1) and the insulating film (3) can be brought into close contact even after being thinned. Specifically, it is preferably about 2 to 5 μm, more preferably about 2 to 4 μm.

(Insulating film (3)) Examples of the upper limit of the thermal expansion coefficient of the insulating film (3) at 100°C to 200°C include: 30, 25, 23, 20, 15, 13, 10, 9, 5, etc.; the lower limit Examples include: 25, 23, 20, 15, 13, 10, 9, 5, 4, etc. The upper limit value and the lower limit value of the thermal expansion coefficient of the insulating film (3) at 100°C to 200°C are not limited to the above-mentioned values. In one embodiment, the thermal expansion coefficient of the insulating film (3) at 100°C to 200°C is preferably about 4 to 30 ppm/°C, and more Preferably, it is about 13 to 23 ppm/°C. In addition, in the present disclosure, the thermal expansion coefficient means the value of (shrinkage rate/temperature) of the insulating film (3) in the range of 100°C to 200°C, for example, a thermomechanical analyzer (distance between clamps: 20 mm, the width of the test piece: 4 mm, the load: 10 mg, the heating rate: 10° C./min in the tensile mode).

The thickness of the insulating film (3) is not particularly limited, and depends on the application of the printed wiring board of the present embodiment. Examples of the upper limit of the thickness of the insulating film (3) include: 40, 35, 30, 25, 20, 15, 10, 6 μm, etc.; examples of the lower limit include: 35, 30, 25, 20, 15, 10 , 6, 5 μm, etc. The upper and lower limits of the thickness of the insulating film (3) are not limited to the above-mentioned values, and the range of the thickness of the insulating film (3) can be appropriately set (for example, selected from the above-mentioned upper and lower limits). In one embodiment, the thickness of the insulating film (3) is preferably about 5 to 40 μm.

Examples of the insulating film (3) include polyimide film, polyetherimide film, aromatic polyimide film, polyethylene terephthalate (PET) film, polyethylene naphthalate Ester (PEN) film, liquid crystal polymer film, and composite film composed of flexible epoxy resin/glass cloth, etc. In one embodiment, a polyimide film is preferable from the viewpoint of heat resistance, dimensional stability, and insulating properties.

Examples of polyimide films include methods described in Japanese Patent Laid-Open No. 5-70590, Japanese Patent Laid-Open No. 2000-119419, Japanese Patent Laid-Open No. 2007-56198, and Japanese Patent Laid-Open No. 2005-68408. Examples of commercially available polyimide films other than the obtained polyimide films include XENOMAX (trade name) manufactured by Toyobo Co., Ltd., POMIRAN T (trade name) manufactured by Arakawa Chemical Industry Co., Ltd. ), Kapton (trade name) manufactured by Toray-DuPont Co., Ltd., UPILEX (trade name) manufactured by Ube Industries Co., Ltd., APICAL (trade name) manufactured by KANEKA Co., Ltd., etc.

The polyimide film can be obtained by various known production methods. The method for producing a polyimide film includes a method for obtaining a polyimide film by mixing a tetracarboxylic dianhydride and a diamine compound with a substantially equimolar organic polar solvent. Polymerization, thereby obtaining a polyamic acid polymer solution, and then casting the polyamic acid polymer solution on a support such as a glass plate or a stainless steel belt, and performing partial imidization or partial drying to have degree of self-supporting, thereby obtaining a polyamide film (hereinafter also referred to as a gel film), and then peeling the polyamide film from the support, and removing the polyamide film by means of needles, clips, etc. The ends were fixed and further heated to completely imidize the remaining polyamic acid. Examples of commercially available polyimide films include XENOMAX (trade name) manufactured by Toyobo Co., Ltd., POMIRAN T (trade name) manufactured by Arakawa Chemical Co., Ltd., and Toray-DuPont Co., Ltd. Kapton (trade name), UPILEX (trade name) manufactured by Ube Industries Co., Ltd., APICAL (trade name) manufactured by KANEKA Co., Ltd., etc.

The thickness of the insulating film (3) is not particularly limited, but is usually about 5 μm to 125 μm. Furthermore, the thickness is preferably about 10 to 75 μm, and more preferably about 10 to 50 μm, from the viewpoints of easiness of production and mechanical properties.

(Manufacturing method of copper clad laminate) The copper clad laminate of this embodiment can be obtained by various well-known methods. A non-limiting example of the single-sided aspect shown in FIG. 1 is shown below. Furthermore, the double-sided aspect shown in FIG. 2 is obtained by applying the following first to third steps to the insulating film (3).

The first step: apply the adhesive (2') on the low-roughness surface (the surface with Rz of 0.1 to 0.5) of the insulating film (3) or the copper foil (1), and allow it to dry, thereby forming a Adhesive layer (2) in hardened or partially hardened state. The second step: attach the copper foil (1) to the adhesive layer (2) from its low-roughness surface (the surface with Rz of 0.1 to 0.5), or attach the insulating film (3) to the adhesive layer (2) Lamination, thereby making a copper clad laminate. The third step: after curing the adhesive layer (2).

The coating method of the adhesive (2') is not particularly limited. Examples of the coating method of the adhesive (2') include brush coating, dip coating, spray coating, comma coating, knife coating, die coating, and lip die coating. (lip-die coating), roll coater coating, curtain coating, etc.

The drying temperature in the first step is not particularly limited, but is usually about 40 to 250°C, preferably about 70 to 170°C. In addition, the drying time is usually about 2 to 15 minutes. As a drying apparatus, for example, hot air drying, far-infrared heating, high-frequency induction heating, etc. can be used.

As an example of the bonding means in the second step, a roll laminator, a hot press, or the like can be used. At this time, it is possible to apply a temperature of about 40 to 250°C, preferably about 50 to 200°C.

For the post-hardening of the third step, the following method can be used: drying by hot air, heating by far infrared rays, high temperature drying, etc. Furnaces for frequency induction heating, etc.

The copper clad laminate of the present embodiment obtained in this manner is obtained even when the 10-point average roughness (Rz) of the copper foil ( 1 ) having a low roughness of 0.1 to 1.5 μm is used and the adhesive layer ( 2 ) is used. ) is reduced to a thickness of about 2 to 5 μm, and the following strong adhesion is exhibited: the peel strength of the copper foil (1) is 0.6 N/mm or more, preferably 0.8 to 1.2 N/mm. The peel strength is a measured value based on Japanese Industrial Standards (JIS) C 6481 (Test method for copper-clad laminates for printed wiring boards).

(2. Flexible Printed Wiring Board) The flexible printed wiring board of the present embodiment is an article obtained from the copper-clad laminate of the present embodiment. Specifically, a circuit pattern is formed on the copper foil surface of the copper-clad laminate by various known means, and examples of the pattern forming means include a subtractive method, a semi-additive method, and the like. An example of the semi-additive method includes the following method: after patterning with a resist film on the copper foil surface of the copper-clad laminate of the present embodiment, electrolytic copper plating is performed to remove the resist, and then an alkali liquid for etching. The thickness and L/S ratio of the circuit pattern layer are not particularly limited, and can be appropriately set according to the application. [Example]

Hereinafter, the present invention will be specifically described 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 example, unless otherwise specified, parts and % are based on mass.

In each production example, the number average molecular weight is a value obtained using a commercially available measuring machine (“HLC-8220GPC”, manufactured by Tosoh Corporation).

In each production example, the softening point is a value obtained by using a commercially available measuring machine (“DSC6200”, manufactured by Seiko Instruments Co., Ltd.).

(Production Example 1) Into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen introduction tube, 210.0 g of commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by Evonik Corporation of Japan) was placed. 3,3',4,4'-diphenylketone tetracarboxylic dianhydride), 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane, manufactured by Co., Ltd., and the solution was heated to 60°C . Next, after dripping 341.7 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Nippon Koluoda Co., Ltd.), the imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining A solution of polyimide resin (A-1) having a softening point of about 80° C. and a weight average molecular weight of about 35,000 (30.4% of non-volatile content). In addition, content of the dimer diamine in all the diamine monomers was 100 mol%, and the molar ratio of acid component / amine component was 1.03.

(Production Example 2) Into the same reaction vessel as in Production Example 1, 200.0 g of a commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA1000", SABIC Japan LLC.) was placed Manufactured 4,4'-[prop-2,2-diylbis(1,4-phenyleneoxy)]bis(phthalic anhydride)), 700.0 g of cyclohexanone, and 175.0 g of methylcyclohexane and heated the solution to 60°C. Next, after dropping 190.5 g of commercially available hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Nippon Koloda Co., Ltd.), imidization reaction was performed at 140° C. for 10 hours, Thereby, the solution (non-volatile content 30.1%) of polyimide resin (A-2) with a softening point of about 80 degreeC and a weight average molecular weight of about 35000 was obtained. In addition, the molar ratio of the acid component/amine component was 1.09.

(Production Example 3) In the same reaction vessel as in Production Example 1, 65.0 g of BisDA1000, 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were charged, and the solution was heated to 60°C. Next, after dripping 43.7 g of PRIAMINE 1075 and 5.4 g of 1,3-bis(aminomethyl)cyclohexane, the imidization reaction was performed at 140° C. for 10 hours, thereby obtaining a softening point of about A solution of polyimide resin (A-3) having a weight average molecular weight of about 30,000 at 100° C. (non-volatile content: 29.1%). In addition, the content of the dimer diamine in all the diamine monomers was 68 mol%, and the molar ratio of the acid component/amine component was 1.05.

(Production Example 4) Into the same reaction vessel as in Production Example 1, 190.0 g of a commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", 3,3, manufactured by Evonik Co., Ltd. ',4,4'-diphenylketone tetracarboxylic dianhydride), 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane, and the solution was heated to 60°C. Next, after dropping 288.1 g of PRIAMINE 1075 and 24.7 g of commercially available polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.), it was performed at 140° C. for 10 hours. The imidization reaction was carried out to obtain a solution of polyimide resin (A-4) having a softening point of about 70° C. and a weight average molecular weight of about 25,000 (30.6% of non-volatile content). In addition, the content of the dimer diamine in all the diamine monomers was 95 mol%, and the molar ratio of the acid component/amine component was 1.05.

(Production Example 5) In the same reaction vessel as in Production Example 1, 190.0 g of BTDA-PF, 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane were charged, and the solution was heated to 60°C. Then, after dropping 277.5 g of PRIAMINE 1075 and 23.8 g of KF-8010, the imidization reaction was carried out at 140° C. for 10 hours, thereby obtaining a polyimide having a softening point of about 70° C. and a weight average molecular weight of about 15,000. A solution of amine resin (A-5) (non-volatile content 30.1%). In addition, the content of the dimer diamine in all the diamine monomers was 95 mol%, and the molar ratio of the acid component/amine component was 1.09.

(Mixing example 1) 100.00 g of the solution of the (A-1) component as the (A) component and 7.60 g of tetraglycidyl xylenediamine (trade name "Tetrad-X" as the (B) component ”, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 19.07 g of toluene as the component (C) to obtain an adhesive with a nonvolatile content of 30.0%.

(Mixing example 2) 100.00 g of the solution of the (A-1) component as the (A) component, 8.66 g of Tetrad-X as the (B) component, 31.67 g of toluene as the (C) component, and 4.34 g of cyclic phosphazene (trade name "SPB-100", manufactured by Otsuka Chemical Co., Ltd.) of the component (D) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Mixing example 3) 100.00 g of the solution of the (A-1) component as the (A) component, 3.80 g of Tetrad-X as the (B) component, 19.06 g of toluene as the (C) component, and 3.80 g of SPB-100 of (D) component were mixed, and the adhesive of 30.0% of non-volatile content was obtained.

(Mixing Example 4) 100.00 g of the solution of the (A-1) component as the (A) component, 1.79 g of Tetrad-X as the (B) component, 13.86 g of toluene as the (C) component, and 3.57 g of SPB-100 of (D) component were mixed, and the adhesive agent of 30.0% of non-volatile content was obtained.

(Mixing example 5) 100.00 g of the solution of the (A-1) component as the (A) component, 8.09 g of Tetrad-X as the (B) component, 24.92 g of toluene as the (C) component, and 2.02 g of SPB-100 of (D) component were mixed, and the adhesive of 30.0% of non-volatile content was obtained.

(Example 6 of blending) A solution of 100.00 g of component (A-1) and 33.67 g of component (A-2) as component (A), 11.55 g of Tetrad-X as component (B), and 41.89 g of toluene as the component (C) and 5.78 g of SPB-100 as the component (D) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Example 7 of blending) As the component (A), 100.00 g of the solution of the component (A-1), 50.50 g of the solution of the component (A-2), and 104.47 g of the solution of the component (A-3) were used as 21.66 g of Tetrad-X as component (B), 74.20 g of toluene as component (C), and 10.84 g of SPB-100 as component (D) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Example 8 of blending) As the component (A), 100.00 g of the solution of the component (A-3), 100.00 g of the solution of the component (A-4), and 50.83 g of the solution of the component (A-5) were used as 21.38 g of Tetrad-X as component (B), 74.01 g of toluene as component (C), and 10.70 g of SPB-100 as component (D) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Example 9 of blending) 100.00 g of the solution of the component (A-1), 50.50 g of the solution of the (A-2) component, and 104.47 g of the solution of the (A-3) component were used as the component (A). 21.66 g of Tetrad-X as component (B), 74.20 g of toluene as component (C), and 10.84 g of cyano group-containing cyclic phenoxyphosphazene (trade name "RABITLE FP- 300B", manufactured by Fushimi Pharmaceutical Co., Ltd.) to obtain an adhesive with a non-volatile content of 30.0%.

(Mixing example 10) 100.00 g of the solution of the component (A-1), 50.50 g of the solution of the (A-2) component, and 104.47 g of the solution of the (A-3) component were used as the component (A). 21.70 g of Tetrad-X as component (B), 72.85 g of toluene as component (C), SPB-100 as 10.84 g as component (D), and N-2-( 2.17 g as component (E) Aminoethyl)-3-aminopropyltrimethoxysilane (trade name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd.) in methanol (solid content 10%) was mixed to obtain a non-volatile content of 30.0 % adhesive.

(Example 11 of blending) 100.00 g of the solution of the component (A-1), 50.50 g of the solution of the component (A-2), and 104.47 g of the solution of the component (A-3) were used as the component (A). (B) 10.45 g of N,N-diglycidyl-4-glycidoxyaniline (trade name "jER630", manufactured by Mitsubishi Chemical Co., Ltd.) and 22.61 g of phenol novolak resin (trade name) of component (B) Name "TAMANOL 759", Arakawa Chemical Industry Co., Ltd. product) methyl ethyl ketone solution (solid content 50%), 61.69 g of toluene as (C) component, 10.85 g of SPB-100 as (D) component, as ( 2.17 g of component E) was mixed with a methanol solution of KBM-603 (solid content 10%) to obtain an adhesive with a non-volatile content of 30.0%.

(Example 12 of blending) As the component (A), 100.00 g of the solution of the component (A-1), 50.50 g of the solution of the component (A-2), and 104.47 g of the solution of the component (A-3) were used as (B) Methyl ethyl ketone solution (solid content 40%) of 14.10 g of jER630 and 19.06 g of bisphenol A (Bis-A) type cyanate ester (trade name "CYTESTER TA", manufactured by Mitsubishi Gas Chemical Co., Ltd.) , 61.48 g of toluene as component (C), 10.85 g of SPB-100 as component (D), and a methanol solution (solid content 10%) of 2.17 g of KBM-603 as component (E) were mixed to obtain Adhesive with 30.0% non-volatile content.

(Mixing Example 13) 100.00 g of the solution of the component (A-2), 241.00 g of the solution of the component (A-3), and 2.56 g of jER630 and 6.80 g of the (B) component were used as the (A) component. Bis-A type cyanate ester (trade name "CYTESTER TA", manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter also referred to as "TA") in methyl ethyl ketone solution (solid content 40%), 12.90 g of (C) component toluene, 5.59 g of SPB-100 as component (D), and a methanol solution (solid content 10%) of 2.22 g of KBM-603 as component (E) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Mixing example 14) 100.00 g of the solution of the component (A-2) as the component (A), the solution of the component (A-3) of 241.00 g, and 2.56 g of jER630 and 5.53 g of the component (B) A methyl ethyl ketone solution (solid content 50%) of a phenol novolak resin (trade name "TAMANOL 759", manufactured by Arakawa Chemical Industry Co., Ltd., also referred to as "T759" hereinafter), 14.33 g of toluene as component (C), The methanol solution (solid content 10%) of 5.59 g of SPB-100 as (D) component and 2.22 g of KBM-603 as (E) component was mixed, and the adhesive with 30.0% of nonvolatile content was obtained.

(Mixing example 15) 100.00 g of the solution of the component (A-2) as the component (A), the solution of the component (A-3) of 241.00 g, and 3.20 g of the EXA-7250 ( DIC Co., Ltd.) and 4.14 g of a methyl ethyl ketone solution (50% solid content) of a phenol novolak resin (trade name "TAMANOL 759", manufactured by Arakawa Chemical Industry Co., Ltd.), 14.91 g of toluene as a component (C) 5.59 g of SPB-100 as component (D) and a methanol solution (solid content 10%) of 2.22 g of KBM-603 as component (E) were mixed to obtain an adhesive with a nonvolatile content of 30.0%.

(Comparative blending example 1) 100.00 g of acrylic elastomer solution (manufactured by Nagase ChemteX Co., Ltd., trade name "SG-708-6", methyl ethyl ketone solution, solid content 20.0%) as component (A), 5.70 g of Tetrad-X as the (B) component, 5.86 g of methyl ethyl ketone (hereinafter also referred to as MEK) as the (C) component, and 2.85 g of SPB-100 as the (D) component to obtain a non-volatile component 25.0 % adhesive.

(Comparative Blending Example 2) A methyl ethyl ketone solution (solid content 17.5 g) of 100.00 g of carboxyl group-containing acrylonitrile butadiene rubber (NBR) (manufactured by JSR Co., Ltd., trade name "XER-32C") as the component (A) was %), 4.99 g of Tetrad-X as component (B), 5.86 g of methyl ethyl ketone as component (C), and 2.50 g of SPB-100 as component (D) to obtain a non-volatile content of 22.0% adhesion agent.

<Preparation 1 of copper-clad laminate> Using a gap coater, the adhesives of Blending Examples 1 to 12 and Comparative Blending Examples 1 and 2 were applied to polyimide so that the thickness after drying was 3 μm. The film (trade name "Kapton 50EN", manufactured by Toray-DuPont Co., Ltd., thickness 12.5 μm, thermal expansion coefficient 15 ppm/°C) was dried at 150°C for 5 minutes to obtain a polyimide film with an adhesive layer . Next, the roughened surface of the rolled copper foil (BHY manufactured by JX Nippon Mining & Metals Co., Ltd., 10-point average roughness (Rz) on the roughened surface side: 0.8 μm) was superimposed on the roughened surface with the adhesive layer attached thereon. On the adhesive layer of the imine film, heat and pressure were performed at 170° C. and 3 MPa for 30 minutes, thereby obtaining a copper-clad laminate. These copper-clad laminates were set as Examples 1 to 12 and Comparative Examples 1 and 2, respectively.

<Preparation of copper clad laminate 2> Using a gap coater, the adhesive of Blending Example 1 was applied so that the thickness after drying was 5 μm, and the same as in <Preparation 1 of copper clad laminate> steps to obtain a copper clad laminate. This copper-clad laminate was set as Example 16.

<Adhesion Test> With respect to each of the copper-clad laminates of Examples and Comparative Examples, peel strength (N/mm) was measured in accordance with JIS C-6481 (Test method for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 1.

<Measurement of the dielectric constant and dielectric loss tangent of the adhesive layer> 7 g of the adhesive compositions of blending examples 1 to 15 and comparative blending examples 1 to 2 were poured into a fluororesin PFA flat disc (diameter 75 mm, mutual physicochemical glass The film was obtained by curing under the conditions of 30°C for 10 hours, 70°C for 10 hours, 100°C for 6 hours, 120°C for 6 hours, 150°C for 6 hours, and 180°C for 12 hours. Hardened sheet with a thickness of about 300 μm. Next, the dielectric constant and dielectric loss tangent at 10 GHz were measured using a commercially available dielectric constant measuring apparatus (cavity resonator type, manufactured by AET Corporation) for this cured product sheet according to JIS C2565. The results are shown in Table 1.

<Appearance change> About the copper clad laminated board of an Example, after hardening, it floated in the solder bath of 288 degreeC with the copper foil side down for 30 seconds, and confirmed the presence or absence of change in appearance. In the item of heat resistance, no change was made into (circle), and the case with foaming and swelling was made into x. The results are shown in Table 1.

※有機溶劑(C)中亦可包含除了(C)成分以外的成分中包含的有機溶劑。[Table 1]

*The organic solvent (C) may contain the organic solvent contained in the component other than (C) component.

<Preparation of printed wiring board for circuit evaluation>

For the copper clad laminates of the examples and comparative examples, the copper clad laminates with the resist pattern of line width/pitch=0.2/0.2 (mm) were immersed in a ferric chloride aqueous solution with a concentration of 40%. Etch to form copper circuits. A printed wiring board can be produced in this manner.

1: copper foil

2: Adhesive layer

3: Insulating film

FIG. 1 is a schematic diagram showing an example of a copper clad laminate (single-sided aspect) of the present embodiment.

FIG. 2 is a schematic diagram showing an example of the copper-clad laminate (double-sided aspect) of the present embodiment.

1: copper foil

2: Adhesive layer

3: Insulating film

Claims (8)

A copper-clad laminate for a flexible printed circuit board, comprising: copper foil, the 10-point average roughness Rz of the adhesive surface is 0.1-1.5 μm; ~5μm, the adhesive contains the reactant of the reactive component (α), that is, the acid anhydride group-terminated polyimide (A), the cross-linking agent (B), the organic solvent (C), and the reactive alkoxysilyl compound. (E), the reaction component (α) comprises an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2); and, an insulating film whose thermal expansion coefficient at 100° C. to 200° C. is 4 to 30 ppm/ °C. The copper-clad laminate for a flexible printed wiring board according to claim 1, wherein the aromatic tetracarboxylic anhydride (a1) is represented by the following general formula (1):

In formula (1), X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, or -COO-Y -OCO-, Y represents -(CH ₂ ) ₁ -, or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -, and 1 represents 1-20. For flexible printed wiring boards according to claim 1 or 2 A copper-clad laminate, wherein the reaction component (α) contains a diamine polysiloxane (a3). The copper-clad laminate for a flexible printed wiring board according to claim 1 or 2, wherein the cross-linking agent (B) comprises a polyphenylene ether resin, an epoxy resin, a benzoxazine resin, a bismuth resin At least one of the group consisting of lyimide resin and cyanate resin. The copper-clad laminate for a flexible printed wiring board according to claim 1 or 2, wherein the adhesive further contains a flame retardant (D). The copper-clad laminate for a flexible printed wiring board according to claim 1 or 2, wherein the reactive alkoxysilyl compound (E) is composed of the general formula Q-Si(R ¹ ) _a (OR ² ) _3-a represents, and, in the formula, Q represents a group containing a functional group that reacts with an acid anhydride, R ¹ represents hydrogen or a hydrocarbon group with 1 to 8 carbon atoms, R ² represents a hydrocarbon group with 1 to 8 carbon atoms, and a represents 0, 1 or 2. The copper-clad laminate for a flexible printed wiring board according to claim 1 or 2, wherein the insulating film is a polyimide film. A flexible printed wiring board having a circuit pattern layer on the copper foil surface of the copper-clad laminate for a flexible printed wiring board according to any one of claims 1 to 7.

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