Copper foil with resin and copper-clad laminate

Abstract

To provide a copper-clad laminate obtained by curing a copper foil with resin having a resin layer formed of a resin composition excellent in coatability, and a resin layer formed of a resin composition belonging to the copper foil with resin: the copper-clad laminate excellent in adhesiveness between a cured body of the resin layer and the copper foil, having good heat resistance of the cured body of the resin layer and excellent in a dielectric characteristic.SOLUTION: In a copper foil with resin having a resin layer formed of a resin composition on a roughened surface or the like of a copper foil whose surface roughness (Rz) is 1.1 μm or less or the surface of a non-roughened copper foil, the resin composition is a copper foil with resin containing a polyimide resin (D) of a specific structure, silica (E) whose specific surface area in a BET method is 1.0 to 20 m2 / g, a thermosetting resin (F) and a curing agent (G).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a copper foil with a resin layer composed of a thermosetting resin composition on the surface of the copper foil, and a copper-clad laminate obtained by curing the resin layer of the copper foil with a resin.

Background Art

[0002] Printed wiring boards are indispensable components for mobile communication devices such as smartphones and tablets, communication base station devices, and electronic devices such as computers and car navigation systems. Various resin materials having excellent properties such as adhesion to metal foil, heat resistance, and flexibility are used for printed wiring boards. In recent years, printed wiring boards for next-generation high-frequency wireless communication with high speed and large capacity have been developed. In addition to the above-mentioned various properties, the resin material is required to have low transmission loss, that is, low dielectric constant and low dielectric tangent.

[0003] High-frequency electrical signals are used for communication devices and electronic devices for the purpose of transmitting and processing a large amount of information at high speed. However, since high-frequency signals are very likely to attenuate, printed wiring boards are also required to reduce transmission loss. Transmission loss is roughly classified into conductor loss and dielectric loss. When the frequency of an electrical signal exceeds GHz, the conductor loss depends on the surface state of the copper foil used in the circuit. Therefore, in order to suppress the conductor loss, it is generally preferable to use a copper foil with low roughness or no roughening. That is, a low-dielectric resin having high adhesion to these copper foils is required.

[0004] Polyimide resins having excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance are widely used in electrical and electronic components, semiconductors, communication devices and their circuit components, peripheral devices, and the like. In particular, soluble polyimide resins with improved solvent solubility due to structural improvements are easy to process and coat, and moreover, an imidization process that requires high temperature during use is not required, so they are used in a wide range. On the other hand, it is known that hydrocarbon-based compounds such as petroleum and natural oil exhibit high insulation and low dielectric constant.

[0005] Patent Documents 1 and 2 describe a resin composition containing a polyimide resin into which the skeleton of a dimer diamine having a long-chain alkyl chain is introduced, and a copper foil with resin using the same. These resin compositions have adhesiveness to copper foil and high solder heat resistance. However, in the high-frequency region, further reduction of transmission loss is required. Therefore, it is necessary to reduce components that deteriorate dielectric properties, such as epoxy resin. Also, it is known that when the roughness of the copper foil surface increases, the transmission loss in the high-frequency region increases. Therefore, in order to reduce the transmission loss, it is necessary to reduce the roughness of the copper foil. However, when the roughness of the copper foil decreases, the adhesiveness of the resin composition to the copper foil decreases.

[0006] Patent Document 3 describes an example of adding silica to a polyimide resin into which the skeleton of a dimer diamine is introduced in order to improve dielectric properties. However, the resin composition described in Patent Document 3 has a high content ratio of epoxy resin, and in addition to the insufficient effect of reducing dielectric properties, there is a problem that the coating property to copper foil is poor because the addition amount of the filler is large.

[0007] In response to the above problems, Patent Document 4 describes that high dielectric properties were achieved by reducing the content ratio of epoxy resin in the resin composition. However, the composition of Patent Document 4 has a problem that the crosslinking density of the cured product is low and the heat resistance is low because the content ratio of the thermosetting resin is low.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0009] An object of the present invention is to provide a copper-clad resin foil having a resin layer made of a resin composition excellent in coatability, and a copper-clad laminate obtained by curing a resin layer made of the resin composition of the copper-clad resin foil, which has excellent adhesiveness between the cured product of the resin layer and the copper foil, good heat resistance of the cured product of the resin layer, and excellent dielectric properties.

Means for Solving the Problems

[0010] As a result of intensive studies, the present inventors have found that a copper-clad resin foil having a resin layer made of a resin composition containing a modified polyimide resin having a specific structure, silica having a specific specific surface area, a thermosetting resin, and a curing agent on the roughened surface of a low roughness copper foil or the surface of a non-roughened copper foil solves the above problems, and completed the present invention. That is, the present invention is (1) A copper-clad resin foil having a resin layer made of a resin composition on the roughened surface of a copper foil having a surface roughness (Rz) of 1.1 μm or less or the surface of a non-roughened copper foil, wherein the resin composition contains an aminophenol compound (a1) having at least two amino groups in one molecule, an aliphatic diamino compound (a2) having 6 to 36 carbon atoms, and an aromatic diamino compound (a3) having no phenolic hydroxyl group. A polyimide resin (D) which is a reaction product of an imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) containing and a tetracarboxylic dianhydride (B) and a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, and silica (E) having a specific surface area in the BET method of 1.0 to 20 m 2 / g, a thermosetting resin (F), and a curing agent (G), (2) The copper-clad resin foil according to the above (1), wherein the content of the silica (E) is 5 to 50% by mass based on the solid content of the polyimide resin (D). (3) The copper-clad resin foil according to the above (1) or (2), wherein the average particle diameter of the silica (E) is 0.3 to 5.0 μm. (4) The silica (E) is silica that has not been surface-treated with a silane compound. The copper foil with resin according to any one of the preceding paragraphs (1) to (3), (5) An aminophenol compound (a1) having at least two amino groups in one molecule is represented by the following formula (1)

[0011]

Chemical formula

[0012] (In formula (1), R1 represents a hydrogen atom, a methyl group or an ethyl group, and X represents C(CH3)2, C(CF3)2, SO2, an oxygen atom, a direct bond or the following formula (2)

[0013]

Chemical formula

[0014] represents a divalent linking group represented by.) The copper foil with resin according to the preceding paragraph (1) containing a compound represented by (6) The tetracarboxylic dianhydride (B) is represented by the following formulas (3) to (11)

[0015]

Chemical formula

[0016] (In formula (6), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond or the following formula (2)

[0017]

Chemical formula

[0018] represents a divalent linking group represented by.) The copper foil with resin according to the preceding paragraph (1) containing a compound selected from the group consisting of (7) The resin-coated copper foil according to the preceding paragraph (1), wherein the functional group capable of reacting with the phenolic hydroxyl group in the compound (C) having a functional group capable of reacting with the phenolic hydroxyl group and an ethylenically unsaturated double bond group is an isocyanate group or a carboxylic acid chloride group. (8) The aromatic diamino compound (a3) having no phenolic hydroxyl group is represented by the following formulas (12) to (15)

[0019] [Chemical formula]

[0020] (In formula (14), R2 independently represents a methyl group or a trifluoromethyl group. In formula (15), Z represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond, or a divalent linking group represented by the following formula (2)

[0021] [Chemical formula]

[0022] The resin-coated copper foil according to the preceding paragraph (1), which contains a compound selected from the group consisting of (wherein R3 independently represents a hydrogen atom, a methyl group, an ethyl group, or a trifluoromethyl group).) (9) The resin-coated copper foil according to the preceding paragraph (1), wherein the thermosetting resin (F) contains an aromatic maleimide resin, and (10) A copper-clad laminate obtained by curing a resin layer composed of the resin composition of the resin-coated copper foil according to any one of the preceding paragraphs (1) to (9). Relates to.

Effect of the Invention

[0023] Since the resin composition that forms the resin layer of the copper foil with resin of the present invention is excellent in coatability, the copper foil with resin can be prepared by an easy method. Further, the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the copper foil with resin of the present invention is excellent in the adhesiveness between the cured product of the resin layer and the copper foil, has good heat resistance of the cured product of the resin layer, and is excellent in dielectric properties, and thus can be suitably used for printed wiring boards and the like.

Embodiments for Carrying Out the Invention

[0024] The present invention will be described in detail below. The copper foil with resin of the present invention is (1) A copper foil with resin having a resin layer made of a resin composition on the roughened surface of a copper foil having a surface roughness (Rz) of 1.1 μm or less or on the surface of a non-roughened copper foil, wherein the resin composition contains an aminophenol compound (a1) having at least two amino groups in one molecule (hereinafter also simply referred to as “component (a1)”), an aliphatic diamino compound (a2) having 6 to 36 carbon atoms (hereinafter also simply referred to as “component (a2)”), and an aromatic diamino compound (a3) having no phenolic hydroxyl group (hereinafter also simply referred to as “component (a3)”). The amino compound (A) (hereinafter also simply referred to as “component (A)”) is a polyamic acid resin imide (P) (hereinafter also simply referred to as “imide (P)”) which is a copolymer of a tetracarboxylic dianhydride (B) (hereinafter also simply referred to as “component (B)”), and a polyimide resin (D) (hereinafter also simply referred to as “component (D)”) which is a reaction product of a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group (hereinafter also simply referred to as “component (C)”), silica (E) having a specific surface area in the BET method of 1.0 to 20 m 2 / g (hereinafter also simply referred to as “component (E)”), a thermosetting resin (F) (hereinafter also simply referred to as “component (F)”), and a curing agent (G) (hereinafter also simply referred to as “component (G)”). First, the imide (P) which is an intermediate raw material of the component (D) will be described.

[0025] The component (a1) used in the synthesis of the imidized product (P) is not particularly limited as long as it is a compound having at least two amino groups and at least one phenolic hydroxyl group in one molecule. Specific examples of the component (a1) include 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane, and 9,9'-bis(3-amino-4-hydroxyphenyl)fluorene. These may be used alone or in combination of two or more.

[0026] The component (a1) used in the synthesis of the imidized product (P) preferably contains a compound represented by the following formula (1).

[0027]

Chemical formula

[0028] (In formula (1), R1 represents a hydrogen atom, a methyl group or an ethyl group, and X represents C(CH3)2, C(CF3)2, SO2, an oxygen atom, a direct bond or a divalent linking group represented by the following formula (2).

[0029]

Chemical formula

[0030] When synthesizing the imidized product (P), the amount of the component (a1) used is preferably an amount such that the phenolic hydroxyl group equivalent of the imidized product (P) is in the range of 1,500 to 25,000 g / eq. When the phenolic hydroxyl group equivalent is less than 1,500 g / eq., the polarity of the finally obtained component (D) becomes high, so that the dielectric tangent of the cured product of the resin composition becomes high. When it exceeds 25,000 g / eq., the number of reaction points with the component (C) described later decreases, resulting in a decrease in the number of crosslinking points of the finally obtained component (D), and the heat resistance and adhesion to the substrate of the cured product of the resin composition tend to decrease. In addition, the phenolic hydroxyl group equivalent in this specification means a value measured by a method according to JIS K-0070.

[0031] The imidized product (P) is obtained by an imidization reaction of a polyamic acid resin which is a copolymer of the component (A) and the component (B), that is, a cyclization reaction by dehydration condensation. Therefore, the amounts (ratios) of the component (A) and the component (B) required to synthesize the imidized product (P) having the intended hydroxyl group equivalent and aliphatic chain amount can be easily calculated from the molecular weights of the component (A) and the component (B) used in the copolymerization reaction and the number of phenolic hydroxyl groups in the component (a1).

[0032] The component (a2) used in the synthesis of the imidized product (P) is not particularly limited as long as it is an aliphatic compound having two amino groups in one molecule and having 6 to 36 carbon atoms. The aliphatic structure in the component (a2) may be linear, branched or cyclic, or may have the above structures in combination, and may be either saturated aliphatic or unsaturated aliphatic. Specific examples of the component (a2) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimer diamine, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,4-bis(aminomethyl)cyclohexane, 4,4'-methylenebiscyclohexylamine, and diamino polysiloxane having 6 to 36 carbon atoms. These may be used alone or in combination of two or more. Also, from the viewpoint of the dielectric properties of the finally obtained component (D), it is preferable to use dimer diamine.

[0033] The dimer diamine described in the section of specific examples of the component (a2) is a substance in which two carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, are substituted with primary amino groups (see Japanese Patent Application Laid-Open No. 9-12712, etc.). Specific examples of commercially available products of dimer diamine include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more. Hereinafter, a non-limiting general formula of dimer diamine is shown (in each formula, m + n is preferably 6 to 17, p + q is preferably 8 to 19, and the dashed line portion means a carbon-carbon single bond or a carbon-carbon double bond).

[0034]

Chemical formula

[0035] When synthesizing the imidized product (P), the amount of the component (a2) used is preferably in the range of 10 to 50% by mass of the mass obtained by subtracting the mass of water (water generated by the dehydration condensation reaction) in an amount twice the number of moles of the component (B) from the mass of the component (A) (the mass of the produced imidized product (P)). When the amount of the component (a2) is less than the above range, the aliphatic chain derived from the component (a2) in the finally obtained component (D) is too small, resulting in a high dielectric tangent of the cured product of the resin composition. When it exceeds the above range, the aliphatic chain derived from the component (a2) in the component (D) is too large, resulting in a decrease in the heat resistance of the cured product of the resin composition.

[0036] The component (a3) used in the synthesis of the imidized product (P) is an aromatic diamino compound other than the above-mentioned component (a1), and is not particularly limited as long as it is an aromatic compound having two amino groups in one molecule. Specific examples of the component (a3) include m-phenylenediamine, p-phenylenediamine, m-tolylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl thioether, 3,3'-dimethyl-4,4'-diaminodiphenyl thioether, 3,3'-diethoxy-4,4'-diaminodiphenyl thioether, 3,3'-diaminodiphenyl thioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenyl thioether, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone sulfone, 4,4'-diaminodiphenyl sulfone sulfone, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, o-xylylenediamine, 2,2'-bis(3-aminophenoxyphenyl)propane, 2,2'-bis(4-aminophenoxyphenyl)propane, 1,3-bis(4-aminophenoxyphenyl)benzene, 1,3'-bis(3-aminophenoxyphenyl)propane, bis(4-amino-3-methylphenyl)methane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3-ethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane, bis(4-amino-3-propylphenyl)methane, and bis(4-amino-3,5-dipropylphenyl)methane. These may be used alone or in combination of two or more.

[0037] The component (a3) used in the synthesis of the imidized product (P) preferably contains a compound selected from the group consisting of the following formulas (12) to (15) from the viewpoints of the heat resistance of the cured product of the resin composition and the solubility of the finally obtained component (D) in a solvent.

[0038] [Chemical formula]

[0039] In formula (14), R2 independently represents a methyl group or a trifluoromethyl group. In formula (15), R3 independently represents a hydrogen atom, a methyl group or an ethyl group, and Z represents CH(CH3), SO2, CH2, O-C6H4-O, an oxygen atom, a direct bond or a divalent linking group represented by the above formula (2).

[0040] The component (B) used in the synthesis of the imidized product (P) is not particularly limited as long as it has two acid anhydride groups in one molecule. Specific examples of component (B) include pyromellitic dianhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methylcyclohexene-1,2-dicarboxylic anhydride, 3a,4,5,9b-tetrahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 5,5'-((propane-2,2-diylbis(4,1-phenylene))bis(oxy))bis(isobenzofuran-1,3-dione), and the like. Among them, from the viewpoints of solvent solubility and adhesion to the substrate, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride or 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride is preferable. These may be used alone or in combination of two or more.

[0041] Component (B) used in the synthesis of the imidized product (P) preferably contains a compound selected from the group consisting of the following formulas (3) to (11) from the viewpoint of the solvent solubility of the polyamic acid resin, the imidized product (P) and component (D).

[0042]

Chemical formula

[0043] In formula (6), Y represents C(CF3)2, SO2, CO, an oxygen atom, a direct bond, or a divalent linking group represented by the above formula (2).

[0044] When the number of moles of component (a1) in component (A) used for synthesizing the imidized product (P) is a1M, the number of moles of component (a2) is a2M, and the number of moles of component (a3) is a3M, the value of a1M / (a1M + a2M + a3M) is preferably more than 0.01 and less than 0.3, and more preferably more than 0.03 and less than 0.15. When a1M / (a1M + a2M + a3M) is 0.01 or less, the number of reaction sites with component (C) described later decreases, so the substrate adhesiveness and solder heat resistance of the cured product of the resin composition tend to decrease. When a1M / (a1M + a2M + a3M) is 0.3 or more, the dielectric properties of the cured product of the resin composition tend to decrease.

[0045] Also, the value of a2M / (a1M + a2M + a3M) is preferably more than 0.2 and less than 0.9, and more preferably more than 0.3 and less than 0.6. When a2M / (a1M + a2M + a3M) is 0.2 or less, the dielectric properties of the cured product of the resin composition tend to deteriorate, or the solvent solubility of component (D) tends to deteriorate. When a2M / (a1M + a2M + a3M) is 0.9 or more, the heat resistance of the cured product of the resin composition tends to deteriorate.

[0046] Also, the value of a3M / (a1M + a2M + a3M) is preferably more than 0.1 and less than 0.8, and more preferably more than 0.2 and less than 0.6. When a3M / (a1M + a2M + a3M) is 0.1 or less, the solder heat resistance of the cured product of the resin composition tends to deteriorate. When a3M / (a1M + a2M + a3M) is 0.8 or more, the solvent solubility of component (D) tends to deteriorate.

[0047] Let the number of moles of component (A) be MA and the number of moles of component (B) be MB. When component (A) and component (B) are copolymerized in an amount satisfying the relationship MA / MB > 1, an imidized product (P) of a polyamic acid resin with amino groups at both ends is obtained. At this time, the value of MA / MB is preferably in the range exceeding 1.0 and less than 2.0, and more preferably in the range exceeding 1.0 and less than 1.5. When the above value is 2.0 or more, in addition to insufficient high molecular weight of component (D), the residual ratio of unreacted raw materials increases, and various properties such as heat resistance after curing of the resin composition may decrease.

[0048] Let the number of moles of component (A) be MA and the number of moles of component (B) be MB. When component (A) and component (B) are copolymerized in an amount satisfying the relationship MB / MA > 1, an imidized product (P) of a polyamic acid resin with carboxylic anhydride groups at both ends is obtained. At this time, the value of MB / MA is preferably in the range exceeding 1.0 and less than 2.0, and more preferably in the range exceeding 1.0 and less than 1.5. When the above value is 2.0 or more, in addition to insufficient high molecular weight of component (D), the residual ratio of unreacted raw materials increases, and various properties such as heat resistance after curing of the resin composition may decrease.

[0049] The imidized product (P) can be synthesized by a known method. For example, after dissolving component (A) and component (B) used in the synthesis in a solvent, a copolymerization reaction between diamines and tetracarboxylic dianhydrides occurs by heating and stirring at 10 to 140 °C under an inert atmosphere such as nitrogen, and a polyamic acid resin solution is obtained.

[0050] Next, a dehydrating agent and a catalyst are added to the polyamic acid resin solution obtained above as necessary, and heating and stirring are performed at 100 to 300 °C to cause an imidization reaction (a ring-closing reaction accompanied by dehydration), thereby obtaining an imidized product (P). As the dehydrating agent, toluene, xylene, etc. can be used, and as the catalyst, a tertiary amine and a dehydration catalyst can be used. As the tertiary amine, a heterocyclic tertiary amine is preferable, and examples thereof include pyridine, picoline, quinoline, and isoquinoline. Examples of the dehydration catalyst include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. Incidentally, the reaction time for synthesizing the imidized product (P) is greatly affected by the reaction temperature, but it is preferable to carry out the reaction until the viscosity increase accompanying the progress of the reaction reaches equilibrium and the maximum molecular weight is obtained, and it is usually several minutes to 30 hours.

[0051] The above example is a method for synthesizing the imidized product (P) via polyamic acid. However, after dissolving the components (A) and (B) used in the synthesis in a solvent, a dehydrating agent and a catalyst are added as necessary, and a copolymerization reaction and an imidization reaction are carried out simultaneously by heating and stirring at 100 to 300 °C to obtain the imidized product (P).

[0052] As solvents that can be used in the synthesis of the imidized product (P), there may be mentioned methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexen-1-one, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, tetrahydropyran, ethyl isoamyl ether, ethyl t-butyl ether, ethyl benzyl ether, cresyl methyl ether, anisole, phenetole, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, benzyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, butyl propionate, benzyl propionate, methyl butyrate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, ethyl isovalerate, isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide and the like, but are not limited thereto. These may be used singly or in admixture of two or more.

[0053] The preferred amount of the solvent to be used should be appropriately adjusted according to the viscosity and use of the resulting resin, but is preferably 60 to 10% by mass of the solid content, more preferably 50 to 20% by mass.

[0054] In order to accelerate the dehydration reaction during the synthesis of the imidized product (P), it is preferable to use a catalyst. The amount of the catalyst used is preferably 1 to 30% of twice the number of moles of the component (B) (the number of moles of water generated by dehydration condensation), more preferably 5 to 15%. Specific examples of the catalyst that can be used include known general basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because of its low boiling point and difficulty in remaining.

[0055] Next, the component (D), which is the reaction product of the imidized product (P) and the component (C), will be described. The component (D) is a polyimide resin having a structure in which an ethylenically unsaturated double bond group is introduced through the component (C) into a part or all of the phenolic hydroxyl groups of the imidized product (P). Since the viscosity of the component (D) is lower than that of the imidized product (P) before the introduction of the ethylenically unsaturated double bond group, the laminating property of the resin layer composed of the resin composition containing the component (D) to the copper foil tends to be improved. In addition, since the ethylenically unsaturated double bond groups can react with each other or with various functional groups of the thermosetting resin (F) described later, excellent heat resistance and adhesiveness of the cured product of the resin composition can be achieved simultaneously.

[0056] The component (C) used in the reaction with the imidized product (P) is not particularly limited as long as it is a compound having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group. Examples of the functional group capable of reacting with the phenolic hydroxyl group of the component (C) include an isocyanate group, a carboxylic acid chloride group, an acid anhydride group, an epoxy group, a silyl chloride group, an alkyl halide group, an ester group, a sulfonyl chloride group, and a carboxyl group. In particular, the isocyanate group is preferable because no residual impurities derived from the leaving group from the component (C) are generated. In addition, the ethylenically unsaturated double bond group of the component (C) is not particularly limited as long as it is a C=C bond.

[0057] Furthermore, since the imidized product (P) obtained by copolymerizing component (A) and component (B) in an amount such that the molar number MA of component (A) and the molar number MB of component (B) satisfy the relationship MA / MB > 1 has an amino group at its terminal, a functional group capable of reacting with a phenolic hydroxyl group is an isocyanate group, a carboxylic acid chloride group, an acid anhydride group, an epoxy group, a silyl chloride group, an alkyl halide group, an ester group, a sulfonyl chloride group, or a carboxyl group, and component (C) can also react with the terminal amino group of the imidized product (P).

[0058] Also, since the imidized product (P) obtained by copolymerizing component (A) and component (B) in an amount such that the molar number MA of component (A) and the molar number MB of component (B) satisfy the relationship MA / MB < 1 has an acid anhydride group at its terminal, a functional group capable of reacting with a phenolic hydroxyl group is an isocyanate group, an epoxy group, or a carboxyl group, and component (C) can also react with the terminal acid anhydride group of the imidized product (P).

[0059] Specific examples of component (C) include Karens MOI (manufactured by Showa Denko K.K.), Karens AOI, Karens MOI - BM, Karens MOI - BP, Karens BEI, Karens MOI - EG, AOI - VM, methacrylic acid chloride, acrylic acid chloride, maleimidocaproic acid chloride, allyl bromide, allyl iodide, allyl chloride, 4 - chloro - 1 - butene, 4 - bromo - 1 - butene, crotonoyl chloride, cinnamoyl chloride, and the like.

[0060] Component (D), which is a reaction product of the imidized product (P) and component (C), can be synthesized by a known method. For example, it can be synthesized by mixing a predetermined amount of component (C) into a resin solution of the imidized product (P) and reacting it at 80°C to 150°C.

[0061] Various catalysts may be used to promote the reaction between the imidized product (P) and component (C). Known inorganic acids, organic acids, inorganic bases, organic bases, etc. can be used as the catalyst.

[0062] When the number of moles of component (C) used in the synthesis of component (D) is MC, the number of moles of phenolic hydroxyl groups of the imidized product (P) is MAB, and the number of moles of terminal functional groups of the imidized product (P) is MP, the value of MC / (MAB + MP) is preferably more than 0.3 and less than 1, and more preferably more than 0.5 and less than 1. When MC / (MAB + MP) exceeds 1, the heat resistance of the cured product of the resin composition deteriorates due to the unreacted component (C). When MC / (MAB + MP) is 0.3 or less, the viscosity of the polyimide resin solution increases due to hydrogen bonding of phenolic hydroxyl groups that do not react with component (C), and the laminating property tends to decrease, and the substrate adhesion of the cured product of the resin composition also tends to decrease.

[0063] Next, component (E) will be described. The specific surface area of component (E) by the BET method is preferably 1.0 to 20 m 2 / g. By using component (E) with the specific surface area within the above range, the dispersibility of component (E) in the resin layer is improved, the flexibility of the cured product of the resin layer is improved, and the adhesive strength between the silica and the cured product of the resin component is improved, making it difficult for cohesive failure of the resin layer to occur due to external stress.

[0064] The content of component (E) in the resin composition that forms the resin layer of the copper foil with resin of the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 35% by mass with respect to the solid content of component (D). By setting the content of component (E) within the above range, the adhesiveness between the cured product of the resin layer and the copper foil is improved, and the flexibility of the cured product of the resin layer is increased.

[0065] The average particle diameter of component (E) is preferably 0.3 to 5.0 μm. By setting the average particle diameter of component (E) within the above range, the incorporation of air bubbles into the resin layer can be reduced, and the resin layer can efficiently penetrate into the unevenness of the copper foil, improving the adhesiveness between the cured product of the resin layer and the copper foil. Note that the average particle diameter of component (E) in this specification means the value measured using a particle size distribution measuring device of the laser diffraction scattering method.

[0066] Component (E) is preferably not surface-treated with a silane compound. When component (E) is surface-treated, although the dispersibility is improved, the effect of improving the heat resistance of the cured product of the resin layer and the adhesiveness between the cured product of the resin layer and the copper foil may not be sufficiently obtained.

[0067] Component (E) is preferably spherical. In this case, the resin layer can efficiently penetrate into the unevenness on the surface of the copper foil, and the adhesiveness between the cured product of the resin layer and the copper foil can be further enhanced.

[0068] Next, component (F) will be described. Specific examples of component (F) include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds, and compounds having an ethylenically unsaturated group, etc. These resins or compounds can be used alone or in an appropriate mixture of two or more types according to the physical properties and uses of the copper-clad laminate obtained by curing the resin layer of the copper foil with resin of the present invention. In the present invention, by using component (F) in combination with component (D), heat stability and high adhesiveness can be imparted to the cured product of the resin layer composed of the resin composition. At that time, it is preferable that the terminal functional group (amino group or acid anhydride group) of component (D) or the ethylenically unsaturated double bond group derived from component (C) reacts with component (F).

[0069] As component (F), a maleimide resin or a compound having an ethylenically unsaturated group is preferable because the heat resistance and adhesiveness of the cured product of the resin composition are particularly excellent. In addition, when the number of moles of component (A) used in the synthesis of the polyamic acid resin is MA, the number of moles of component (B) is MB, the number of moles of component (C) is MC, the number of moles of the terminal functional group of the imidized product (P) is MP, and the number of moles of component (a1) is Ma1, for a polyimide resin in which the value of MA / MB exceeds 1 and the value of MC / (MP + Ma1) exceeds 0 and is less than 1, it is also preferable to use an epoxy resin as the thermosetting resin.

[0070] Further, from the viewpoint of suppressing the increase in viscosity when the resin composition is dissolved in a solvent to form a varnish, the (F) component preferably has a molecular weight of 100 to 50,000. In the present specification, the molecular weight means the weight average molecular weight of polystyrene standard by gel permeation chromatography (GPC) method.

[0071] The maleimide resin as the (F) component is not particularly limited as long as it has two or more maleimide groups in one molecule. Specific examples of the maleimide resin having two or more maleimide groups in one molecule include polyfunctional maleimide compounds obtained by the reaction of 3,4,4'-triaminodiphenylmethane, triaminophenol, etc. with maleic anhydride, tris-(4-aminophenyl)-phosphate, tris(4-aminophenyl)-phosphate, tos(4-aminophenyl)-thiophosphate and maleic anhydride Maleimide compounds obtained by reaction, tris maleimide compounds such as tris(4-maleimidophenyl)methane, bis(3,4-dimaleimidophenyl)methane, tetramaleimide benzophenone, tetramaleimide naphthalene, triethylenetetramine and maleic anhydride Tetramaleimide compounds such as maleimide obtained by reaction, phenol novolac type maleimide resin, isopropylidene bis(phenoxyphenyl maleimide) phenyl maleimide aralkyl resin, biphenylene type phenyl maleimide aralkyl resin, etc. Examples of commercially available products include MIR-3000, MIR-5000 (both manufactured by Nippon Kayaku Co., Ltd.), BMI-70, BMI-80 (both manufactured by K.I. Kasei Co., Ltd.), BMI-1000, BMI-2000, BMI-3000, (all manufactured by Yamato Kasei Kogyo Co., Ltd.), etc.

[0072] In particular, since the resin layer made of the cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy, a maleimide resin having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring is preferable, and specific examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.), MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.). The maleimide resin is added for the purpose of reacting with the ethylenically unsaturated double bond groups possessed by the component (D). As a result, the crosslink density of the resin layer composed of the cured product of the resin composition increases, the resistance to polar solvents is improved, and the adhesion to copper foil and heat resistance are also improved. When the resin composition that forms the resin layer contains a maleimide resin, the curing temperature is preferably 150 to 250 °C. The curing time depends on the curing temperature, but is generally about several minutes to several hours. The content of the maleimide resin in the resin composition that forms the resin layer is preferably an amount such that the maleimide group equivalent of the maleimide resin is 0.1 to 500 equivalents with respect to 1 equivalent of the ethylenically unsaturated double bond groups of the component (D). In addition, the maleimide group equivalent in this specification means the theoretical maleimide equivalent calculated from the amine equivalent of the amine used as the raw material.

[0073] The epoxy resin as the component (F) is not particularly limited as long as it has two or more epoxy groups in one molecule. However, since the resin layer composed of the cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy, epoxy resins having aromatic rings such as benzene rings, biphenyl rings, and naphthalene rings are preferred. Specific examples thereof include jER828 (manufactured by Mitsubishi Chemical Corporation), NC-3000, XD-1000 (all manufactured by Nippon Kayaku Co., Ltd.), and the like. The epoxy resin is added for the purpose of reacting with the terminal amino group or acid anhydride group of the component (D). As a result, the crosslink density of the resin layer composed of the cured product of the resin composition increases, the resistance to polar solvents is improved, and the adhesion to copper foil and heat resistance are also improved. When the resin composition contains an epoxy resin, the curing temperature is preferably 150 to 250 °C. The curing time depends on the curing temperature, but is generally about several minutes to several hours.

[0074] When the resin composition that forms the resin layer contains an epoxy resin, the content of the epoxy resin is preferably an amount such that the epoxy group equivalent of the epoxy resin is 0.1 to 500 equivalents with respect to the active hydrogen of the terminal amino group and 1 equivalent of the terminal acid anhydride group of the component (D). The epoxy equivalent in this specification means the value measured by the method described in JIS K-7236.

[0075] (F) The compound having an ethylenically unsaturated group as a component is not particularly limited as long as it has one or more ethylenically unsaturated groups in one molecule. Specific examples of the compound having an ethylenically unsaturated group include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, polyethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate monomethyl ether, phenylethyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, glycol di(meth)acrylate, diethylene di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanurate, polypropylene glycol di(meth)acrylate, adipic acid epoxy di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide (meth)acrylate, bisphenol di(meth)acrylate, ε-caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethanolpropane tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tri(meth)acrylate, and its ethylene oxide adduct; pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and its ethylene oxide adduct, etc.

[0076] In addition, other examples of compounds having an ethylenically unsaturated group include urethane (meth) acrylates having a (meth) acryloyl group and a urethane bond in the same molecule; polyester (meth) acrylates having a (meth) acryloyl group and an ester bond in the same molecule; epoxy (meth) acrylates derived from an epoxy resin and having a (meth) acryloyl group; and reactive oligomers in which these bonds are used in combination.

[0077] Urethane (meth) acrylates include reaction products of a hydroxyl group-containing (meth) acrylate, a polyisocyanate, and other alcohols used as necessary. For example, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; glycerin (meth) acrylates such as glycerin mono (meth) acrylate and glycerin di (meth) acrylate; sugar alcohol (meth) acrylates such as pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate, and polyisocyanates such as toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexane methylene diisocyanate, and their isocyanurates and biuret reaction products.

[0078] Polyester (meth) acrylates include, for example, monofunctional (poly)ester (meth) acrylates such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate; di(poly)ester (meth) acrylates such as hydroxypivalic acid ester neopentyl glycol di(meth) acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth) acrylate, epichlorohydrin-modified phthalic acid di(meth) acrylate; and mono-, di- or tri(meth) acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of trimethylolpropane or glycerin.

[0079] Also included are mono-, di-, tri- or tetra(meth) acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane or tetramethylolpropane; mono(meth) acrylates or poly(meth) acrylates of polyhydric alcohols such as triols, tetraols, pentaols or hexaols which are mono- or poly(meth) acrylates of triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, δ-valerolactone to 1 mol of dipentaerythritol.

[0080] Furthermore, (meth)acrylates of polyester polyols which are reaction products of diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, etc., polybasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, etc., and anhydrides thereof; polyfunctional (poly)ester (meth)acrylates such as (meth)acrylates of cyclic lactone-modified polyester diols composed of diol components, polybasic acids and their anhydrides, and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. can be mentioned.

[0081] Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, trishydroxyphenylmethane type epoxy (meth)acrylate, dicyclopentadiene phenol type epoxy (meth)acrylate, bisphenol A type epoxy (meth)acrylate, bisphenol F type epoxy (meth)acrylate, biphenol type epoxy (meth)acrylate, bisphenol A novolac type epoxy (meth)acrylate, naphthalene skeleton-containing epoxy (meth)acrylate, glyoxal type epoxy (meth)acrylate, heterocyclic epoxy (meth)acrylate, etc., and acid anhydride-modified epoxy acrylates thereof can be mentioned.

[0082] For example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, etc.; styrenes such as styrene, methyl styrene, ethyl styrene, divinylbenzene, etc., and compounds having a vinyl group such as triallyl isocyanurate, trimethallyl isocyanurate, and bisallyl nadimide can also be mentioned as specific examples of compounds having an ethylenically unsaturated group.

[0083] As the compound having an ethylenically unsaturated group, commercially available products can be used. For example, KAYARAD (registered trademark) ZCA-601H (product name, manufactured by Nippon Kayaku Co., Ltd.), propylene glycol monomethyl ether acetate of TrisP-PA epoxy acrylate compound (KAYARAD (registered trademark) ZCR-6007H (product name), KAYARAD (registered trademark) ZCR-6001H (product name), KAYARAD (registered trademark) ZCR-6002H (product name), and KAYARAD (registered trademark) ZCR-6006H (product name) manufactured by Nippon Kayaku Co., Ltd.) can be mentioned. These compounds having an ethylenically unsaturated group can be used alone or in appropriate mixtures of two or more.

[0084] The content of the compound having an ethylenically unsaturated group in the resin composition to be the resin layer is preferably an amount of 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of the component (D). In addition, the ethylenically unsaturated double bond group equivalent in this specification means the theoretical ethylenically unsaturated double bond group equivalent calculated from the raw materials.

[0085] Next, the component (G) will be described. The component (G) is not particularly limited as long as it promotes the curing reaction of the component (F), and conventionally known ones can be used as the curing agent for the component (F). Only one type of the component (G) may be used, or two or more types may be used in combination.

[0086] When the component (F) is a maleimide resin, known amine compounds, thiol compounds, and radical initiators can be used as the component (G). Specific examples of the amino compound include, but are not limited to, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, polyoxypropylenediamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin, etc. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains a maleimide resin as the component (F), the addition amount of the amine compound is preferably 5 times or less, more preferably 2 times or less, of the component (F) in terms of mass ratio. Specific examples of the thiol compound include, but are not limited to, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate, etc. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains a maleimide resin as the component (F), the addition amount of the thiol compound is preferably 5 times or less, more preferably 2 times or less, of the component (F) of the present invention in terms of mass ratio. Specific examples of the radical initiator include peroxides such as dicumyl peroxide and dibutyl peroxide, azo compounds such as 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile), etc., but are not limited thereto. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains a maleimide resin as the component (F), the addition amount of the radical initiator is 0.1 to 10% by mass based on the maleimide resin. Particularly from the viewpoints of reaction rate and dielectric properties, it is preferable to use a radical initiator.

[0087] When the component (F) is an epoxy resin, known imidazole compounds, phosphine compounds, phenol resins, and amino compounds can be used as the component (G). Specific examples of the imidazole compound and the phosphine compound include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; metal compounds such as tin octylate, etc., but are not limited thereto. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains an epoxy resin as the component (F), the addition amount of the imidazole compound or the phosphine compound is 0.1 to 10% by mass based on the epoxy resin. Specific examples of the phenolic resin include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanol (benzenedimethanol, α,α,α’,α’-benzenedimethanol, biphenyldimethanol, α,α,α’,α’-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyl (α,α’-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, and modified products thereof, but are not limited thereto. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains an epoxy resin as the component (F), the addition amount of the phenolic resin is preferably 5 times or less, more preferably 2 times or less, in terms of mass ratio with respect to the epoxy resin, in the range of the component (F). Specific examples of the amino compound include, but are not limited to, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, polyoxypropylenediamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin, etc. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains an epoxy resin as the component (F), the addition amount of the amine compound is preferably 5 times or less, more preferably 2 times or less, by weight, of the component (F). From the viewpoint of dielectric properties, it is preferable to use an imidazole compound or a phosphine compound.

[0088] When the component (F) is a compound having an ethylenically unsaturated group, it is preferable to use a radical initiator as the component (G). Specific examples of the radical initiator include, but are not limited to, peroxides such as dicumyl peroxide and dibutyl peroxide, azo compounds such as 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile), etc. These may be used alone or in combination of two or more. When the resin composition forming the resin layer contains a compound having an ethylenically unsaturated group, the addition amount of the radical initiator is 0.1 to 10% by mass based on all the ethylenically unsaturated groups in the composition.

[0089] An organic solvent can be used in combination with the resin composition forming the resin layer to obtain a varnish-like composition (hereinafter simply referred to as varnish). Examples of solvents that can be used in combination include amide solvents such as γ-butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic solvents such as toluene and xylene. The organic solvent is preferably used in a range such that the concentration of components other than the organic solvent in the varnish is 10 to 80% by mass, more preferably 20 to 70% by mass.

[0090] Known additives may be used in combination with the resin composition to be the resin layer, if necessary. Specific examples of additives that can be used in combination include polybutadiene or modified products thereof, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, silicone oil, and alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder, and those having a specific surface area of 1.0 to 20 m 2Inorganic fillers such as silica other than / g, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, colorants such as phthalocyanine blue and phthalocyanine green, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and defoaming agents, hydroquinone, hydroquinone monomethyl ether, phenolic polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photo base generators, photoacid generators, etc. may be mentioned. The blending amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass in total of components (D), (E), (F) and (G), provided that the effects of the present invention are not impaired.

[0091] The method for preparing the resin composition to form the resin layer is not particularly limited, and it may be sufficient to simply mix each component uniformly. For mixing each component, in the absence of a solvent, for example, an extruder, kneader, roll, etc. are used, and in the presence of a solvent, a reaction kettle with a stirrer, etc. is used.

[0092] Next, a method for obtaining the copper foil with resin of the present invention by providing a resin layer made of a resin composition on the roughened surface of a copper foil with a surface roughness (Rz) of 1.1 μm or less or on the surface of a non-roughened copper foil will be described. The copper foil with resin of the present invention can be obtained by various known methods. Specifically, methods such as heating the resin composition to lower the viscosity and casting, and applying a solution and drying the solvent can be mentioned. The coating means of the resin composition is not particularly limited, and examples include a curtain coater, roll coater, laminator, etc. Also, various leveling means may be used in combination. As for the copper foil, various known ones can be used without particular limitation as long as it is the roughened surface of a copper foil with a surface roughness (Rz) of 1.1 μm or less or a non-roughened copper foil. Specifically, rolled copper foil, electrolytic copper foil, etc. may be mentioned. Its thickness is also not particularly limited, and it may be one with surface treatment (roughening, rust prevention).

[0093] The resin layer made of the resin composition may be uncured or may be partially cured under heating. The partially cured resin layer is in a state called the so-called B-stage. Incidentally, the thickness of the resin layer is not limited, but is preferably about 12 to 105 μm.

[0094] By heating the resin layer made of the resin composition provided on the surface of the copper foil to form a cured product (resin layer), the copper-clad laminate of the present invention can be obtained. The curing temperature and curing time of the resin layer made of the resin composition may be selected in consideration of the combination of the functional group of the (D) component and the reactive group of the (F) component. For example, when the resin composition contains a maleimide resin or an epoxy resin, the curing temperature is preferably 120 to 250 ° C, and the curing time is generally about several tens of minutes to several hours.

[0095] In addition, a polyimide film or LCP (liquid crystal polymer) or the like can be laminated on the surface of the resin layer made of the resin composition, and after hot pressing, heat curing can be performed to obtain a base material provided with the copper-clad laminate of the present invention. Examples of the base material provided with the copper-clad laminate include a copper-clad laminate (CCL), a printed wiring board or a multilayer wiring board having a circuit pattern on the copper foil of the CCL.

Examples

[0096] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. "Parts" in the Examples means parts by mass, and "%" means mass%. The measurement conditions of GPC in the Examples are as follows. Model: TOSOH ECOSEC Elite HLC-8420GPC Column: TSKgel Super AWM-H Eluent: NMP (N-methylpyrrolidone); 0.5 ml / min, 40 °C Detector: UV (differential refractometer) Molecular weight standard: polystyrene

[0097] Synthesis Example 1 (Synthesis of Component (D) (Polyimide Resin 1)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 0.67 part of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.69 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539.52 g / mol), 5.89 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 68.24 parts of anisole were added and heated to 70°C. Next, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Mannak Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine and 18.97 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P) solution (P-1) (phenolic OH equivalent, 7,953 g / eq., molecular weight 99,300). Subsequently, 0.60 part of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.08 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130°C for 4 hours, the remaining triethylamine and toluene were continuously removed at 130°C to obtain a polyimide resin 1 solution (polyimide 1). In Synthesis Example 1, the molar ratio of the diamine components ((a1) component, (a2) component and (a3) component) to the acid anhydride component ((B) component) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Also, assuming the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group as MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) solution (P-1) as MAB, and the number of moles of the terminal functional group of the imidized product (P) solution (P-1) as MP, MC / (MAB + MP) = 0.91.

[0098] Synthesis Example 2 (Synthesis of Component (D) (Polyimide Resin 2)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device, and a stirring device, 0.70 part of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4‘-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.22 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 5.16 parts of APB-N (1,3-bis(3-aminophenoxy)benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol), and 65.66 parts of anisole were added and heated to 70 °C. Next, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Mannak Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine, and 18.64 parts of toluene were added, and the reaction was carried out at 130 °C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P) solution (P-2) (phenolic OH equivalent, 7,302.3 g / eq., molecular weight 101,200). Subsequently, 0.60 part of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.09 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130 °C for 4 hours, the remaining triethylamine and toluene were subsequently removed at 130 °C to obtain a polyimide resin 2 solution (polyimide 2). In Synthesis Example 2, the molar ratio of the diamine components ((a1) component, (a2) component, and (a3) component) to the acid anhydride component ((B) component) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Also, when the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group was MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) solution (P-2) was MAB, and the number of moles of the terminal functional group of the imidized product solution (P-2) was MP, MC / (MAB + MP) = 0.90.

[0099] Synthesis Example 3 (Synthesis of Component (D) (Polyimide Resin 3)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device, and a stirring device, 0.69 part of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.45 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 5.05 parts of APB-N (1,3-bis(3-aminophenoxy)benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol), and 70.0 parts of anisole were added and heated to 70°C. Next, 12.88 parts of BTDA (3,3',4,4'-benzophenonetetracarboxylic dianhydride, manufactured by Daicel Corporation, molecular weight 322.01 g / mol), 0.81 part of triethylamine, and 18.80 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated during the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P) solution (P-3) (phenolic OH equivalent, 7,614.3 g / eq., molecular weight 86,200). Subsequently, 0.60 part of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.09 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130°C for 4 hours, the remaining triethylamine and toluene were continuously removed at 10°C to obtain a polyimide resin 3 solution (polyimide 3). In Synthesis Example 3, the molar ratio of the diamine components ((a1) component, (a2) component, and (a3) component) to the acid anhydride component ((B) component) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Also, when the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group was MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) solution (P-3) was MAB, and the number of moles of the terminal functional group of the imidized product (P) solution (P-3) was MP, MC / (MAB + MP) = 0.90.

[0100] Synthesis Example 4 (Synthesis of Component (D) (Polyimide Resin 4)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 0.69 part of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.92 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), 6.01 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 69.0 parts of anisole were added and heated to 70°C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Mannak Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine and 19.08 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P) solution (P-4) (phenolic OH equivalent, 7,895 g / eq., molecular weight 64,000). Subsequently, 0.58 part of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 0.09 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130°C for 4 hours, the remaining triethylamine and toluene were continuously removed at 130°C to obtain a polyimide resin 4 solution (polyimide 4). In Synthesis Example 4, the molar ratio of the diamine components ((a1) component, (a2) component and (a3) component) to the acid anhydride component ((B) component) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Also, assuming the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) solution (P-4) is MAB, and the number of moles of the terminal functional group of the imidized product (P) solution (P-4) is MP, then MC / (MAB + MP) = 0.85.

[0101] Synthesis Example 5 (Synthesis of Component (D) (Comparative Polyimide Resin 1)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device and a stirring device, 0.67 part of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4'-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 11.69 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539.52 g / mol), 5.89 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 68.24 parts of anisole were added and heated to 70 °C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Mannak Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine and 18.97 parts of toluene were added, and the reaction was carried out at 130 °C for 8 hours while removing the water generated by the ring closure of the amic acid by azeotropy with toluene to obtain a comparative polyimide resin 1 solution (comparative polyimide 1) (phenolic OH equivalent, 7,953 g / eq., molecular weight 99,300). The molar ratio (number of moles of diamine component / number of moles of acid anhydride component) of the diamine components ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 5 was 1.01.

[0102] Synthesis Example 6 (Synthesis of Component (D) (Comparative Polyimide Resin 2)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet apparatus, and a stirring apparatus, 11.38 parts of PRIAMINE 1075 (manufactured by Clariant Japan Co., Ltd., molecular weight 534.38 g / mol), 5.64 parts of BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Corporation, molecular weight 348.16 g / mol), and 170.06 parts of anisole were placed and heated to 70°C. Next, 12.88 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine, and 18.75 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated during the ring closure of the amic acid by azeotropy with toluene. Then, the remaining triethylamine and toluene were continuously removed at 130°C to obtain a comparative polyimide resin 2 solution (comparative polyimide 2) (molecular weight 89,400). The molar ratio of the diamine components ((a1) component, (a2) component, and (a3) component) to the acid anhydride component ((B) component) used in Synthesis Example 6 (number of moles of diamine component / number of moles of acid anhydride component) was 1.01.

[0103] Synthesis Example 7 (Synthesis of Component (D) (Comparative Polyimide Resin 3)) Into a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark apparatus, a powder inlet, a nitrogen inlet device, and a stirring device, 6.60 parts of DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 4,4‘-(hexafluoroisopropylidene)bis(2-aminophenol), manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol), 12.07 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol), and 70.20 parts of anisole were placed and heated to 70°C. Then, 12.88 parts of ODPA (oxydiphthalic anhydride, manufactured by MANAC Co., Ltd., molecular weight 310.22 g / mol), 0.81 part of triethylamine, and 19.23 parts of toluene were added, and the reaction was carried out at 130°C for 8 hours while removing the water generated during the ring closure of the amic acid by azeotropy with toluene to obtain an imidized product (P) solution (P-7) (phenolic OH equivalent, 835 g / eq., molecular weight 32,200). Subsequently, 5.96 parts of KARENZ MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g / mol) and 1.0 part of BHT (2,6-di-tert-butyl-p-cresol) as a polymerization inhibitor were added, and after reacting at 130°C for 4 hours, the remaining triethylamine and toluene were continuously removed at 130°C to obtain a comparative polyimide resin 3 solution (comparative polyimide 3). In Synthesis Example 7, the molar ratio of the diamine components ((a1) component, (a2) component, and (a3) component) to the acid anhydride component ((B) component) (number of moles of diamine component / number of moles of acid anhydride component) was 1.01. Also, when the number of moles of the compound (C) component having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group was MC, the number of moles of the phenolic hydroxyl group of the imidized product (P) solution (P-7) was MAB, and the number of moles of the terminal functional group of the imidized product (P) solution (P-7) was MP, MC / (MAB + MP) = 0.55.

[0104] Formulation Examples 1 to 30 (Adjustment of the resin composition (Formulation Examples 1 to 20 are resin compositions for copper foils with resins of the present invention, and Formulation Examples 21 to 30 are resin compositions for copper foils with resins of comparative examples) After compounding each component in the compounding amounts shown in Tables 1 to 3 (the unit is "parts", and the number of parts in the table is the number of parts in terms of solid content excluding the solvent), anisole in an amount such that the solid content concentration becomes 20% by mass was added as a solvent and uniformly mixed to adjust resin compositions that would form resin layers of copper foils with resin, respectively.

[0105] Each component in Tables 1 to 3 is as follows. The specific surface area of the inorganic filler is a value measured by the BET method. <Polyimide resin> (D-1) to (D-4); Polyimides 1 to 4 obtained in Synthesis Examples 1 to 4 (D-5) to (D-7); Comparative Polyimides 1 to 3 obtained in Synthesis Examples 5 to 7 <Thermosetting resin> MIR-3000-70MT; Maleimide resin, manufactured by Nippon Kayaku Co., Ltd. XD-1000; Epoxy resin, manufactured by Nippon Kayaku Co., Ltd. ZXR-1889H; Epoxy acrylate resin, manufactured by Nippon Kayaku Co., Ltd. <Inorganic filler> (E-1); SFP-30M (manufactured by Denka Co., Ltd., fused silica, average particle diameter 0.6 μm, specific surface area 6.2 m 2 / g) (E-2); SFP-20M (manufactured by Denka Co., Ltd., fused silica, average particle diameter 0.4 μm, specific surface area 11.2 m 2 / g) (E-3); FB-3SDC (manufactured by Denka Co., Ltd., fused silica, average particle diameter 3.1 μm, specific surface area 3.6 m 2 / g) (E-4); Sciqas0.7μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle diameter 0.7 μm, specific surface area 4.3 m 2 / g) (E-5) BA-1 (manufactured by Diary Catalyst Kasei Co., Ltd., hollow silica, average particle diameter 16 μm, specific surface area 2.0 m 2 / g) (E-6); Sciqas0.7μm (manufactured by Sakai Chemical Industry Co., Ltd., surface epoxy silane-treated fused silica, average particle diameter 0.7 μm, specific surface area 4.3 m 2 / g) (E-7); Sciqas 0.7μm (manufactured by Sakai Chemical Industry Co., Ltd., surface polysiloxane-treated fused silica, average particle size 0.7μm, specific surface area 4.3m 2 / g) (E-8); 10SX-CH1 (manufactured by Admatechs Co., Ltd., surface aminosilane-treated fused silica, average particle size 1.1μm after 5μm coarse particle cut, specific surface area 15m 2 / g) (E-9); Sciqas 0.1μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle size 0.1μm, specific surface area 21.5m 2 / g) (E-10); Nano Ace D600 (manufactured by Nippon Talc Co., Ltd., talc, average particle size 0.6μm, specific surface area 24m 2 / g) (E-11); DAW-03 (manufactured by Denka Co., Ltd., alumina, average particle size 4.9μm, specific surface area 0.5m 2 / g) <Hardener> DCP; Dicumyl peroxide, manufactured by Kayaku Nucreon Co., Ltd. <Additive> KR-513; Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd. TT-LX; Lubricant additive, manufactured by Johoku Chemical Co., Ltd. KTL-8FH; Teflon (registered trademark) powder, average particle size 3.5μm, manufactured by Kitamura Co., Ltd.

[0106] Examples 1 to 20 and Comparative Examples 1 to 10 (Preparation of Resin-Coated Copper Foil of the Present Invention and Comparative Examples) On the rough surface of the ultra-low roughness non-roughening electrolytic copper foil CF-T9DA-SV (hereinafter referred to as "T9DA") manufactured by Fukuda Metal Foil & Powder Co., Ltd. (copper foil thickness 12μm, surface roughness 0.85μm), using an automatic applicator, the resin compositions of Formulation Examples 1 to 20 in an amount such that the film thickness of the resin layer after coating and drying is 30μm were respectively applied, and heated and dried at 120°C for 10 minutes to prepare the resin-coated copper foils of Examples 1 to 20. Also, using the resin compositions of Formulation Examples 21 to 30, the resin-coated copper foils of Comparative Examples 1 to 10 were prepared in the same manner as above.

[0107] (Evaluation of the Variation in the Film Thickness of the Resin Layer of the Copper Foil with Resin) For the copper foils with resin obtained in Examples 1 to 20 and Comparative Examples 1 to 10, the film thicknesses of the resin layer at 10 arbitrarily selected locations were determined by dividing the measured values of the thickness at 10 locations by the thickness of the copper foil. Among the 10 film thicknesses obtained above, the difference between the maximum film thickness and the minimum film thickness was calculated, and the variation in the film thickness was evaluated according to the following evaluation criteria. The results are shown in Tables 1 to 3. 〇 ··· The difference between the maximum film thickness and the minimum film thickness is less than 4.0 μm × ··· The difference between the maximum film thickness and the minimum film thickness is 4.0 μm or more

[0108] Examples 21 to 40 and Comparative Examples 11 to 20 (Preparation of Copper-Clad Laminates of the Present Invention and Comparative Examples) PPE prepreg (Meteorwave4000, manufactured by AGC nelco Co., Ltd.) was overlaid on the resin layer of the copper foils with resin obtained in Examples 1 to 20 and Comparative Examples 1 to 10, and vacuum-pressed at 200 °C for 60 minutes under the condition of 3 MPa to cure the resin layer, thereby preparing the copper-clad laminates of Examples 21 to 40 and Comparative Examples 11 to 20, respectively.

[0109] (Evaluation of the Adhesion Strength of the Copper-Clad Laminate) Each of the copper-clad laminates obtained in Examples 21 to 40 and Comparative Examples 11 to 20 was cut into a width of 10 mm, and using an autograph AGS-X-500N (manufactured by Shimadzu Corporation), the 90° peel strength (peeling rate was 50 mm / min) between the copper foil having a resin layer composed of the cured product of the PPE prepreg and the resin composition was measured, and the adhesion strength was evaluated according to the following evaluation criteria. In addition, when the samples after the test were visually confirmed, cohesive failure occurred in all of them. The results are shown in Tables 1 to 3. ◎ ··· 6.5 N / cm or more 〇 ··· 5.5 N / cm or more and less than 6.5 N / cm △ ··· 4.5 N / cm or more and less than 5.5 N / cm × ··· Less than 4.5 N / cm

[0110] (Evaluation of the Thermal Properties of the Copper-Clad Laminate) The copper foils with resin obtained in Examples 1 to 20 and Comparative Examples 1 to 10 were floated in a solder bath heated to 288 °C with POT-200C (manufactured by Taiyo Electric Industry Co., Ltd.), the time until blistering occurred was measured, and the thermal properties were evaluated according to the following evaluation criteria. The results are shown in Tables 1 to 3. ◎ ··· No blistering for 10 minutes or more 〇 ··· Blistering occurred in 1 minute or more and less than 10 minutes × ··· Blistering occurred in less than 1 minute

[0111] (Evaluation of Dielectric Constant and Dissipation Factor of Resin Layer Composed of Cured Product of Resin Composition) Copper foils with resin were produced in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 10, except that the coating amount of the resin compositions in Formulation Examples 1 to 30 was changed from the amount that made the film thickness of the resin layer 30 μm to the amount that made it 100 μm. After that, the resin layers were cured by heating at 200 °C for 60 minutes to obtain copper-clad laminates respectively. The copper foils of the copper-clad laminates obtained above were etched and removed with an iron(III) chloride solution having a liquid specific gravity of 45 Baumé, washed with ion-exchanged water, and dried at 105 °C for 10 minutes to obtain resin layers composed of cured products of the resin compositions respectively. For the resin layers obtained above, the breaking stress, breaking elongation, and elastic modulus were measured using Autograph AGS-X-500N (manufactured by Shimadzu Corporation), and the dielectric constant and dissipation factor at 10 GHz were measured by the cavity resonance method using a network analyzer 8719ET (manufactured by Agilent Technologies). The results are shown in Tables 1 to 3.

[0112] [Table 1]

[0113] [Table 2]

[0114] [Table 3]

[0115] From the results in Tables 1 to 3, it is clear that the copper foil with resin of the present invention has little variation in film thickness, and the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the copper foil with resin has high adhesive strength and heat resistance. Furthermore, the cured product of the resin layer composed of the resin composition is excellent in dielectric properties.

Industrial Applicability

[0116] Since the resin composition that forms the resin layer of the copper foil with resin of the present invention has excellent coatability, the copper foil with resin can be prepared by an easy method. In addition, the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the copper foil with resin of the present invention has excellent adhesiveness between the cured product of the resin layer and the copper foil, good heat resistance of the cured product of the resin layer, and excellent dielectric properties, and thus can be suitably used for printed wiring boards and the like.

Claims

1. A copper foil with a resin layer made of a resin composition on the roughened surface of a copper foil having a surface roughness (Rz) of 1.1 μm or less or on the surface of a non-roughened copper foil, wherein the resin composition is an imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) containing an aminophenol compound (a1) having at least two amino groups in one molecule, an aliphatic diamino compound (a2) having 6 to 36 carbon atoms, and an aromatic diamino compound (a3) having no phenolic hydroxyl group, and a tetracarboxylic dianhydride (B), and a polyimide resin (D) which is a reaction product of a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group, silica (E) having a specific surface area in the BET method of 1.0 to 20 m ２ / g, a thermosetting resin (F), and a curing agent (G).

2. The copper foil with resin according to Claim 1, wherein the content of silica (E) is 5 to 50% by mass based on the solid content of the polyimide resin (D).

3. The copper foil with resin according to Claim 1 or 2, wherein the average particle diameter of silica (E) is 0.3 to 5.0 μm.

4. The copper foil with resin according to any one of Claims 1 to 3, wherein silica (E) is silica that has not been surface-treated with a silane compound.

5. The aminophenol compound (a1) having at least two amino groups in one molecule represents a divalent linking group represented by the following formula (1). 【Chemical 1】 (In formula (1), R １ represents a hydrogen atom, a methyl group or an ethyl group, and X is C(CH ３ ) ２ , C(CF ３ ) ２ , SO ２ , an oxygen atom, a direct bond or the following formula (2) 【Chemical Formula 2】 (It represents a divalent linking group.) The copper foil with resin according to Claim 1, comprising a compound represented by the formula.

6. The tetracarboxylic dianhydride (B) represents a divalent linking group represented by the following formulas (3) to (11). [Chemical 3] (In formula (6), Y is C(CF ３ ), ２ SO ２ , CO, an oxygen atom, a direct bond or the following formula (2) 【Chemical 4】 (It represents a divalent linking group.) The copper foil with resin according to Claim 1, comprising a compound selected from the group consisting of the following formulas.

7. The functional group capable of reacting with the phenolic hydroxyl group of the compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group is an isocyanate group or a carboxylic acid chloride group. The copper foil with resin according to Claim 1.

8. The aromatic diamino compound (a3) having no phenolic hydroxyl group is represented by the following formulas (12) to (15). 【Chemical Formula 5】 (In formula (14), R ２ independently represents a methyl group or a trifluoromethyl group, and in formula (15), Z is CH(CH ３ ), SO ２ ), CH ２ ), O-C ６ H ４ -O, an oxygen atom, a direct bond, or the following formula (2) [Chemical Formula 6] The divalent linking group represented by is R ３ independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. The copper foil with resin according to claim 1, comprising a compound selected from the group consisting of).

9. The copper foil with resin according to Claim 1, wherein the thermosetting resin (F) contains an aromatic maleimide resin.

10. A copper-clad laminate obtained by curing a resin layer composed of a resin composition of the copper foil with resin according to any one of Claims 1 to 9.

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