JP2023075383A - Polyimide resin composition and cured body thereof - Google Patents

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

The present invention relates to a resin-coated copper foil having a resin layer made 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 resin-coated copper foil.

BACKGROUND ART Printed wiring boards are indispensable members for electronic devices such as mobile communication devices such as smartphones and tablets, communication base station devices, computers and car navigation systems. 2. Description of the Related Art 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, high-speed, large-capacity printed wiring boards for next-generation high-frequency radio have been developed. It is required to be tangent.

High-frequency electrical signals are used in communication equipment and electronic equipment for the purpose of transmitting and processing large amounts of information at high speed. A device to reduce the transmission loss is required. Transmission loss is roughly divided into conductor loss and dielectric loss. When the frequency of the electrical signal exceeds GHz, conductor loss depends on the surface condition of the copper foil used in the circuit. In general, it is preferable to use low-roughness or non-roughened copper foils, ie, low dielectric resins with high adhesion to these copper foils are desired.

Polyimide resins, which are excellent in properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, are widely used in electrical and electronic parts, semiconductors, communication equipment and its circuit parts, peripheral equipment, and the like. In particular, soluble polyimide resins, whose solvent solubility has been improved by structural devising, etc., are easy to process and coat, and are used in a wide range because they do not require imidization processes that require high temperatures when used.
On the other hand, it is known that hydrocarbon compounds such as petroleum and natural oils exhibit high insulating properties and low dielectric constants.

Patent Documents 1 and 2 describe a resin composition containing a polyimide resin into which a dimer diamine skeleton having a long alkyl chain is introduced and a resin-coated copper foil using the same, and these resin compositions are Adhesion to copper foil and high solder heat resistance.
However, since further reduction in transmission loss is required in the high frequency region, it is necessary to reduce components such as epoxy resin that deteriorate dielectric properties. In addition, it is known that the transmission loss in the high-frequency region increases when the surface roughness of the copper foil increases. If the roughness of the resin composition becomes small, the adhesiveness of the resin composition to the copper foil is lowered.

Patent Document 3 describes an example in which silica is added to a polyimide resin into which a dimer diamine skeleton has been introduced in order to improve dielectric properties. However, the resin composition described in Patent Document 3 has a high epoxy resin content, and in addition to an insufficient effect of reducing dielectric properties, there is a problem that the amount of filler added is poor, so that the coating properties on copper foil are poor. there were.

In response to the above problem, Patent Document 4 describes that high dielectric properties are achieved by reducing the content of epoxy resin in the resin composition. However, since the composition of Patent Document 4 contains a low thermosetting resin content, the cured product has a low crosslink density and low heat resistance.

JP 2018-168369 A JP 2017-119361 A Japanese Patent Application Laid-Open No. 2019-173010 WO2020/071154

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

As a result of extensive studies, the present inventors found that a modified polyimide resin with a specific structure, silica having a specific specific surface area, a thermosetting resin The inventors have found that a resin-coated copper foil having a resin layer made of a resin composition containing a curing agent and a curing agent can solve the above problems, and completed the present invention.
That is, the present invention
(1) A resin-coated copper foil having a resin layer made of a resin composition on the roughened surface of the copper foil or the surface of the non-roughened copper foil having a surface roughness (Rz) of 1.1 μm or less, wherein the resin composition The substance is 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 An imidized product (P) of a polyamic acid resin which is a copolymer of an amino compound (A) and a tetrabasic dianhydride (B) containing a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated di Polyimide resin (D) which is a reaction product with compound (C) having a heavy bond group, silica (E) having a specific surface area determined by BET method of 1.0 to 20 m ² /g, thermosetting resin (F) and a resin-coated copper foil containing a curing agent (G),
(2) The resin-coated copper foil according to (1) above, wherein the content of silica (E) is 5 to 50% by mass with respect to the solid content of the polyimide resin (D);
(3) The resin-coated copper foil according to (1) or (2) above, wherein the silica (E) has an average particle size of 0.3 to 5.0 μm;
(4) The resin-coated copper foil according to any one of (1) to (3) above, wherein the silica (E) is silica not surface-treated with a silane compound;
(5) an aminophenol compound (a1) having at least two amino groups in one molecule, represented by the following formula (1)

(In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (2) )

Represents a divalent linking group represented by )
The resin-coated copper foil according to the preceding item (1) containing a compound represented by
(6) Tetrabasic dianhydride (B) is represented by the following formulas (3) to (11)

(In formula (6), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (2)

Represents a divalent linking group represented by )
The resin-coated copper foil according to the preceding item (1) containing a compound selected from the group consisting of
(7) The functional group capable of reacting with the phenolic hydroxyl group in 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 resin-coated copper foil according to (1),
(8) The aromatic diamino compound (a3) having no phenolic hydroxyl group is represented by the following formulas (12) to (15)

(In formula (14), R ₂ independently represents a methyl group or a trifluoromethyl group; 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)

_R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. ) The resin-coated copper foil according to the preceding item (1) containing a compound selected from the group consisting of
(9) The resin-coated copper foil according to the preceding item (1), wherein the thermosetting resin (F) contains an aromatic maleimide resin, and (10) The resin-coated copper foil according to any one of the preceding items (1) to (9). A copper-clad laminate obtained by curing a resin layer made of a resin composition possessed by the resin-coated copper foil of
Regarding.

Since the resin composition that forms the resin layer of the resin-coated copper foil of the present invention has excellent coatability, the resin-coated copper foil can be prepared by a simple method. In addition, the copper-clad laminate obtained by curing the resin layer made of the resin composition of the resin-coated copper foil of the present invention has excellent adhesion between the cured resin layer and the copper foil, and the cured resin layer has excellent adhesion. It has good heat resistance and excellent dielectric properties, so it can be suitably used for printed wiring boards and the like.

The present invention will be described in detail below.
The resin-coated copper foil of the present invention is
(1) A resin-coated copper foil having a resin layer made of a resin composition on the roughened surface of the copper foil or the surface of the non-roughened copper foil having a surface roughness (Rz) of 1.1 μm or less, wherein the resin composition The substance is 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 having 6 to 36 carbon atoms (a2) ( hereinafter simply referred to as "(a2) component") and an amino compound (A) containing an aromatic diamino compound (a3) having no phenolic hydroxyl group (hereinafter also simply referred to as "(a3) component") Hereinafter, simply referred to as "component (A)") and tetrabasic dianhydride (B) (hereinafter also simply referred to as "component (B)"), which is an imidized polyamic acid resin. (P) (hereinafter also simply referred to as “imidated product (P)”) and a compound (C) having a functional group capable of reacting with a phenolic hydroxyl group and an ethylenically unsaturated double bond group (hereinafter simply referred to as “( Polyimide resin (D) (hereinafter also simply referred to as "(D) component"), which is a reaction product with (also referred to as "component C)", has a specific surface area in the BET method of 1.0 to 20 m ² /g A certain silica (E) (hereinafter simply referred to as "(E) component"), a thermosetting resin (F) (hereinafter simply referred to as "(F) component") and a curing agent (G) (hereinafter simply referred to as "(F) component") It has a resin layer made of a resin composition (hereinafter also simply referred to as "resin composition") containing (also simply referred to as "component (G)").
First, the imidized product (P), which is an intermediate raw material for the component (D), will be described.

The component (a1) used for synthesizing the imidized compound (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 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 and the like. These may be used alone or in combination of two or more.

The component (a1) used for synthesizing the imidized compound (P) preferably contains a compound represented by the following formula (1).

(In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (2) ) represents a divalent linking group.

The amount of component (a1) used when synthesizing the imidized product (P) is such that the phenolic hydroxyl equivalent of the imidized product (P) is 1,500 to 25,000 g/eq. is preferred. A phenolic hydroxyl equivalent of 1,500 g/eq. is lower than 25,000 g/eq. If it exceeds, the number of cross-linking points of the finally obtained component (D) decreases due to the decrease in the reaction points with the component (C) described later, and the heat resistance of the cured product of the resin composition and the compatibility with the substrate. Adhesion tends to decrease.
Incidentally, the phenolic hydroxyl group equivalent in the present specification means a value measured by a method according to JIS K-0070.

The imidized product (P) is obtained by an imidization reaction of a polyamic acid resin which is a copolymer of the components (A) and (B), ie, a cyclization reaction by dehydration condensation. Therefore, the amounts (ratios) of the components (A) and (B) necessary for synthesizing the imidized product (P) having the intended hydroxyl group equivalent and aliphatic chain content are and (B) components and the number of phenolic hydroxyl groups in component (a1).

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 6 to 36 carbon atoms and having two amino groups in one molecule. The aliphatic structure in the component (a2) may be linear, branched or cyclic, or may have the above structures, and may be saturated or unsaturated. may
Specific examples of component (a2) include hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,3-bisaminomethylcyclohexane, norbornanediamine, isophoronediamine, dimerdiamine, 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, diaminopolysiloxane having 6 to 36 carbon atoms, and the like. These may be used alone or in combination of two or more. From the viewpoint of the dielectric properties of the finally obtained component (D), dimer diamine is preferably used.

The dimer diamine described in the specific examples of component (a2) is obtained by substituting primary amino groups for the two carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid. See Japanese Laid-Open Patent Publication No. 9-12712, etc.). Specific examples of commercially available dimer diamines include PRIAMINE 1074 and PRIAMINE 1075 (both manufactured by Croda Japan Co., Ltd.) and Versamin 551 (manufactured by Cognis Japan Co., Ltd.). These may be used alone or in combination of two or more. Hereinafter, non-limiting general formulas of dimer diamines are shown (in each formula, m + n = 6 to 17 is preferable, p + q = 8 to 19 is preferable, and the broken line indicates a carbon-carbon single bond or a carbon-carbon double bond. means).

The amount of component (a2) used when synthesizing the imidized product (P) is determined by dividing the mass of component (A) by the number of moles of water (water generated by the dehydration condensation reaction) that is twice the number of moles of component (B). ) (the mass of the imidized product (P) produced) is preferably in the range of 10 to 50% by mass. If the amount of component (a2) is less than the above range, the number of aliphatic chains derived from component (a2) in component (D) finally obtained is too small, and the dielectric loss tangent of the cured product of the resin composition is high. When the above range is exceeded, the number of aliphatic chains derived from component (a2) in component (D) is too large, and the heat resistance of the cured product of the resin composition is lowered.

The component (a3) used in the synthesis of the imidized product (P) may be an aromatic diamino compound other than the component (a1), and may be an aromatic compound having two amino groups in one molecule. is not particularly limited. Specific examples of 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'-diaminodiphenylthioether, 3,3'-dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3, 3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylthioether, 2,2′-bis(3-aminophenyl)propane, 2,2′-bis(4-aminophenyl)propane, 4,4 '-diaminodiphenylsulfoxide, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 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-amino phenoxyphenyl)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.

The (a3) component used for the synthesis of the imidized product (P) is the following formula (12) from the viewpoint of the heat resistance of the cured product of the resin composition and the solubility of the finally obtained component (D) in a solvent. It preferably contains a compound selected from the group consisting of (15).

In formula (14), _R2 independently represents a methyl group or a trifluoromethyl group. In formula (15), R ₃ is independently a hydrogen atom, a methyl group or an ethyl group; Z is CH(CH ₃ ), SO ₂ , CH ₂ , O—C ₆ H ₄ —O, an oxygen atom, or a direct bond; Or represents a divalent linking group represented by the above formula (2).

The component (B) used for synthesis of the imidized compound (P) is not particularly limited as long as it has two acid anhydride groups in one molecule.
Specific examples of component (B) include pyromellitic anhydride, ethylene glycol-bis(anhydrotrimellitate), glycerin-bis(anhydrotrimellitate) monoacetate, 1,2,3,4,-butane Tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4 ,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic 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, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3′,4,4′-benzophenonetetracarboxylic acid are preferred in terms of solvent solubility and adhesion to substrates. The dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride or 3,3′,4,4′-diphenylethertetracarboxylic dianhydride is preferred. These may be used alone or in combination of two or more.

The (B) component used in the synthesis of the imidized product (P) is a 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 the (D) component. It is preferable to contain more selected compounds.

In formula (6), Y represents C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or a divalent linking group represented by formula (2) above.

When the number of moles of component (a1) in component (A) used for synthesis of imidized compound (P) is a1M, the number of moles of component (a2) is a2M, and the number of moles of component (a3) is a3M, a1M The value of /(a1M+a2M+a3M) is preferably greater than 0.01 and less than 0.3, more preferably greater 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), which will be described later, is reduced, so that the substrate adhesiveness and soldering heat resistance of the cured product of the resin composition tend to decrease. . Further, when a1M/(a1M+a2M+a3M) is 0.3 or more, the dielectric properties of the cured product of the resin composition tend to deteriorate.

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

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

The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of the polyamic acid resin of the group is obtained. At this time, the value of MA/MB is preferably in the range of more than 1.0 and less than 2.0, more preferably more than 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the component (D), the residual rate of unreacted raw materials increases, and heat resistance after curing of the resin composition, etc. properties may be degraded.

The number of moles of component (A) is MA, and the number of moles of component (B) is MB. An imidized product (P) of a polyamic acid resin having an acid anhydride group is obtained. At this time, the value of MB/MA is preferably in the range of more than 1.0 and less than 2.0, more preferably more than 1.0 and less than 1.5. If the above value is 2.0 or more, in addition to insufficient increase in the molecular weight of the component (D), the residual rate of unreacted raw materials increases, and heat resistance after curing of the resin composition, etc. properties may be degraded.

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

Then, if necessary, a dehydrating agent or a catalyst is added to the polyamic acid resin solution obtained above, and the mixture is heated and stirred at 100 to 300° C. to cause an imidization reaction (a ring closure reaction accompanied by dehydration) to obtain an imidized product (P). be done. Toluene, xylene and the like can be used as dehydrating agents, and tertiary amines and dehydrating catalysts can be used as catalysts. Preferred tertiary amines are heterocyclic tertiary amines such as pyridine, picoline, quinoline, and isoquinoline. Dehydration catalysts include, for example, acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. The reaction time for synthesizing the imidized compound (P) is greatly affected by the reaction temperature. Usually from a few minutes to 30 hours.

The above example is a method of synthesizing the imidized product (P) via polyamic acid. After dissolving the components (A) and (B) used in the synthesis in a solvent, a dehydrating agent and a catalyst are added as necessary. In addition, the copolymerization reaction and the imidization reaction may be performed together by heating and stirring at 100 to 300° C. to obtain the imidized product (P).

Solvents that can be used in synthesizing the imidized compound (P) include 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, and cyclopentanone. , cyclohexanone, methylcyclohexanone, acetylacetone, γ-butyrolactone, diacetone alcohol, cyclohexene-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, aceto Methyl acetate, 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, isovaleric acid Ethyl, isoamyl isovalerate, diethyl oxalate, dibutyl oxalate, methyl benzoate, ethyl benzoate, propyl benzoate, methyl salicylate, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Examples include, but are not limited to, sulfoxides. These may be used alone or in combination of two or more.

The preferred amount of the solvent to be used should be appropriately adjusted depending on the viscosity of the resin to be obtained and the intended use.

In order to promote the dehydration reaction during the synthesis of the imidized product (P), it is preferable to use a catalyst. ), preferably 1 to 30%, more preferably 5 to 15%. Specific examples of usable catalysts include known basic catalysts such as triethylamine and pyridine. Among them, triethylamine is preferable because it has a low boiling point and does not easily remain.

Next, the (D) component, which is the reaction product of the imidized product (P) and the (C) component, will be described.
The component (D) is a polyimide resin having a structure in which an ethylenically unsaturated double bond group is introduced via the component (C) into some 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 made of the resin composition containing the component (D) to the copper foil is improved. There is a tendency. 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, the cured product of the resin composition has excellent heat resistance and adhesiveness. do.

The (C) component used for 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 functional groups capable of reacting with phenolic hydroxyl groups of component (C) include isocyanate groups, carboxylic acid chloride groups, acid anhydride groups, epoxy groups, silyl chloride groups, halogenated alkyl groups, ester groups, and sulfonyl chloride groups. and a carboxyl group. In particular, an isocyanate group is preferred because residual impurities derived from the leaving group from component (C) do not occur.
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.

Incidentally, the imidized product (P ) has an amino group at the end, so the functional groups that can react with phenolic hydroxyl groups are isocyanate group, carboxylic acid chloride group, acid anhydride group, epoxy group, silyl chloride group, halogenated alkyl group, ester group, sulfonyl chloride The group or carboxyl group (C) component can also react with the terminal amino group of the imidide (P).

Further, the imidized product (P ) has an acid anhydride group at the end, so the functional group that can react with the phenolic hydroxyl group is an isocyanate group, an epoxy group, or a carboxyl group. can.

Specific examples of component (C) include Karenz MOI (manufactured by Showa Denko KK), Karenz AOI, Karenz MOI-BM, Karenz MOI-BP, Karenz BEI, Karenz MOI-EG, AOI-VM, methacrylic acid chloride, and acrylic. Acid chloride, maleimidocaproic chloride, allyl bromide, allyl iodide, allyl chloride, 4-chloro-1-butene, 4-bromo-1-butene, crotnoyl chloride, cinnamoyl chloride and the like.

Component (D), which is a reaction product of 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) with a resin solution of imidized compound (P) and reacting the mixture at 80°C to 150°C.

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

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

Next, the (E) component will be explained.
The BET specific surface area of component (E) is preferably 1.0 to 20 m ² /g. By using the component (E) having a specific surface area within the above range, the dispersibility of the component (E) in the resin layer is improved, the flexibility of the cured product of the resin layer is improved, and the silica and the resin component are improved. The adhesive strength with the cured product of is improved, and cohesive failure of the resin layer due to external stress is less likely to occur.

The content of component (E) in the resin composition that forms the resin layer of the resin-coated copper foil of the present invention is preferably 5 to 50% by mass, preferably 10 to 45% by mass, based on the solid content of component (D). and more preferably 15 to 35% by mass. By setting the content of the component (E) within the above range, the adhesion between the cured resin layer and the copper foil is improved, and the cured resin layer has increased flexibility.

The average particle size of component (E) is preferably 0.3 to 5.0 μm. By setting the average particle size of the component (E) within the above range, it is possible to reduce the inclusion of air bubbles in the resin layer, and the resin layer efficiently penetrates into the unevenness of the copper foil to separate the cured product of the resin layer and the copper foil. improves adhesion.
The average particle size of component (E) in the present specification means a value measured using a laser diffraction scattering type particle size distribution analyzer.

Component (E) is preferably not surface-treated with a silane compound. If the component (E) is surface-treated, the dispersibility is improved, but the effect of improving the heat resistance of the cured resin layer and the adhesion between the cured resin layer and the copper foil cannot be sufficiently obtained. There is

Component (E) is preferably spherical. In this case, the resin layer efficiently penetrates into the unevenness of the surface of the copper foil, and the adhesion between the cured resin layer and the copper foil can be further enhanced.

Next, the (F) component will be explained.
Specific examples of component (F) include epoxy resins, maleimide resins, carbodiimide resins, benzoxazine compounds and compounds having ethylenically unsaturated groups. These resins or compounds may be used alone or in admixture of two or more depending on the physical properties and application of the copper-clad laminate obtained by curing the resin layer of the resin-coated copper foil of the present invention. be able to.
In the present invention, by using component (D) in combination with component (F), it is possible to impart thermal stability and high adhesiveness to the cured product of the resin layer composed of the resin composition. At that time, it is preferred 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) react with component (F).

As the 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, the number of moles of component (A) used for 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, and the number of terminal functional groups of the imide (P) is When the number of moles is MP and the number of moles of component (a1) is Ma1, 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.

In addition, the component (F) preferably has a molecular weight of 100 to 50,000 from the viewpoint of suppressing an increase in viscosity when the resin composition is dissolved in a solvent to form a varnish. The term "molecular weight" as used herein means the weight-average molecular weight of a polystyrene standard determined by gel permeation chromatography (GPC).

The maleimide resin as component (F) is not particularly limited as long as it has two or more maleimide groups in one molecule.
Specific examples of maleimide resins having two or more maleimide groups in one molecule include tris- (4-aminophenyl)-phosphate, tris(4-aminophenyl)-phosphate, maleimide compound obtained by reaction of tos(4-aminophenyl)-thiophosphate with maleic anhydride, tris(4-maleimidophenyl)methane tetramaleimide compounds such as bis(3,4-dimaleimidophenyl)methane, tetramaleimidobenzophenone, tetramaleimidonaphthalene, maleimide obtained by the reaction of triethylenetetramine and maleic anhydride, phenol novolac type maleimide resins, isopropylidenebis(phenoxyphenylmaleimide)phenylmaleimide alkyl resins, biphenylene-type phenylmaleimide alkyl resins, etc. Commercially available products include MIR-3000, MIR-5000 (both manufactured by Nippon Kayaku Co., Ltd.), BMI- 70, BMI-80 (all manufactured by KI Kasei Co., Ltd.), BMI-1000, BMI-2000, BMI-3000 (all manufactured by Daiwa Kasei Kogyo Co., Ltd.), and the like.

In particular, a maleimide resin having an aromatic ring such as a benzene ring, a biphenyl ring and a naphthalene ring is preferable because the resin layer composed of a cured product of the resin composition is excellent in properties such as mechanical strength and flame retardancy. Examples thereof include MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) and MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.).
The maleimide resin is added for the purpose of reacting with the ethylenically unsaturated double bond group of the component (D), thereby increasing the crosslink density of the resin layer composed of the cured product of the resin composition and resistance to the copper foil is improved, and adhesion to the copper foil and heat resistance are 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 several minutes to several hours.
The content of the maleimide resin in the resin composition for the resin layer is 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). is preferred.
In addition, the maleimide group equivalent in this specification means the theoretical maleimide equivalent calculated from the amine equivalent of the amine used as a raw material.

The epoxy resin as the component (F) is not particularly limited as long as it has two or more epoxy groups in one molecule. Epoxy resins having aromatic rings such as benzene rings, biphenyl rings and naphthalene rings are preferred because they are excellent in 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), thereby increasing the cross-linking density of the resin layer composed of the cured product of the resin composition and making it resistant to polar solvents. The resistance is improved, and the adhesion to the copper foil and heat resistance are improved.
The curing temperature of the resin composition containing the epoxy resin is preferably 150 to 250°C. The curing time depends on the curing temperature, but is generally several minutes to several hours.

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

The compound having an ethylenically unsaturated group as the component (F) is not particularly limited as long as it has one or more ethylenically unsaturated groups in one molecule.
Specific examples of compounds 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 ) 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, adipate 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 Neopen 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 ) acrylate, triethylolpropane 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 ethylene oxide adducts thereof.

In addition to these, urethane (meth)acrylates having both a (meth)acryloyl group and a urethane bond in the same molecule; polyester (meth)acrylates having both a (meth)acryloyl group and an ester bond in the same molecule; epoxy Epoxy (meth) acrylates derived from resins and having (meth) acryloyl groups; reactive oligomers in which these bonds are used in combination are also specific examples of compounds having ethylenically unsaturated groups.

Urethane (meth)acrylates include reaction products of hydroxyl group-containing (meth)acrylates, polyisocyanates, and other alcohols used as necessary. For example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; ) acrylates; sugar alcohol (meth)acrylates such as pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and toluene diisocyanate , hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, dicyclohexanemethylene diisocyanate, and their isocyanurates, burette reaction products, etc., reacted with polyisocyanates, etc., urethane ( meth)acrylates.

Polyester (meth)acrylates include, for example, 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 tetrahydro Monofunctional (poly)ester (meth)acrylates such as furfuryl (meth)acrylate; hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di(meth)acrylate, epichlorohydrin-modified Di (poly) ester (meth) acrylates such as phthalic acid di (meth) acrylate; 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone per 1 mol of trimethylolpropane or glycerin Mono-, di- or tri(meth)acrylates of adducted triols may be mentioned.

Also, a triol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, or δ-valerolactone to 1 mol of pentaerythritol, dimethylolpropane, trimethylolpropane, or tetramethylolpropane. mono-, di-, tri-, or tetra-(meth)acrylates; mono-triols obtained by adding 1 mol or more of cyclic lactone compounds such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone to 1 mol of dipentaerythritol, or Examples include mono(meth)acrylates or poly(meth)acrylates of polyhydric alcohols such as triols, tetraols, pentaols or hexaols of poly(meth)acrylates.

Furthermore, diol components such as (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, (poly)butylene glycol, 3-methyl-1,5-pentanediol, hexanediol, maleic acid, fumaric Polybasic acids such as acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium sulfoisophthalic acid, and anhydrides thereof (meth)acrylate of polyester polyol which is the reaction product of; (meth)acrylate of cyclic lactone-modified polyester diol composed of diol component, polybasic acid and their anhydrides and ε-caprolactone, γ-butyrolactone, δ-valerolactone, etc. and polyfunctional (poly)ester (meth)acrylates such as

Epoxy (meth)acrylates are carboxylate compounds of a compound having an epoxy group and (meth)acrylic acid. For example, phenol novolak type epoxy (meth)acrylate, cresol novolak 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)acrylates, and acid anhydride-modified epoxy acrylates thereof.

For example, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether; styrenes such as styrene, methylstyrene, ethylstyrene, and divinylbenzene; A compound having a vinyl group such as lunadiimide is also included as a specific example of the compound having an ethylenically unsaturated group.

As the compound having an ethylenically unsaturated group, commercially available products can be used. Propylene glycol monomethyl ether acetate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD (registered trademark) ZCR-6007H (trade name), KAYARAD (registered trademark) ZCR-6001H (trade name), KAYARAD (registered trademark) ZCR-6002H (trade name) , and KAYARAD (registered trademark) ZCR-6006H (trade name) These compounds having an ethylenically unsaturated group can be used singly or in admixture of two or more.

The content of the compound having an ethylenically unsaturated group in the resin composition forming the resin layer is preferably 0.1 to 500 equivalents relative to the ethylenically unsaturated double bond group equivalent of 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 material.

Next, the (G) component will be explained.
Component (G) is not particularly limited as long as it accelerates the curing reaction of component (F), and conventionally known curing agents for component (F) can be used. (G) A component may use only 1 type and may use 2 or more types together.

When the (F) component is a maleimide resin, known amine compounds, thiol compounds and radical initiators can be used as the (G) component.
Specific examples of amino compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, and 1,3-bisaminomethyl. Cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, polyoxypropylene Diamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin, etc., but not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a maleimide resin as the component (F), the amount of the amine compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) in mass ratio. be.
Further, specific examples of thiol compounds include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipenta Examples include, but are not limited to, erythritol hexakis(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanate, and the like. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a maleimide resin as the component (F), the amount of the thiol compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) of the present invention in mass ratio. is in the range.
Further, specific examples of radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4- dimethylvaleronitrile) and the like, but are not limited to these. 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 amount of the radical initiator added is 0.1 to 10% by mass based on the maleimide resin.
In particular, from the viewpoint of reaction rate and dielectric properties, it is preferable to use a radical initiator.

When the (F) component is an epoxy resin, known imidazole compounds, phosphine compounds, phenolic resins and amino compounds can be used as the (G) component.
Specific examples of imidazole compounds and phosphine compounds include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and 2-phenyl-4-methyl- imidazoles such as 5-hydroxymethylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7, triphenylphosphine, etc. phosphines, metal compounds such as tin octylate, and the like, but are not limited to these. 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 amount of the imidazole compound or phosphine compound added is 0.1 to 10% by mass relative to the epoxy resin.
Specific examples of phenol resins include 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, alkylaldehyde, 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.), phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensation products of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) Examples include, but are not limited to, polycondensates, polycondensates of bisphenols and various aldehydes, and modified products thereof. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains an epoxy resin as the component (F), the amount of the phenol resin added is preferably 5 times or less, more preferably 2 times the mass ratio of the component (F) to the epoxy resin. It is in the range of less than double.
Specific examples of amino compounds include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bis Aminomethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, metaphenylenediamine, diaminodiphenylsulfone, dicyandiamide, poly Oxypropylenediamine, polyoxypropylenetriamine, N-aminoethylpiperazine, aniline-formalin resin and the like, but not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains an epoxy resin as the component (F), the amount of the amine compound added is preferably 5 times or less, more preferably 2 times or less, that of the component (F) by weight. be.
From the viewpoint of dielectric properties, it is preferable to use an imidazole compound or a phosphine compound.

When component (F) is a compound having an ethylenically unsaturated group, it is preferred to use a radical initiator as component (G).
Specific examples of radical initiators include peroxides such as dicumyl peroxide and dibutyl peroxide, 2,2′-azobis(isobutyronitrile) and 2,2′-azobis(2,4-dimethylvalero nitrile) and other azo compounds, but are not limited to these. These may be used alone or in combination of two or more. When the resin composition that forms the resin layer contains a compound having an ethylenically unsaturated group, the amount of the radical initiator added is 0.1 to 10% by mass with respect to all ethylenically unsaturated groups in the composition. be.

A varnish-like composition (hereinafter simply referred to as varnish) can be obtained by using an organic solvent in combination with the resin composition that forms the resin layer.
Examples of solvents that can be used in combination include γ-butyrolactones, amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone, and tetramethylenesulfone. sulfones, 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, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone and aromatic solvents such as toluene and xylene.
The organic solvent is used in such a range that the concentration of components other than the organic solvent in the varnish is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.

You may use a well-known additive together with the resin composition used as a resin layer as needed.
Specific examples of additives that can be used in combination include polybutadiene or its modified product, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate ester compound, silicone gel, and silicone. Oil, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, glass powder and silica with a specific surface area other than 1.0 to 20 m ² /g Inorganic fillers such as, surface treatment agents for fillers such as silane coupling agents, release agents, coloring agents such as carbon black, phthalocyanine blue and phthalocyanine green, thixotropy imparting agents such as Aerosil, silicone-based, fluorine-based Leveling agents, antifoaming agents, hydroquinone, hydroquinone monomethyl ether, phenol polymerization inhibitors, stabilizers, antioxidants, photopolymerization initiators, photobase generators, photoacid generators and the like. The amount of these additives is preferably 1,000 parts by mass or less, more preferably 700 parts by mass, per 100 parts by mass in total of components (D), (E), (F) and (G). The following range is a precondition that the effects of the present invention are not impaired.

The method of preparing the resin composition that forms the resin layer is not particularly limited, but it is also possible to simply mix the components uniformly. For mixing each component, for example, an extruder, kneader, roll, or the like is used in the absence of a solvent, and a reactor equipped with a stirrer is used in the presence of a solvent.

Next, a method of obtaining a resin-coated copper foil of the present invention by providing 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. explain.
The resin-coated copper foil of the present invention can be obtained by various known methods. Specifically, a technique of heating the resin composition to lower its viscosity and casting, and a technique of applying a solution and drying the solvent can be used.
The coating means of the resin composition is not particularly limited, and includes curtain coaters, roll coaters, laminators and the like. In addition, various leveling means may be used in combination. As the copper foil, any known copper foil having a surface roughness (Rz) of 1.1 μm or less with a roughened surface or a non-roughened copper foil is particularly limited. can be used without Specific examples include rolled copper foil and electrolytic copper foil. Its thickness is not particularly limited, and it may be one subjected to surface treatment (roughening, rust prevention).

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 so-called B-stage state. Although the thickness of the resin layer is not limited, it is preferably about 12 to 105 μm.

The copper-clad laminate of the present invention can be obtained 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 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 component (D) and the reactive group of the component (F). When the composition contains a maleimide resin or an epoxy resin, the curing temperature is preferably 120 to 250° C., and the curing time is approximately several tens of minutes to several hours.

A base material having the copper-clad laminate of the present invention can be obtained by laminating a polyimide film or LCP (liquid crystal polymer) or the like on the surface of a resin layer made of a resin composition, followed by hot pressing and heat curing. can also Examples of the base material provided with a copper-clad laminate include copper-clad laminates (CCL), printed wiring boards and multilayer wiring boards having a circuit pattern on the copper foil of CCL.

EXAMPLES The present invention will be described in more detail below 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 % by mass. The GPC measurement conditions 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

Synthesis Example 1 (Synthesis of component (D) (polyimide resin 1))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.67 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539 .52 g / mol) 11.69 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 5.89 parts, and anisole 68.24 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 18.97 parts of toluene were added, and the amic acid was added. The reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure by azeotrope with toluene. 99,300), followed by 0.60 parts of Karenz MOI (manufactured by Showa Denko KK, molecular weight: 155.15 g/mol), and BHT (2,6-di-tert-butyl-p- 0.08 part of cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 1 solution (polyimide 1).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 1 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, 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, and the imide (P) solution (P- MC/(MAB+MP)=0.91, where MAB is the number of moles of phenolic hydroxyl groups in 1) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-1).

Synthesis Example 2 (Synthesis of component (D) (polyimide resin 2))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'- (hexafluoroisopropylidene) bis (2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.70 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.22 parts, APB-N (1,3-bis (3-aminophenoxy) benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol) 5.16 parts, and anisole 65.66 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight 310.22 g/mol), 0.81 parts of triethylamine and 18.64 parts of toluene were added, The reaction was carried out at 130° C. for 8 hours while removing the water generated due to the ring closure of the amic acid by azeotropic distillation with toluene. eq., molecular weight 101,200), followed by 0.60 parts of Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g/mol) and BHT (2,6-di-tert- 0.09 part of butyl-p-cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 2 solution (polyimide 2).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 2 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, 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, and the imide (P) solution (P- MC/(MAB+MP)=0.90, where MAB is the number of moles of phenolic hydroxyl groups in 2) and MP is the number of moles of terminal functional groups in the imide solution (P-2).

Synthesis Example 3 (Synthesis of component (D) (polyimide resin 3))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'-(hexafluoroisopropylidene) bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.69 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.45 parts, APB-N (1,3-bis (3-aminophenoxy) benzene, Mitsui Chemicals Fine Co., Ltd., molecular weight 292.12 g / mol) 5.05 parts, and anisole 70.0 parts and heated to 70° C. Then, BTDA (3,3′,4,4′-benzophenonetetracarboxylic dianhydride, manufactured by Daicel Corporation, molecular weight 322.01 g/mol) 12.88 parts, triethylamine Add 0.81 part and 18.80 parts of toluene, and react at 130 ° C. for 8 hours while removing water generated due to ring closure of amic acid by azeotrope with toluene. Imidide (P) solution (P-3) (Phenolic OH equivalent, 7,614.3 g/eq., molecular weight 86,200) Subsequently, Karenz MOI (manufactured by Showa Denko K.K., molecular weight 155.15 g/mol) 0.60 parts, polymerization prohibited 0.09 parts of BHT (2,6-di-tert-butyl-p-cresol) was added as an agent and reacted at 130° C. for 4 hours, followed by removal of residual triethylamine and toluene at 10° C. to produce a polyimide. A resin 3 solution (polyimide 3) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 3 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, 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, and the imide (P) solution (P- MC/(MAB+MP)=0.90, where MAB is the number of moles of phenolic hydroxyl groups in 3) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-3).

Synthesis Example 4 (Synthesis of component (D) (polyimide resin 4))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4'-(hexafluoroisopropylidene) bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.69 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g / mol) 11.92 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 6.01 parts, and anisole 69.0 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 19.08 parts of toluene were added, and the amic acid was added. The reaction was carried out at 130 ° C. for 8 hours while removing the water generated due to the ring closure by azeotrope with toluene, and the imidide (P) solution (P-4) (phenolic OH equivalent, 7,895 g / eq., molecular weight Subsequently, 0.58 parts of Karenz MOI (manufactured by Showa Denko KK, molecular weight 155.15 g/mol) and BHT (2,6-di-tert-butyl-p- 0.09 part of cresol) was added and reacted at 130° C. for 4 hours, and then residual triethylamine and toluene were removed at 130° C. to obtain a polyimide resin 4 solution (polyimide 4).
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 4 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, 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, and the imide (P) solution (P- MC/(MAB+MP)=0.85, where MAB is the number of moles of phenolic hydroxyl groups in 4) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-4).

Synthesis Example 5 (Synthesis of component (D) (comparative polyimide resin 1))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 0.67 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 539 .52 g / mol) 11.69 parts, BAFL (9,9-bis (4-aminophenyl) fluorene, JFE Chemical Co., Ltd., molecular weight 348.16 g / mol) 5.89 parts, and anisole 68.24 parts and heated to 70° C. Then, 12.41 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., Ltd., molecular weight of 310.22 g/mol), 0.81 parts of triethylamine and 18.97 parts of toluene were added, and the amic acid was added. While removing the water generated due to the ring closure by azeotrope with toluene, the reaction was performed at 130 ° C. for 8 hours to give a solution of comparative polyimide resin 1 (comparative polyimide 1) (phenolic OH equivalent, 7,953 g / eq., A molecular weight of 99,300) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 5 (moles of diamine component / number of acid anhydride components number of moles) was 1.01.

Synthesis Example 6 (Synthesis of component (D) (comparative polyimide resin 2))
11.38 parts of PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534.38 g / mol) was added to a 300 ml reactor equipped with a thermometer, a reflux condenser, a Dean-Stark device, a powder inlet, a nitrogen introduction device and a stirring device. , BAFL (9,9-bis(4-aminophenyl)fluorene, manufactured by JFE Chemical Co., Ltd., molecular weight 348.16 g/mol) and 170.06 parts of anisole were added 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 are added, and the water generated due to ring closure of amic acid is removed. After reaction at 130° C. for 8 hours with azeotropic removal with toluene, residual triethylamine and toluene were subsequently removed at 130° C. to give a solution of Comparative Polyimide Resin 2 (Comparative Polyimide 2) (molecular weight 89,400). ). The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 6 (moles of diamine component / number of acid anhydride components number of moles) was 1.01.

Synthesis Example 7 (Synthesis of component (D) (comparative polyimide resin 3))
DAPBAF (2,2-bis(3-amino-4-hydroxyphenyl)hexafluoro) was added to a 300 ml reactor equipped with a thermometer, reflux condenser, Dean-Stark apparatus, powder inlet, nitrogen inlet and stirring apparatus. Propane 4,4′-(hexafluoroisopropylidene)bis(2-aminophenol) (manufactured by Wakayama Seika Kogyo Co., Ltd., molecular weight 366.26 g / mol) 6.60 parts, PRIAMINE 1075 (manufactured by Croda Japan Co., Ltd., molecular weight 534 .38 g/mol) and 70.20 parts of anisole were added and heated to 70° C. Then, 12.88 parts of ODPA (oxydiphthalic anhydride, manufactured by Manac Co., molecular weight: 310.22 g/mol). , 0.81 parts 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 due to the ring closure of the amic acid by azeotrope with toluene. -7) (phenolic OH equivalent, 835 g / eq., molecular weight 32,200) was obtained.Next, Karenz MOI (manufactured by Showa Denko KK, molecular weight 155.15 g / mol) 5.96 parts, polymerization inhibitor 1.0 parts of BHT (2,6-di-tert-butyl-p-cresol) was added as a solution and reacted at 130°C for 4 hours. A polyimide resin 3 solution (comparative polyimide 3) was obtained.
The molar ratio of the diamine component ((a1) component, (a2) component and (a3) component) and the acid anhydride component ((B) component) used in Synthesis Example 7 (moles of diamine component / number of acid anhydride components The number of moles) is 1.01, 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, and the imide (P) solution (P- MC/(MAB+MP)=0.55, where MAB is the number of moles of phenolic hydroxyl groups in 7) and MP is the number of moles of terminal functional groups in the imide (P) solution (P-7).

Formulation Examples 1 to 30 (Adjustment of resin composition (Formulation Examples 1 to 20 are resin compositions for resin-coated copper foils of the present invention, Formulation Examples 21 to 30 are resin compositions for resin-coated copper foils of comparative examples)
After blending each component in the blending amount shown in Tables 1 to 3 (unit is "part", the number of parts in the table is the number of parts converted to solid content without solvent), the solid content concentration is 20% by mass. By adding an appropriate amount of anisole as a solvent and uniformly mixing, each resin composition that will be the resin layer of the resin-coated copper foil was prepared.

Each component in Tables 1 to 3 is as follows. Incidentally, 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, Nippon Kayaku Co., Ltd. XD-1000; Epoxy resin, Nippon Kayaku Co., Ltd. ZXR-1889H; Epoxy acrylate resin, Nippon Kayaku Co., Ltd. <Inorganic filler>
(E-1); SFP-30M (manufactured by Denka Co., Ltd., fused silica, average particle size 0.6 μm, specific surface area 6.2 m ² /g)
(E-2); SFP-20M (manufactured by Denka Co., Ltd., fused silica, average particle size 0.4 μm, specific surface area 11.2 m ² /g)
(E-3); FB-3SDC (manufactured by Denka Co., Ltd., fused silica, average particle size 3.1 μm, specific surface area 3.6 m ² /g)
(E-4); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle size 0.7 μm, specific surface area 4.3 m ² /g)
(E-5) BA-1 (manufactured by Nikki Shokubai Kasei Co., Ltd., hollow silica, average particle diameter 16 μm, specific surface area 2.0 m ² /g)
(E-6); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., surface epoxysilane-treated fused silica, average particle size 0.7 μm, specific surface area 4.3 m ² /g)
(E-7); Sciqas 0.7 μm (manufactured by Sakai Chemical Industry Co., Ltd., surface polysiloxane-treated fused silica, average particle size 0.7 μm, specific surface area 4.3 m ² /g)
(E-8); 10SX-CH1 (manufactured by Admatechs Co., Ltd., surface aminosilane-treated fused silica, average particle size after cutting 5 μm coarse particles: 1.1 μm, specific surface area: 15 m ² /g)
(E-9); Sciqas 0.1 μm (manufactured by Sakai Chemical Industry Co., Ltd., fused silica, average particle size 0.1 μm, specific surface area 21.5 m ² /g)
(E-10); Nanoace D600 (manufactured by Nippon Talc Co., Ltd., talc, average particle size 0.6 μm, specific surface area 24 m ² /g)
(E-11); DAW-03 (manufactured by Denka Co., Ltd., alumina, average particle size 4.9 μm, specific surface area 0.5 m ² /g)
<Curing agent>
DCP; dicumyl peroxide, manufactured by Kayaku Nourion Co., Ltd. <Additive>
KR-513; Silane coupling agent, Shin-Etsu Chemical Co., Ltd. TT-LX; Lubricating oil additive, Johoku Chemical Co., Ltd. KTL-8FH; Teflon (registered trademark) powder, average particle size 3.5 μm, Co., Ltd. Made in Kitamura

Examples 1 to 20 and Comparative Examples 1 to 10 (Preparation of resin-coated copper foils of the present invention and comparative examples)
Fukuda Metal Foil & Powder Co., Ltd. ultra-low roughness non-roughening treated electrolytic copper foil CF-T9DA-SV (hereinafter referred to as “T9DA”. Copper foil thickness 12 μm, surface roughness 0.85 μm.) Using an automatic applicator, each of the resin compositions of Formulation Examples 1 to 20 was applied to the rough surface of , and dried by heating at 120 ° C. for 10 minutes. The resin-coated copper foils of Examples 1 to 20 were prepared. Further, using the resin compositions of Formulation Examples 21 to 30, resin-coated copper foils of Comparative Examples 1 to 10 were produced in the same manner as described above.

(Evaluation of variation in film thickness of resin layer possessed by resin-coated copper foil)
For the resin-coated copper foils obtained in Examples 1 to 20 and Comparative Examples 1 to 10, the thickness of the copper foil is divided from the thickness measurement values at 10 arbitrarily selected locations, and the thickness of the resin layer is obtained at 10 locations. I asked for the thickness. 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 film thickness was evaluated according to the following evaluation criteria. The results are shown in Tables 1-3.
○: 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

Examples 21 to 40 and Comparative Examples 11 to 20 (Production of copper-clad laminates of the present invention and comparative examples)
PPE prepreg (Meteorwave 4000, manufactured by AGC nelco Co., Ltd.) was superimposed on the resin layer of the resin-coated copper foil obtained in Examples 1 to 20 and Comparative Examples 1 to 10, and vacuum was applied at 200 ° C. for 60 minutes at 3 MPa. Copper-clad laminates of Examples 21 to 40 and Comparative Examples 11 to 20 were produced by pressing to cure the resin layers.

(Evaluation of adhesive strength of copper-clad laminate)
Each copper-clad laminate obtained in Examples 21 to 40 and Comparative Examples 11 to 20 was cut into 10 mm widths, and PPE prepregs and resin compositions were prepared using Autograph AGS-X-500N (manufactured by Shimadzu Corporation). 90° peeling strength (peeling speed: 50 mm/min) between a copper foil having a resin layer composed of a cured product of (1) was measured, and the adhesive strength was evaluated according to the following evaluation criteria. Incidentally, when the samples after the test were visually checked, cohesive failure had occurred in all of them. The results are shown in Tables 1-3.
◎: 6.5 N/cm or more ○: 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 ×: 4.5 N/cm less than cm

(Evaluation of thermal properties of copper clad laminate)
The resin-coated copper foils 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 Denki Sangyo Co., Ltd.) until blisters appeared. The time was measured and the thermal properties were evaluated according to the following evaluation criteria. The results are shown in Tables 1-3.
◎: No swelling for 10 minutes or more ○: Blistering occurred for 1 minute or more and less than 10 minutes ×: Blistering occurred for less than 1 minute

(Evaluation of Dielectric Constant and Dielectric Loss Tangent of Resin Layer Consisting of Cured Resin Composition)
Resins were prepared in the same manner as in Examples 1 to 20 and Comparative Examples 1 to 10, except that the coating amount of the resin composition of Formulation Examples 1 to 30 was changed from an amount that resulted in a film thickness of the resin layer of 30 µm to an amount that resulted in a film thickness of 100 µm. After the coated copper foil was produced, the resin layer was cured by heating at 200° C. for 60 minutes to obtain a copper-clad laminate. The copper foil of the copper clad laminate obtained above is removed by etching with an iron (III) chloride solution having a liquid specific gravity of 45 Baume degrees, washed with ion-exchanged water, and dried at 105 ° C. for 10 minutes to obtain a resin. A resin layer composed of a cured product of the composition was obtained. For the resin layer obtained above, the stress at break, elongation at break, and elastic modulus were measured using Autograph AGS-X-500N (manufactured by Shimadzu Corporation), and using a network analyzer 8719ET (manufactured by Agilent Technologies). The dielectric constant and dielectric loss tangent at 10 GHz were measured by the cavity resonance method. The results are shown in Tables 1-3.

From the results in Tables 1 to 3, the resin-coated copper foil 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 resin-coated copper foil has an adhesive strength. and high heat resistance, and it is clear that the cured product of the resin layer made of the resin composition is excellent in dielectric properties.

Since the resin composition that forms the resin layer of the resin-coated copper foil of the present invention has excellent coatability, the resin-coated copper foil can be prepared by a simple method. In addition, the copper-clad laminate obtained by curing the resin layer composed of the resin composition of the resin-coated copper foil of the present invention has excellent adhesion between the cured resin layer and the copper foil, and the cured resin layer has excellent adhesion. Since it has good heat resistance and excellent dielectric properties, it can be suitably used for printed wiring boards and the like.

Claims (10)

A resin-coated copper foil having a resin layer made of a resin composition on the roughened surface of the copper foil or the surface of the non-roughened copper foil having a surface roughness (Rz) of 1.1 μm or less, wherein the resin composition is Amino 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 An imidized product (P) of a polyamic acid resin which is a copolymer of a compound (A) and a tetrabasic dianhydride (B), a functional group capable of reacting with a phenolic hydroxyl group, and an ethylenically unsaturated double bond group Polyimide resin ( ^D ) which is a reaction product with compound (C) having A resin-coated copper foil containing (G). 2. The resin-coated copper foil 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 resin-coated copper foil according to claim 1, wherein silica (E) has an average particle size of 0.3 to 5.0 [mu]m. The resin-coated copper foil according to any one of claims 1 to 3, wherein the silica (E) is silica that has not been surface-treated with a silane compound. An aminophenol compound (a1) having at least two amino groups in one molecule is represented by the following formula (1)

(In formula (1), R ₁ represents a hydrogen atom, a methyl group or an ethyl group, X is C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , SO ₂ , an oxygen atom, a direct bond or the following formula (2) )

Represents a divalent linking group represented by )
The resin-coated copper foil according to claim 1, comprising a compound represented by. Tetrabasic dianhydride (B) is represented by the following formulas (3) to (11)

(In formula (6), Y is C(CF ₃ ) ₂ , SO ₂ , CO, an oxygen atom, a direct bond, or the following formula (2)

Represents a divalent linking group represented by )
The resin-coated copper foil according to claim 1, comprising a compound selected from the group consisting of 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. Resin-coated copper foil as described. An aromatic diamino compound (a3) having no phenolic hydroxyl group is represented by the following formulas (12) to (15)

(In formula (14), R ₂ independently represents a methyl group or a trifluoromethyl group; 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)

_R3 independently represents a hydrogen atom, a methyl group, an ethyl group or a trifluoromethyl group. 2. The resin-coated copper foil according to claim 1, comprising a compound selected from the group consisting of ). The resin-coated copper foil according to claim 1, wherein the thermosetting resin (F) contains an aromatic maleimide resin. A copper-clad laminate obtained by curing a resin layer composed of a resin composition contained in the resin-coated copper foil according to any one of claims 1 to 9.