JP2005105061A - Resin composition, conductive foil with resin, prepreg, sheet, sheet with conductive foil, laminated plate and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having a low transmission loss (a low dielectric constant, a low dielectric loss) serviceable under high frequency conditions, good handling properties, high heat resistance, low water absorption and high flame retardancy, a conductive foil with a resin, a prepreg, a sheet, a sheet with the conductive foil, a laminated plate and a printed wiring board. <P>SOLUTION: The resin composition comprises an oligomer (A) of a thermosetting polyphenylene ether, a flexibility-imparting agent (B) comprising at least one of polybutadiene and styrene-butadiene copolymers and a flame-retardant (C). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition used in the field of electronic materials such as electronic / electrical parts and printed wiring boards and uses thereof, and more specifically, a resin composition and a resin-coated conductor foil, a prepreg, a sheet, The present invention relates to a sheet with conductive foil, a laminated board, and a printed wiring board.

  In recent years, with the development of electronic and information communication equipment, for example, printed circuit boards constituting materials for integrated circuits such as portable terminals and materials used therefor are required to have various characteristics more severely.

  First, particularly in portable terminals and the like, it is required that the substrate constituent material be able to cope with usage conditions using a high frequency (a quasi-microwave of 1 GHz or more). Specifically, it is required to be able to suppress high-frequency transmission loss. To that end, it is necessary to keep the dielectric constant and dielectric loss tangent of the resin composition or the like low.

  In the element circuit, energy loss in the transmission process called dielectric loss occurs. However, energy loss is not preferable because it is consumed in the element circuit as heat energy and released as heat. As shown in Equation 1 below, the magnitude of the transmission loss of the transmission line formed by the printed wiring board may be proportional to the square root of the dielectric constant of the dielectric constituting the printed wiring board and the dielectric loss tangent of this dielectric. Are known. Therefore, it can be seen that it is necessary to reduce the dielectric constant and the dielectric loss tangent in order to reduce the transmission loss.

(Formula 1)
(Transmission loss) = (Coefficient) x (Frequency) x (Dielectric constant) ^1/2 x (Dielectric loss tangent)

  Further, chip component mounting uses SMT (surface mount technology) technology, printing cream solder, and melting and bonding the solder by reflow. However, with the recent change in solder material associated with lead-free soldering, the reflow temperature has risen, and the substrate constituent material is required to have multiple resistances at a MAX of 260 to 280 ° C.

  In addition, along with the demands for circuit impedance control and downsizing, new technology trends that include inductors and capacitors are also emerging, and it is necessary to reduce the drift of dielectric characteristics due to low water absorption, while at the same time requiring thinner substrate materials. Has been.

  In order to meet the above requirements, various organic materials and substrates using the same are marketed on the market. Specifically, polyimide, bismaleimide triazine, cyanate ester, polyvinyl benzyl ether, crosslinkable polyphenylene oxide (ether), fluorine, (epoxy or phenol resin + aromatic ester-based cured resin), low water absorption epoxy resin, syndiotactic Examples thereof include organic materials of tick polystyrene and printed circuit boards using these materials. However, none of them satisfy the above requirements, particularly heat resistance and low water absorption.

  In order to reduce the transmission loss, it is necessary to reduce the conductor loss in addition to the dielectric loss reduction, and the most effective is the reduction of the conductor roughening necessary for securing the adhesion strength. A high-frequency signal has a phenomenon called a skin effect in which current flows only on the surface of a conductor. In the case of copper, the skin depth is expressed by the following formula 2. When the skin depth in the GHz band is calculated from the following formula, it becomes 2.09 μm at 1 GHz and 0.93 μm at 5 GHz. If it is going to reduce this, there exists a fault that an insulating layer is applied to conductor foil, and the insulating layer is easy to crack and drop off at the time of making a conductor foil with resin after drying.

(Formula 2)
(Skin depth) = 2.09 / ((frequency) × (specific conductivity)) ^1/2

  An organic material that can meet this requirement is polyphenylene ether (PPE) having excellent physical properties such as high-frequency characteristics, dielectric characteristics, heat resistance, and low water absorption. For example, by creating a composite dielectric material in which a dielectric ceramic powder having excellent high frequency characteristics is mixed with PPE, a material whose physical properties are maintained can be realized. However, it is said that the insulation layer coating on the conductive foil mentioned above, cracking of the insulation layer at the time of creation of the conductor foil with resin after drying, dropout becomes remarkable, and the conductor peel strength of the cured product is reduced. There are drawbacks.

Under such circumstances, thermosetting PPE oligomers that have toughness and do not impair the excellent properties of PPE (low dielectric constant, low dielectric loss tangent, high glass transition temperature, low water absorption, etc.) have been proposed. (See Patent Document 1). However, unfortunately, when a resin-coated conductive foil with an insulating layer coated on a low-roughened conductor foil with only the above compounds is created, cracks and falling off of the insulating layer can easily occur, causing problems in cutting and handling. At the same time as it occurs, there is a problem that the amount of deflection until breakage decreases due to an increase in the flexural modulus.
JP 2003-221990 A

  Thus, conventionally, there has been a demand for a substrate constituent material such as a resin composition capable of realizing good handling properties and flame retardancy while maintaining the excellent characteristics of PPE, and a printed wiring board composed thereof. .

In view of the above circumstances, the present invention provides a resin composition, a prepreg, a conductor foil with resin, a prepreg, a sheet, a sheet with conductor foil, a laminate, and a printed wiring board that can be suitably used for various electronic devices. With the goal.
The present invention also has low transmission loss (low dielectric constant, low dielectric loss) that can be used under high frequency conditions, good handling properties, high heat resistance, low water absorption, and high flame retardancy. An object is to provide a resin composition, a copper foil with a resin, a prepreg, a sheet, a sheet with a conductive foil, a laminate, and a printed wiring board.

（式中、−（Ｏ−Ｘ−Ｏ）−は一般式（２）で示され、Ｒ１、Ｒ２、Ｒ７、Ｒ８は同一または異なっていてもよく、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ｒ３、Ｒ４、Ｒ５、Ｒ６は同一または異なっていてもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ａは炭素数２０以下の直鎖状もしくは分岐状もしくは環状の炭化水素である。−（Ｙ−Ｏ）−は一般式（３）で示され、Ｒ９、Ｒ１０は同一または異なっていてもよく、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ｒ１１、Ｒ１２は同一または異なっていてもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。−（Ｙ−Ｏ）−は一般式（３）で定義される１種類の構造、または一般式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｚは炭素数１以上の有機基であり、酸素原子を含むこともある。ａ、ｂは少なくともいずれか一方が０でない、０〜３００の整数を示す。ｉはそれぞれ独立に０または１の整数を示す。） In order to achieve the above object, the resin composition according to the first aspect of the present invention comprises:
A thermosetting polyphenylene ether oligomer (A) represented by the following general formula (1), and a flexibility-imparting agent (B) selected from any one or more of polybutadiene or styrene-polybutadiene copolymer; A flame retardant (C).

(In the formula, — (O—X—O) — is represented by the general formula (2), and R 1, R 2, R 7 and R 8 may be the same or different, and are a halogen atom or an alkyl group having 6 or less carbon atoms, or R3, R4, R5 and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a straight chain having 20 or less carbon atoms. Or a branched or cyclic hydrocarbon,-(YO)-is represented by the general formula (3), R9 and R10 may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms; R11 and R12 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. One type of structure defined by the formula (3) or two or more types of structures defined by the general formula (3) are randomly arranged, Z is an organic group having 1 or more carbon atoms, oxygen (A and b each represents an integer of 0 to 300, at least one of which is not 0. Each i independently represents an integer of 0 or 1.)

  In the resin composition having the above configuration, the blending ratio of the thermosetting polyphenylene ether oligomer (A) and the flexibility-imparting agent (B) is 5 to 66 parts by weight with respect to 100 parts by weight. It is preferable.

（式中、ｎは０以上の整数である。） In the resin composition having the above structure, the flexibility imparting agent (B) includes, for example, polybutadiene represented by the following general formula (4) and having an oligomer skeleton in which 1,2-vinyl bond is 80% or more. Composed.

(In the formula, n is an integer of 0 or more.)

In the resin composition having the above-described configuration, the flexibility imparting agent (B) includes, for example, a styrene-butadiene copolymer represented by the following general formula (5).

  In the resin composition having the above structure, the flame retardant (C) includes, for example, a halogenated aromatic flame retardant or a compound in which at least one of hydroxyl groups of a halogenated phenol is substituted with a vinylbenzyl group. Consists of.

  In the resin composition having the above-described configuration, the flame retardant (C) is blended in an amount of the thermosetting polyphenylene ether oligomer (A) and one or more of polybutadiene or styrene-polybutadiene copolymer (B). It is preferable that it is 5-100 weight part with respect to a total of 100 weight part.

In order to achieve the above object, the resin-coated conductor foil according to the second aspect of the present invention is:
On the conductor foil, the resin composition according to the first aspect is formed by coating and drying.

  In the conductor foil with resin having the above-described configuration, the conductor foil is made of, for example, any one of copper, silver, gold, aluminum, nickel-chromium, and nickel. For example, the conductor foil has a thickness of 3 to 70 μm. Is in range.

  In the conductor foil with resin having the above configuration, for example, the surface roughness of the conductor foil is in the range of 0.2 to 3.5 μm.

  In the resin-coated conductor foil having the above configuration, for example, the thickness of the resin layer formed on the conductor foil is 5 to 200 μm.

In order to achieve the above object, a printed wiring board according to a third aspect of the present invention includes:
The resin-coated conductor foil according to the second aspect is formed by heating and pressurizing one side or both sides.

In order to achieve the above object, the resin-coated conductor foil according to the fourth aspect of the present invention is:
The resin composition according to the first aspect is applied on a support, dried, placed on a conductor foil previously patterned in a predetermined shape, heated and pressurized, and then peeled off from the support. .

In order to achieve the above object, a printed wiring board according to the fifth aspect of the present invention comprises:
It is formed by laminating resin-coated conductor foils according to the fourth aspect.

In order to achieve the above object, the prepreg according to the sixth aspect of the present invention is:
The resin composition according to the first aspect is impregnated with a substrate.

In order to achieve the above object, the sheet according to the seventh aspect of the present invention is:
One or more prepregs according to the sixth aspect are stacked and cured.

In order to achieve the above object, the sheet with conductor foil according to the eighth aspect of the present invention is:
The prepreg according to the sixth aspect is configured by overlapping and curing a conductor foil on one or both sides of the prepreg.

In order to achieve the above object, a laminated board according to the ninth aspect of the present invention,
It is configured by sandwiching and curing a base material between the sheet according to the seventh aspect or the sheet with conductive foil according to the eighth aspect.

In order to achieve the above object, a printed wiring board according to a tenth aspect of the present invention is:
The sheet according to the seventh aspect, the sheet with conductive foil according to the eighth aspect, or the laminated board according to the ninth aspect is used.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can be used conveniently for various electronic devices, resin foil with a resin, a prepreg, a sheet | seat, a sheet | seat with conductor foil, a laminated board, and a printed wiring board are provided.
Further, according to the present invention, low transmission loss (low dielectric constant, low dielectric loss) that can be used under high frequency conditions, good handling properties, high heat resistance, low water absorption, high flame retardancy, A resin composition having resin, a conductor foil with resin, a prepreg, a sheet, a sheet with conductor foil, a laminate, and a printed wiring board are provided.

  As a result of intensive studies, the present inventors have completed the resin composition, the resin-coated conductor foil, and the printed wiring board according to the embodiments of the present invention, and will be described in detail below.

1. Resin Composition The resin composition according to the present embodiment is a flexible resin selected from at least one of thermosetting polyphenylene ether (PolyPhenyleneEther; PPE) oligomer (A) and polybutadiene or styrene-polybutadiene copolymer. It includes a property-imparting agent (B) and a flame retardant (C).

(A) Thermosetting PPE oligomer The thermosetting PPE oligomer (A) according to this embodiment is a bifunctional PPE obtained by oxidative polymerization of dihydric phenol and monohydric phenol, and halogen such as allyl bromide. And allyl resin obtained by dehydrohalogenation reaction under basic conditions in the presence of a phase transfer catalyst.

  The PPE oligomer (A) constituting the resin composition is a thermosetting material that inherits the excellent dielectric properties and toughness of PPE. This resin composition is free from cracks and insulation layer dropping in the resin-coated conductor foil described later in the B-stage state, has excellent handling properties, can impart toughness even in a cured product, and deteriorates dielectric properties, material strength, and water absorption Thus, it is possible to provide a conductive foil with resin and a printed wiring board imparted with flame retardancy.

（式中、−（Ｏ−Ｘ−Ｏ）−は一般式（２）で示され、Ｒ１、Ｒ２、Ｒ７、Ｒ８は同一または異なっていてもよく、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ｒ３、Ｒ４、Ｒ５、Ｒ６は同一または異なっていてもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ａは炭素数２０以下の直鎖状もしくは分岐状もしくは環状の炭化水素である。−（Ｙ−Ｏ）−は一般式（３）で示され、Ｒ９、Ｒ１０は同一または異なっていてもよく、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。Ｒ１１、Ｒ１２は同一または異なっていてもよく、水素原子、ハロゲン原子または炭素数６以下のアルキル基もしくはフェニル基である。−（Ｙ−Ｏ）−は一般式（３）で定義される１種類の構造、または一般式（３）で定義される２種類以上の構造がランダムに配列したものである。Ｚは炭素数１以上の有機基であり、酸素原子を含むこともある。ａ、ｂは少なくともいずれか一方が０でない、０〜３００の整数を示す。ｉはそれぞれ独立に０または１の整数を示す。） The thermosetting PPE oligomer (A) contained in the resin composition is represented by the following general formula (1).

(In the formula, — (O—X—O) — is represented by the general formula (2), and R 1, R 2, R 7 and R 8 may be the same or different, and are a halogen atom or an alkyl group having 6 or less carbon atoms, or R3, R4, R5 and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a straight chain having 20 or less carbon atoms. Or a branched or cyclic hydrocarbon,-(YO)-is represented by the general formula (3), R9 and R10 may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms; R11 and R12 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. One type of structure defined by the formula (3) or two or more types of structures defined by the general formula (3) are randomly arranged, Z is an organic group having 1 or more carbon atoms, oxygen (A and b each represents an integer of 0 to 300, at least one of which is not 0. Each i independently represents an integer of 0 or 1.)

This PPE oligomer (A) is an allyl terminal-modified material that is bifunctionalized without substantially impairing the characteristics of PPE, and has a low dielectric constant, low dielectric loss tangent, high glass transition temperature (T _g ), and low water absorption. Excellent characteristics. Moreover, since this PPE oligomer does not generate polar groups such as hydroxyl groups by the curing reaction, it has excellent dielectric properties and low water absorption. It also has the excellent heat resistance of PPE resin.

（式中、ｎは０以上の整数であり、５〜２００が好ましく、特に、１０〜１００が好ましい。） (B) Flexibility imparting agent The flexibility imparting agent (B) is selected from at least one polybutadiene or styrene-polybutadiene copolymer.
The polybutadiene resin has a structure represented by the following general formula (4) and is preferably an oligomer skeleton having 1,2-vinyl bond of 80% or more.

(In the formula, n is an integer of 0 or more, preferably 5 to 200, and particularly preferably 10 to 100.)

  The polybutadiene resin is excellent in compatibility and dispersibility with the thermosetting PPE oligomer (A), and also plays a role as a plastic component when forming the resin-coated conductor foil, and contributes to imparting flexibility in the B-stage state. Furthermore, since the chemical structure has few polar groups in the skeleton, the dipole moment is small and the dielectric properties are not deteriorated.

  The viscosity of the flexibility imparting agent (B) is preferably 0.1 to 500 Pa · s (1 to 5000 poise), more preferably 0.5 to 50 Pa · s (5 to 500 poise) at a temperature of 45 ° C. .

（式中、ｎは０〜８４０、ｍは０〜１４００の整数を表す。） Since the styrene-polybutadiene copolymer includes a diene portion of a soft segment, it has excellent rubber elasticity, and is excellent in compatibility with the thermosetting PPE oligomer (A) and dispersibility, and therefore can be suitably used. Among them, a styrene-polybutadiene copolymer having a structure represented by the following general formula (5) is preferable.

(In the formula, n represents an integer of 0 to 840 and m represents an integer of 0 to 1400.)

  Since the styrene-polybutadiene copolymer having the above structure is excellent in compatibility and dispersibility with the thermosetting PPE oligomer (A), it is also effective in cracking and insulating layer removal when forming a resin-coated conductor foil, which will be described later. Furthermore, it is possible to impart toughness without lowering dielectric properties and bending strength. Moreover, adhesiveness with conductor foil can also be improved. This is because the styrene-polybutadiene copolymer is excellent in rubber elasticity because it contains a diene portion of a soft segment, and because it contains an epoxy group, it can have high adhesion to a conductor foil. Furthermore, because of the chemical structure with few polar groups in the skeleton, there is little dipole moment and the dielectric properties are not degraded.

  The styrene ratio of the styrene-polybutadiene copolymer is not particularly limited, but is preferably in the range of 20 to 80%, particularly 30 to 70%. If the styrene ratio is less than the above lower limit, the compatibility tends to decrease. If it is greater than the above upper limit, sufficient crack resistance and insulating layer falling-off preventing effects may not be obtained in the B stage state.

  The number average molecular weight of the styrene-polybutadiene copolymer is not particularly limited, but is preferably 10,000 to 150,000, particularly preferably 50,000 to 100,000. If the amount is less than the above lower limit, sufficient crack resistance and the effect of preventing the insulating layer from falling off may not be obtained. The number average molecular weight can be measured by an analytical means such as GPC.

The blending ratio of the thermosetting PPE oligomer (A) and the polybutadiene or styrene-polybutadiene copolymer is preferably 5 to 66 parts by weight, particularly preferably 5 to 25 parts by weight with respect to 100 parts by weight. If the weight ratio is less than the above lower limit, sufficient crack resistance and insulating layer falling-off preventing effects may not be obtained, and if the weight ratio is larger than the above upper limit, the compatibility may decrease.
Moreover, the ratio of polybutadiene and a styrene-polybutadiene copolymer may be individual, and may use 2 types together. What is necessary is just to use properly by the thickness of the conductor foil to be used, the roughening amount, the thickness of an insulating layer, and the addition amount of the dielectric powder to mix | blend.

  Further, in order to promote radical polymerization of the double bond between the thermosetting PPE oligomer (A) and polybutadiene or styrene-polybutadiene copolymer, peroxides such as ketone peroxide, diacyl peroxide, peroxyketal, Oxyesters, hydroperoxides, peroxycarbonates, dialkyl peroxides and the like may be added.

(C) Flame retardant The flame retardant (C) used is preferably a halogenated aromatic addition type flame retardant or a compound in which at least one of the hydroxyl groups of the halogenated phenol is substituted with a vinylbenzyl group.

  Halogen-based aromatic flame retardants are less affected by deterioration in properties such as heat resistance and dielectric properties, and are less affected by lowering of fluidity because a flame retardant effect can be obtained with a small amount of addition. Specific examples of usable halogenated aromatic flame retardants are not particularly limited, but octabromodiphenyl oxide, tetrabromobisphenol A, bis (tribromophenoxy) ethane, tetrabromobisphenol A epoxy oligomer, ethylenebistetra Bromophthalimide, ethylenebispentabromodiphenyl, tris (tribromophenoxy) triazine, tribromoneopentyl alcohol, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), polydibromophenylene ether, brominated polystyrene, hexabromo Benzene, tetrabromobisphenol S, tris (tribromoneopentyl) phosphate, octabromotrimethylphenylindane, brominated polyphenylene oxide And the like.

  Furthermore, the flame retardant (C) can be properly used according to various required characteristics. Especially, regarding heat resistance, it is an electronic component, and a circuit board has a level of MAX 260 ° C./10 seconds × several times due to the problem of joining with lead-free solder. A reflow resistance and a solder DIP test at a level of 260 to 350 ° C./several seconds is required, and a flame retardant that does not decompose in this temperature range is required. Examples of materials satisfying such requirements include decabromodiphenyl oxide, ethylene bistetrabromophthalimide, ethylene bispentabromodiphenyl, tris (tribromophenoxy) triazine, tribromoneopentyl alcohol, brominated polystyrene, octane Examples include bromotrimethylphenylindane and brominated polyphenylene oxide.

  A compound in which at least one of the hydroxyl groups of the halogenated phenol is substituted with a vinylbenzyl group can use the production method taught in Japanese Patent Application Laid-Open No. 2001-253992. As the halogenated phenol compound used in the present embodiment, a commercially available halogenated phenol compound can be used. For example, chlorinated products such as dichlorophenol, trichlorophenol, pentachlorophenol, tetrachlorobisphenol A, dibromophenol, Brominated compounds such as tolubromophenol, pentabromophenol, tetrabromocatechol, tetrabromobisphenol A, brominated novolak and the like can be mentioned.

  As the halogenated phenol compound used in the present embodiment has a higher halogen content, the effect of the resulting halogen-containing vinyl benzyl ether compound as a flame retardant increases. The halogen content of the halogenated phenol compound is preferably 20% by weight or more, more preferably 40% by weight or more. When the halogen content is less than 20% by weight, the flame-retardant effect of the obtained halogen-containing vinyl benzyl ether compound is lowered, and the expected performance cannot be obtained.

  Examples of the vinyl benzyl halide that can be used in the present embodiment include p-vinyl benzyl chloride, m-vinyl benzyl chloride, p-vinyl benzyl bromide, m-vinyl benzyl bromide, and mixtures thereof. The amount of vinylbenzyl halide used varies depending on the type of halogenated phenol compound to be used, and thus cannot be specified unconditionally, but is preferably 0.1 to 1.5 equivalents, preferably 1 to 1.5 equivalents relative to 1 equivalent of the phenolic hydroxyl group of the halogenated phenol compound. Is 0.5 to 1.2 equivalents.

  When a compound in which at least one of the hydroxyl groups of the halogenated phenol is substituted with a vinylbenzyl group is used, the compound is excellent in compatibility with the thermosetting PPE oligomer (A) and cured by radical polymerization of double bonds. Since it is completely taken into the product, it is advantageous that there is little influence of strength reduction, cracks when forming the resin-coated conductor foil, and falling off of the insulating layer. Among them, TBBA-VB (tetrabromobisphenol A modified polyvinyl benzyl ether compound) is preferable from the viewpoint of ensuring compatibility and adhesion.

The blending ratio of the flame retardant (C) is 100 parts by weight of the total (A + B) of the flexibility imparting agent (B) composed of at least one of PPE oligomer (A), polybutadiene or styrene-polybutadiene copolymer. On the other hand, the flame retardant (C) is preferably 5 to 100 parts by weight, and may be appropriately selected depending on the required flame retardance rank and the type of the flame retardant (C). Specifically, when the bromo content is 10% by weight or more, a combustion test result that can obtain UL94 V-0 at 1/16 inch is obtained. The UL94 standard is a flame retardance standard that is generally used, and is required to pass the conditions of V-1, preferably V-0, in a vertical combustion test.
However, the optimum addition amount differs depending on the addition amount of the flexibility imparting agent (B) and the addition amount of the dielectric powder. Moreover, you may use together the compound by which at least 1 or more was substituted by the vinyl benzyl group among the hydroxyl groups of halogenated aromatic addition type flame retardant or halogenated phenol.

  The flame retardant (C) is not limited to the above materials, and other materials generally used as flame retardants can be used. Specifically, aluminum hydroxide, magnesium hydroxide, silica, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide Metal oxides such as antimony oxide, nickel oxide, copper oxide, tungsten oxide, metals such as aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, cobalt, tin, antimony Examples thereof include powder, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium carbonate, calcium carbonate, and barium carbonate.

  Moreover, about the above-mentioned material, you may surface-treat for dispersibility improvement and an interface state improvement. Specific examples include surface treatment with a silane compound (chlorosilane, alkoxysilane, organofunctional silane, silazane), titanate-based, aluminum-based coupling agent, and the like. The surface treatment method includes a dry method, a wet method, an integral blend method, and the like, but can be selected at any time according to required properties, processes, and facilities.

  Moreover, when using the styrene-polybutadiene copolymer mentioned below, it can also combine with the hardening | curing agent which reacts with the epoxy group in molecular structure. Curing agents used in the present embodiment include dicyandiamide, tetramethylguanidine, aromatic amine, phenol novolac resin, cresol novolac resin, acid anhydride, other aliphatic and alicyclic amines, and active esters. 1 type (s) or 2 or more types can be used.

  Furthermore, a general epoxy resin curing accelerator can be used as the curing accelerator combined with the curing agent. Examples of preferable curing accelerators include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, and triphenyl. Organic phosphine compounds such as phosphine and tributylphosphine, organic phosphite compounds such as trimethyl phosphite and triethyl phosphite, phosphonium salts such as ethyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, and trialkylamines such as triethylamine and tributylamine 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4 0) -undecene-7 (hereinafter abbreviated as DBU) and salts of DBU with terephthalic acid or 2,6-naphthalenedicarboxylic acid, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, Quaternary ammonium salts such as tetrabutylammonium bromide, tetrahexylammonium bromide, benzyltrimethylammonium chloride, 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenyl Urea, urea compounds such as 3- (4-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, alkalis such as sodium hydroxide and potassium hydroxide , Potassium phenoki And salts of crown ethers, such as de, potassium acetate and the like, imidazoles, triphenylphosphine, 4-dimethylaminopyridine, and the like.

(D) Other components The resin composition according to the present embodiment can be used as a material for electronic devices, electronic components, and circuit boards, and is formed into pellets (powder) as a molding material and powder coating. As an insulating material such as an adhesive material, a casting material, or a resist, it can be used in various forms such as varnish or paste. Therefore, depending on the form of use, in addition to the above components, fillers, additives and the like can be appropriately blended and used.

  For example, when the resin composition is applied to a conductor foil as described later, the thermosetting PPE oligomer (A) and polybutadiene or styrene-polybutadiene copolymer (B) are dissolved in a solvent and uniform. A solution (resin varnish) is prepared. The solvent used for preparing the resin varnish is not particularly limited as long as it is a solvent in which the PPE oligomer (A) and the polybutadiene or styrene-polybutadiene copolymer are highly soluble, but toluene, xylene, mesitylene, cyclohexanone and the like can be raised. Among these, nonpolar solvents such as toluene and xylene are particularly preferable because they are highly compatible and hardly affect the dielectric properties due to remaining in the insulating layer.

  In preparing such a resin varnish, a kneader, a kneader, a ball mill, a stirrer, a roll or the like can be used so as to obtain a uniform solution.

Furthermore, various fillers and various additives can be blended according to the improvement of electrical characteristics, mechanical and physical properties, and the necessity of material form.
Specific examples of fillers include dielectric materials such as carbon black and titanium oxide, magnetic materials such as ferrite and soft magnetic metals, silica, alumina, zirconia, potassium titanate whisker, barium titanate whisker, zinc oxide whisker, and glass. Examples thereof include fibers, glass beads, carbon fibers, magnesium oxide (talc), glass beads, glass hollow spheres, and the like, which can be properly used according to required properties.
Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a pigment, a dye, and a colorant.

2. Conductor foil with resin (RCC)
The conductor foil with resin according to the present embodiment can be obtained by applying the resin varnish to the conductor foil and drying it.

  The conductive foil to be used is selected from, for example, copper, silver, gold, aluminum, nickel-chrome, or nickel. Although not particularly limited, copper is most preferably used from the viewpoint of availability, conductivity, and cost. Copper foil includes electrolytic copper foil and rolled copper foil, either of which may be used.

  The thickness of the conductor foil to be used is preferably in the range of 3 to 70 μm from the viewpoint of availability, and may be properly used depending on the required characteristics. For example, when it is desired to reduce the conductor resistance as much as possible, or for a wiring through which a large amount of current flows, a relatively thick 18 to 70 μm copper foil may be used. When pattern accuracy is required with a thin line or a high-frequency signal, a semi-additive method is used. For example, a relatively thin 3 to 18 μm copper foil may be used.

  The surface roughness (Rz) of the conductive foil (copper foil) to be used is usually 4 to 8 μm, but is preferably in the range of 0.2 μm to 3.5 μm in order to reduce the conductor loss at high frequencies. If the thickness is less than 0.2 μm, the production of the conductor foil itself is difficult and there are problems in terms of availability and cost. If the thickness is more than 3.5 μm, the effect of reducing the previous conductor loss is reduced.

  In order to improve the adhesion to the resin, for example, the roughened surface of the conductor foil may be subjected to a coupling treatment such as a heat-resistant plating film such as zinc-nickel and an olefin coupling agent.

  The conductor foil with resin is obtained by applying a resin varnish in which the resin composition is dissolved to the conductor foil by a general method such as a doctor blade method, and drying at 80 ° C. to 150 ° C., for example. It can be obtained by drying.

  The resin layer thickness of the conductor foil with resin is preferably 5 to 200 μm, particularly preferably 10 to 100 μm. If it is less than the above lower limit, coating may be difficult and insulation resistance may be a problem. If it is greater than the above upper limit, cracks may occur or the insulating layer may drop off.

3. Printed Wiring Board The printed wiring board according to the present embodiment can be produced by superposing the resin-coated conductor foil on one or both surfaces of the inner circuit board and heating and pressing. Although the temperature and time to heat are not specifically limited, 150 to 240 degreeC and 0.5 to 10 hours are preferable. Further, step cure may be performed as necessary. Although it does not specifically limit about the pressure to pressurize, 1-6 Mpa is preferable. Further, when vacuum pressing is performed, generation of insulating layer voids after pressing can be suppressed. The degree of vacuum is not particularly limited, but is preferably 5.3 kPa (40 torr) or less.

  In addition, the inner layer circuit pattern is formed on, for example, a copper-clad laminate and a multilayer laminate, and as a conductor surface treatment, blackening treatment, roughening treatment by microetching due to intergranular corrosion with formic acid or hydrogen peroxide solution, The method by acicular tin plating formation etc. are mentioned.

  Further, a resin varnish is coated on a support such as a PET film, dried, placed on a conductor foil that has been patterned in advance, heated and pressed, and then separated from the support after the wiring substrate transfer resin is obtained. A printed wiring board can also be produced by laminating.

The present invention is not limited to the above-described embodiment, and various changes and modifications can be made.
In the said embodiment, the conductor foil with resin and the printed wiring board shall be manufactured using a resin composition. However, a prepreg, a sheet, a sheet with conductive foil, and a laminate can be produced using the resin composition according to the present embodiment.

  For example, the prepreg can be produced by impregnating a base material into a preparation solution of a resin composition. As a substrate, glass cloth of E glass, glass cloth of D glass, glass cloth of NE glass, glass cloth of H glass, glass cloth of T glass, glass nonwoven fabric, porous film of aramid, porous film of polyamide, And a porous film of polytetrafluoroethylene, carbon fiber cloth, paper and the like.

  One or more prepregs thus obtained are stacked and heat-cured to produce a sheet, and one or more prepregs are stacked and the upper and lower surfaces or one-sided conductive foil is stacked and heat-cured to form a conductive foil. An attached sheet can be manufactured. Further, the laminate may be manufactured by sandwiching the base material between the sheet manufactured as described above and the sheet with conductor foil and curing by heating. By using a plurality of these, a multilayer printed wiring board can be configured.

  Furthermore, it is possible to create a molded product of any shape by heat-curing the resin composition according to the embodiment in a mold. For electronic devices, electronic components, circuit boards It can be used widely as a material.

(Example 1)
Preparation of conductor foil with resin: OPE-2St (R) (Mitsubishi Gas Chemical Co., Ltd.) 100 g which is a reaction product of PPE oligomer and chloromethylstyrene, and NISSO-PB B-1000 which is a butadiene homopolymer ( R) (manufactured by Nisso Co., Ltd.) 11 g and tetrabromobisphenol A modified vinyl benzyl resin Shounol ARS-069 (R) (39% toluene solution, Showa High Polymer Co., Ltd.) 92.3 g (solid content 36 g) And 45 g of toluene were placed in a 500 ml plastic bottle and placed on a pot stand for 4 hours to create a completely dissolved uniform resin varnish. This resin varnish was applied to an electrolytic copper foil (for example, JTM-1 / 2oz (R) (manufactured by Nikko Materials Co., Ltd., Rz 8 μm)) and dried at 120 ° C./6 minutes. The thickness of the obtained sample was 68 μm including the copper foil.

  Preparation of double-sided copper-clad sample for copper foil peel strength test: The above-mentioned conductor foil with resin is overlapped with the resin surface facing each other, and is heated at 4 ° C./min with a vacuum hot press (KVHC type, manufactured by Kitagawa Seiki Co., Ltd.) A vacuum heating and pressing press was performed stepwise at 150 ° C./60 minutes, 4 ° C./minute, and 200 ° C./3 hours under conditions of 3 MPa and 3.9 kPa (30 torr) or less. The thickness of the obtained sample was 135 μm including the copper foil.

Dielectric properties, flexural strength, flexural modulus, the glass transition temperature T _g, the creation of samples for flame retardancy test: OPE-2ST is the reaction product of a PPE oligomer and chloromethylstyrene (Mitsubishi Gas Chemical Co., Ltd.) 100 g, 11 g of butadiene homopolymer NISSO-PB B-1000 (R) (manufactured by Nisso Co., Ltd.), tetrabromobisphenol A modified vinylbenzyl resin Shounol ARS-069 (R) (39% toluene solution, Showa 92.3 g (Polymer Co., Ltd.) (solid content 36 g) and toluene 45 g were put in a 500 ml plastic bottle and put on a pot stand for 4 hours to prepare a completely dissolved uniform resin varnish. This resin varnish was applied to a 50 μm thick PET film and dried at 120 ° C./6 minutes. The thickness of the obtained sample was 100 μm including the PET film. This was sequentially pressure-bonded on a hot plate heated to 120 ° C. with the resin surfaces, and a B-stage plate having a thickness of 820 μm was obtained. Place this B stage plate in a kraft paper with a thickness of 800μm that is hollowed in the same shape, and stack the release film, jig plate, and cushioning material one after the other in a vacuum heat press (KVHC type, Kitagawa Seiki Co., Ltd.) 4 A vacuum heating and pressing press was performed stepwise at 3 ° C./min, 3.9 kPa (30 torr) at 150 ° C./min, 150 ° C./60 min, 4 ° C./min, and 200 ° C./3 hr. The thickness of the obtained sample was 800 μm.

(Example 2)
In the formulation of Example 1, ARS-069 was changed to 15.4 g of ethane-1,2-bis (pentabromophenyl) SAYTEX 8010 (R) (manufactured by Albemarle Asano Co., Ltd.), and toluene was used as 80 g. A sample was prepared in the same manner as in Example 1.

(Example 3)
11 g of epoxidized polybutadiene Epofriend CT310 (R) (manufactured by Daicel Chemical Industries, Ltd.) and 44 g of toluene were placed in a 500 ml plastic bottle and taken on a pot stand for 4 hours to obtain a completely dissolved transparent solution. Further, 100 g of a reaction product OPE-2St (R) (manufactured by Mitsubishi Gas Chemical Co., Inc.) of a PPE oligomer and chloromethylstyrene, tetrabromobisphenol A modified vinylbenzyl resin Shounol ARS-069 (R) (39% toluene) The solution, 92.3 g (manufactured by Showa Polymer Co., Ltd.), and a solid content of 36 g were put into a pot stand for 4 hours to form a completely dissolved uniform resin varnish. A sample was prepared in the same manner as in Example 1 using this resin varnish.

Example 4
In the formulation of Example 1, ARS-069 (R) was changed to 15.4 g of ethane-1,2-bis (pentabromophenyl) SAYTEX 8010 (R) (manufactured by Albemarle Asano Co., Ltd.), and toluene was changed to 40 g. Samples were prepared as in Example 1.

(Example 5)
11 g of epoxidized polybutadiene Epofriend CT310 (R) (manufactured by Daicel Chemical Industries, Ltd.) and 44 g of toluene were placed in a 500 ml plastic bottle and taken on a pot stand for 4 hours to obtain a completely dissolved transparent solution. Furthermore, 100 g of a reaction product of PPE oligomer and chloromethylstyrene, OPE-2St (R) (Mitsubishi Gas Chemical Co., Ltd.) and butadiene homopolymer NISSO-PB B-1000 (R) (Nisso Co., Ltd.) 11 g And 102.6 g (solid content 40 g) of tetrabromobisphenol A-modified vinyl benzyl resin Shounol ARS-069 (R) (39% toluene solution, manufactured by Showa Polymer Co., Ltd.), and placed in a pot stand for 4 hours A uniform resin varnish completely dissolved was prepared. A sample was prepared in the same manner as in Example 1 using this resin varnish.

(Example 6)
In the formulation of Example 5, ARS-069 (R) was changed to 16.9 g of ethane-1,2-bis (pentabromophenyl) SAYTEX 8010 (R) (manufactured by Albemarle Asano Co., Ltd.), except that 47 g of toluene was added. A sample was prepared in the same manner as in Example 5.

(Comparative Example 1)
100 g of a reaction product of PPE oligomer and chloromethylstyrene OPE-2St (R) (Mitsubishi Gas Chemical Co., Ltd.) and 66.7 g of toluene are placed in a 500 ml plastic bottle and placed on a pot stand for 4 hours. A dissolved uniform resin varnish was prepared. A sample was prepared in the same manner as in Example 1 using this resin varnish.

(Comparative Example 2)
In the formulation of Example 5, the epoxidized polybutadiene Epofriend CT310 (R) (manufactured by Daicel Chemical Industries, Ltd.) was changed to 35 g, the toluene was changed to 175 g, and the butadiene homopolymer NISSO-PB B-1000 (R) (Nisso) The product was changed to 35 g, and ARS-069 was changed to 23.6 g of ethane-1,2-bis (pentabromophenyl) SAYTEX 8010 (R) (manufactured by Albemarle Asano Co., Ltd.). A sample was created.

<Method for evaluating resin varnish dispersion>
200 ml of each resin varnish blended and dissolved was placed in a 250 ml plastic bottle and allowed to stand at room temperature for 24 hours, and the presence or absence of turbidity was visually evaluated. The sample with no separation and turbidity was marked with ◯, the sample with no turbidity was marked with Δ, and the sample with both separation and turbidity was marked with ×.

<Removal of RCC insulation layer, crack>
The above-mentioned resin varnish was applied to the following copper foil, and a dried sample sheet was prepared.
(A) 18 μm electrolytic copper foil, Rz 8 μm
(B) 18 μm electrolytic copper foil, Rz 3.5 μm
(C) 18 μm electrolytic copper foil, Rz 2.1 μm
(D) 12 μm electrolytic copper foil, Rz 2.1 μm
(E) 18 μm rolled copper foil, Rz 1.1 μm
(F) 12 μm rolled copper foil, Rz 1.1 μm
Bending the sample sheet at a 90 ° angle and evaluating whether or not the RCC (resin-coated copper foil) insulation layer is partially removed starting from the crack. There is no clear crack and the insulation layer is removed. The case where there was no crack was marked as ◯, the case where a crack entered but the insulating layer did not fall off was marked as Δ, and the case where both the crack and the insulating layer were dropped was marked as x.

<Dielectric constant ε>
Using a device for measuring dielectric properties in the frequency range of 1 to 10 GHz prepared by the present applicants, the test sample sheet is cut into a size of 100 × 1.5 × 0.8 mm to form a 2 GHz cavity. The dielectric constant ε was calculated from the change in the resonance frequency and the Q value when taken in and out.

<After water absorption △ ε>
After measuring the initial value of the sample with the above dielectric property measuring apparatus, the sample was placed in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 168 hours, and the change rate Δε of the dielectric constant compared with the value re-measured immediately after removal was calculated .

<Bending strength, flexural modulus>
The test sample sheet was cut into a size of 40 mm × 25 mm × 0.8 mm by a test method according to JIS C 6481, and AGS1000D (manufactured by Shimadzu Corporation) was used. A constant speed load-displacement curve was taken at min, and bending strength and bending elastic modulus were calculated from the following mathematical formulas 3 and 4.

(Formula 3)
(Bending strength) = 3 × (strength at break) × (distance between fulcrums) / (2 × (sample width) × (sample thickness) ² )

(Formula 4)
(Flexural modulus) = (distance between fulcrums) ³ × (strength at break) / (4 × (sample width) × (sample thickness) ³ × (displacement at break))

<Glass transition temperature ( _Tg )>
The test sample sheet was cut into a size of 40 mm × 10 mm × 0.8 mm by a test method according to JIS C 6481 and 2 in a tensile sine wave mode using DMS6100 (R Seiko Instruments Inc.). The heat resistance temperature (glass transition temperature T _g ) was determined from the peak of the dielectric loss tangent tan δ using the DMA method, measured at ° C./min, room temperature to 340 ° C., and a frequency of 1 Hz.

<Copper foil peel strength>
Preparation of double-sided copper-clad sample for copper foil peel strength test: The above-mentioned conductor foil with resin is overlapped with the resin surface facing each other, and is heated at 4 ° C./min with a vacuum hot press (KVHC type, manufactured by Kitagawa Seiki Co., Ltd.) A vacuum heating and pressing press was performed stepwise at 150 ° C./60 minutes, 4 ° C./minute, and 200 ° C./3 hours under conditions of 3 MPa and 3.9 kPa (30 torr) or less. The thickness of the obtained sample was 135 μm including the copper foil. This sample was diced to a width of 10 mm in accordance with JIS C 6481, and the copper foil was peeled off in the direction of 90 ° at a speed of 50 mm / min with a load tester MODEL 1605N (R) (manufactured by Aiko Engineering Co., Ltd.) The peel strength was determined.

The test was performed on a sample sheet obtained by coating a resin varnish on a copper foil having the following thickness and Rz, and obtaining the peel strength of the copper foil.
(G) 18 μm electrolytic copper foil, Rz 2.1 μm
(H) 18 μm rolled copper foil, Rz 1.1 μm copper foil was used.

<Flame retardance test>
In accordance with the UL94 V-0 test method, the test sample sheet was cut into 127 × 12.7 × 0.8 mm (1/32 inch), and after pretreatment at 70 ° C. for 168 hours, a flame with a height of 10 mm was applied. The sample was flame-contacted twice for 10 seconds, and the sample burning time was set to V-0 when the burning time of the sample was double-flamed for 10 seconds or less and the burning time of 5 samples was 50 seconds or less.

(result)
Table 1 shows the test results for Examples 1 to 6 and Comparative Examples 1 and 2.

  As shown in Table 1, the samples according to Examples 1 to 6 are excellent in the results of various tests as compared with Comparative Examples 1 and 2. This will be described in detail below.

  First, in Comparative Example 1 which does not include any of the flexible materials (B) (CT310 (R) and B1000 (R)), the insulation layer falling off and cracks in the resin-coated conductor foil are remarkable in the low-roughened copper foil. On the other hand, in each of Examples 1 to 6, the result of the insulating layer drop-off test is good. Therefore, it can be seen that the resin-coated conductor foil using the resin composition containing the PPE oligomer (A) and the flexible material (B) is easy to cut and exhibits good handling properties.

  Moreover, in the comparative example 1 which does not use a flame retardant (C), UL-94 V-0 is not achieved in a flame retardance test (HB). However, in Examples 1-6 which use a flame retardant (C), all achieve UL-94 V-0 and it turns out that high flame retardance is implement | achieved.

  In Comparative Example 2 in which the flexible material (B) (CT310 (R) and B1000 (R)) was blended in a total amount of 70 parts by weight, exceeding a preferred ratio (5 to 66 parts by weight), after standing overnight The liquid dispersibility is poor. On the other hand, in Examples 1-6 which used a flexible material in a desirable ratio, all have good liquid dispersibility.

Moreover, compared with the comparative example 1 which uses only a PPE oligomer (A), in Examples 1-6 which mix | blend and use a flexible material (B), the characteristic which PPE originally has, ie, dielectric property (low) Dielectric constant, low dielectric loss tangent), water absorption characteristics (change in dielectric constant after low water absorption), bending characteristics (bending strength, bending elastic modulus), and heat resistance (high glass transition temperature T _g ) are well maintained. Furthermore, after the said characteristic is maintained, in Examples 1-6, the flexibility is provided and the improvement of copper foil peel strength is aimed at.
Thus, it can be seen that the samples of Examples 1 to 6 have the characteristics of PPE fully utilized and the handling properties are further improved.

Claims (18)

A thermosetting polyphenylene ether oligomer (A) represented by the following general formula (1), and a flexibility-imparting agent (B) selected from any one or more of polybutadiene or styrene-polybutadiene copolymer; A resin composition comprising: a flame retardant (C).

(In the formula, — (O—X—O) — is represented by the general formula (2), and R 1, R 2, R 7 and R 8 may be the same or different, and are a halogen atom or an alkyl group having 6 or less carbon atoms, or R3, R4, R5 and R6 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and A is a straight chain having 20 or less carbon atoms. Or a branched or cyclic hydrocarbon,-(YO)-is represented by the general formula (3), R9 and R10 may be the same or different and are a halogen atom or an alkyl group having 6 or less carbon atoms; R11 and R12 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. One type of structure defined by the formula (3) or two or more types of structures defined by the general formula (3) are randomly arranged, Z is an organic group having 1 or more carbon atoms, oxygen (A and b each represents an integer of 0 to 300, at least one of which is not 0. Each i independently represents an integer of 0 or 1.)   The blending ratio of the thermosetting polyphenylene ether oligomer (A) and the flexibility-imparting agent (B) is 5 to 66 parts by weight with respect to 100 parts by weight. 2. The resin composition according to 1. The flexibility imparting agent (B) is represented by the following general formula (4), and is configured to include polybutadiene having an oligomer skeleton in which 1,2-vinyl bond is 80% or more. Item 3. The resin composition according to Item 1 or 2.

(In the formula, n is an integer of 0 or more.) The said flexibility imparting agent (B) is comprised including the styrene-butadiene copolymer represented by following General formula (5), Either of Claim 1 thru | or 3 characterized by the above-mentioned. The resin composition as described.

  The flame retardant (C) includes a halogenated aromatic additive-type flame retardant or a compound in which at least one of hydroxyl groups of a halogenated phenol is substituted with a vinylbenzyl group. The resin composition according to any one of claims 1 to 4.   The blending ratio of the flame retardant (C) is 100 parts by weight in total of the thermosetting polyphenylene ether oligomer (A) and one or more of polybutadiene or styrene-polybutadiene copolymer (B). It is 5-100 weight part, The resin composition of any one of Claims 1 thru | or 5 characterized by the above-mentioned.   A conductor foil with resin, wherein the resin composition according to any one of claims 1 to 6 is formed by coating and drying on a conductor foil.   The conductive foil is made of any one of copper, silver, gold, aluminum, nickel-chromium, and nickel, and the thickness of the conductive foil is in the range of 3 to 70 μm. The conductor foil with resin as described.   9. The conductor foil with resin according to claim 7, wherein the surface roughness of the conductor foil is in a range of 0.2 to 3.5 μm.   The resin-coated conductor foil according to claim 7, wherein the resin layer formed on the conductor foil has a thickness of 5 to 200 μm.   A printed wiring board, wherein the resin-coated conductor foil according to any one of claims 7 to 10 is formed by heating and pressurizing one side or both sides.   The resin composition according to any one of claims 1 to 6 is applied on a support, dried, placed on a conductor foil previously patterned into a predetermined shape, heated and pressurized, and then peeled off from the support A conductive foil with resin, characterized in that it is formed.   A printed wiring board, which is formed by laminating the conductor foil with resin according to claim 12.   A prepreg comprising the resin composition according to any one of claims 1 to 6 impregnated with a base material.   A sheet comprising one or more prepregs according to claim 14 which are stacked and cured.   A sheet with a conductive foil, characterized in that the conductive foil is laminated and cured on one side or both sides of the prepreg according to claim 14.   A laminate comprising: a sheet according to claim 15 or a sheet with conductor foil according to claim 16;   A printed wiring board comprising a plurality of the sheets according to claim 15, the sheet with conductor foil according to claim 16, or the laminate according to claim 17.