WO2008153208A1 - Resin composition for interlayer insulation of multilayer printed wiring board - Google Patents

Abstract

Disclosed is a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board. Specifically disclosed is a resin composition for interlayer insulation of a multilayer printed wiring board, which contains the following components (A), (B) and (C). (A) a polyimide resin having a polybutadiene structure, a urethane structure and an imide structure in a molecule, while having a phenol structure at an end of the molecule (B) an epoxy resin (C) an inorganic filler having a specific surface area of 18-50 m2/g

Description

 Specification

Resin composition for interlayer insulation of multilayer printed wiring board

Technical field

 TECHNICAL FIELD The present invention relates to a resin composition suitable for interlayer insulation of a multilayer printed le spring board, particularly for interlayer insulation of a flexible multilayer printed board. The present invention also relates to an adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board prepared from the resin composition, and a multilayer printed wiring board formed with an interlayer insulating layer strength s from the resin composition. Related.

Background art

 Because of the ability to bend flexographical multi-layer prints and boards in narrow spaces, they are indispensable for media β that is becoming smaller and thinner. As a material used for interlayer insulation of a flexible multilayer printed wiring board, for example, JP-A-2006-037083 discloses an effect composition comprising a polyimide having a polybutadiene structure and an epoxy resin. It is disclosed that the obtained interlayer layer is excellent in flexibility, bow, dielectric properties, and the like.

Disclosure of the invention

Inventive power S Problems to be solved

 An object of the present invention is to provide a resin composition suitable for interlayer insulation of a flexible multilayer printed wiring board.

Means for solving the problem

The polyimide contained in the resin composition of Japanese Patent Application Laid-Open No. 2006-037083 has a force that allows the terminal to be an acid anhydride group or a carboxy group, and these groups react with an epoxy group to generate a resting combination that is easily carohydrated. Therefore, considering application to precision electronic products, it is desirable to reduce or eliminate the presence of these groups in the resin composition from the viewpoint of reliability. In view of the above points, the present inventors used a polyimide resin having a phenol structure introduced at the end in order to reduce or eliminate the force propyloxy group in a polyimide resin having a polybutadiene structure, As a result, it has been found that an interlaminar layer having excellent flexibility, mechanical strength, and induction characteristics can be obtained. On the other hand, when a resin composition is used as an interlaminar layer, a method of adding an inorganic filler typified by silica for the purpose of suppressing the coefficient of thermal expansion and tack is known. And a composition containing an epoxy resin, There was a problem that the inorganic filler easily settled and it was difficult to obtain a uniform resin composition. The inventors of the present invention have further studied diligently, and by using a normally used male surface area having a much smaller specific surface area, it is possible to easily disperse the invisible material and to obtain a uniform resin. It was found that a composition was obtained. The present inventors completed the present invention based on the above findings. That is, the present invention includes the following contents.

 [1] Interstitial resin waste for multilayer printed wakeboard containing the following ingredients (Α), (Β) and (C):

 (Ii) A polybutadiene structure in the liver, a urethane difficult, an imide structure, and a polyimide structure having a phenol structure in ¾¾¾,

 (Β) Epoxy resin,

 (C) An inorganic filler with a ratio of 18 to 50 mVg.

 [2] Multi-layer printed wakeboard interstitial fragrances containing the following components (A), (B) and (C):

 (A) [a] a polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule, and [b] a diisocyanate compound to react to form a diisocyanate prepolymer,

[c] tetrasalt male dianhydride, and [d] a polyfunctional phenol compound having two or more phenolic hydroxyl groups in 1 ^, a polyimide resin having a phenol structure at the end of the liver,

(B) epoxy resin,

(C) A fine filler having a specific surface ratio of 18-50 m ² / g.

[3] The resin composition according to the above [1] or [2], wherein the inorganic filler as the component (C) has a specific surface area of 18 to 40 m ² Zg.

[4] The resin composition according to the above [1] or [2], wherein the inorganic filler as the component (C) has a specific surface area of 18 to 35 m ² Zg.

[5] The resin composition as described in [1] or [2] above, wherein the inorganic filler of component (C) has a specific surface area of 20 to 30 m ² / g.

 [6] The resin composition according to the above [1] or [2], wherein the inorganic filler is silica.

[7] The resin composition according to the above [1] or [2], wherein the phenolic compound is a phenol nopolac resin. [8] The resin composition according to [1] or [2] above, which is a polybutadiene polyol compound-added polybutadiene polyol compound.

 [9] In the component (A) polyimide resin, the reaction component [a] the functional group of the isocyanate group of the reaction component [b] diisocyanate compound with respect to the hydroxyl group of a polybutadiene polyol having two or more alcoholic hydroxyl groups in 1 kg. The resin composition according to the above [2], wherein the basic St is reacted at a ratio of 1: 1.5 to 1: 2.5.

 [10] The measuring composition according to the above [1] or [2], further comprising a polyfunctional phenol compound having two or more phenolic hydroxyl groups in the component [D] 1.

 [11] Component (A) is 40 to 85% by weight with respect to the total of 100% by weight of component (A) polyimide resin, component (B) epoxy resin and component (D) polyfunctional phenolic compound, The resin fiber according to [10] above, wherein (B) is contained in an amount of 15 to 40% by weight and component (D) force is ~ 20% by weight.

 [12] An adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board having a layer of resin composition as described in [1] or [2] above.

 [13] A multilayer printed wiring board in which an interlayer insulating layer is formed from the resin composition described in [1] or [2].

The invention's effect

 According to the present invention, the resin composition is excellent in flexibility, mechanical strength, dielectric properties, etc., and is suitable for use in insulation between layers of flexible multilayer printed wiring boards.

BEST MODE FOR CARRYING OUT THE INVENTION

 The polyimide resin of component (A) in the present invention has a polybutadiene structure, a urethane structure, and an imide structure inside, and has a phenol structure in the force liver. Such a polyimide resin having phenol at the terminal end can be obtained by the following method using the reaction components [a] to [d]. That is,

 [a] a polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule, and

[b] Reacting a di-socyanate compound to form a di-socyanate prepolymer, and

 [c] tetrabasic acid dianhydride, and

 [d] 1 polyfunctional phenolic compound having two or more phenolic M hydroxy groups in one liver,

React. [a] As a polybutadiene polyol compound having two or more alcoholic 7-acid groups in one molecule, a compound having a number average liver mass of 300 to 5,000 is preferable. When the number average liver mass is 300 or less, the modified polyimide shelf tends to be inflexible. If it is 5,000 or more, the modified polyimide resin tends to lack compatibility with the thermosetting resin, and also tends to lack heat resistance and chemical resistance. In the present invention, the number average amount of T is a value measured by gel permeation chromatography (GPC) method (polystyrene gel). The number average ^ according to the GPC method is, specifically, Shod ex GPC System 21 made by Showa Denko Co., Ltd. as the measuring device, and Shodex LF-804 / KF-803ZKF made by Showa Denko Co., Ltd. as the column. — 804 can be measured using a column of 40 using NMP as the mobile phase and calculated using a standard polystyrene calibration. As the polybutadiene polyol, a hydrogenated polybutadiene polyol which has an unrestricted binding force S and is hydrogenated may be used. The polybutadiene polyol is preferably a polybutadiene diol having a hydroxyl group at the terminal. Alcohol I raw hydroxyl group is a form in which the hydrogen atom of fatty female hydrocarbon «t is replaced with a hydroxyl group! ? ^ This refers to a hydroxyl group that hesitates. Specific examples of the polybutadiene polyol include, for example, G-1000, G-2000, G-3Q00, GI-1000, GI-2000 (above, Nippon Soda Co., Ltd.), R-4 SEP I (Idemitsu Petrochemical Co., Ltd.)

 [b] A diisocyanate compound is a compound having two isocyanate groups in it. , Such as diphenylmethane diisocyanate and isophosphonate societies.

 [c] Tetrasalt dianhydride is a compound having two acid anhydride groups in the liver, such as pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic Acid dianhydride, naphthalenetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-cyclohexene mono 1,2-dicarboxylic anhydride, 3, 3 '-4 , 4'-diphenylsulfonate tetracarboxylic dianhydride, 1, 3, 3 a, 4, 5, 9 b-Hexahydro-5- (tetrahydro-1,2,5-dioxo-3-furanyl) mononaphtho [ 1, 2-C] Furan 1, 3-dione.

[d] One example of a polyfunctional phenolic compound having two or more phenolic hydroxyl groups in one liver is For example, bisphenol A, bisphenol F, bisphenol S, pifenol, phenol novolac resin, alkylphenol nopolac resin, bisphenol A type novolac resin, dicyclobenenol segregated phenol nopolac resin, triazine Examples thereof include age-old phenolic nopolac resins, biphenol Jk-containing phenolic nopolac resins, phenyl group-containing phenolic nopolac resins, terpene-modified phenolic resins, and polyvinyl phenols. In particular, alkylphenol nopolac reversal is preferred. The phenol JM hydroxyl group means a hydroxyl group that exists in a form in which a hydrogen atom of an aromatic ring structure is substituted with a hydroxyl group (hydroxyl group).

 In order to obtain the polyimide resin in the present invention efficiently, it is preferable to follow the following procedure. First, the polybutadiene polyol of the reaction component [a] and the diisocyanate compound of the reaction component [b] are reacted at a ratio in which the functional group equivalent of the isocyanate group of the diisocyanate compound to the hydroxyl group of the voluptadiene polyol exceeds 1. The reaction ratio between the polybutadiene polyol and the diisocyanate compound is such that the functional group St of the isocyanate group of the diisocyanate compound with respect to the hydroxyl group of the polybutadiene is 1 1.5 1: '2.5.

Reaction component [a] iA In the case of a polybutadiene diol having a hydroxyl group at the molecular end, the polybutenediol can be represented by the following formula (a,).

(R 1 represents a divalent organic group having a polybutadiene structure.)

 The diisocyanate compound as the reaction component [b] can be effectively expressed by the following formula (b).

 0CN-R 2 -NC0 (b)

 (R 2 represents a divalent organic group.)

 The tetrasalt dianhydride as the reaction component [c] can be represented by the following formula (c).

 (R 3 represents a tetravalent organic group.)

A polybutadiene polyol having a hydroxyl group at the molecular end and a disocene 1, compound are reacted. The diisocyanate prepolymer obtained can be represented by the following formula (a′-b).

_{0CN + R} r 0 Sr ⁰ Y 0 ^{N +} ~ ^R2 " ^{NC0 (a} '— ^b)

 (R 1 and R 2 have the same meanings as above, and n represents an integer of 1 or more and 1 0 0 or less (1≤n≤ 1 0 0). N is preferably 1 or more and 1 0 or less (l≤n≤l 0) Indicates an integer.

 Next, the diisocyanate prepolymer obtained by the above reaction is reacted with a tetrasalt dianhydride as a reaction component [c] and a polyfunctional phenol compound as a reaction component [d]. The reaction rate is not particularly limited, but it is envisaged that as much as possible the isocyanate groups remain in the destruction. In order to keep the isocyanate group in the reaction system as much as possible, it is preferable to confirm the disappearance of the isocyanate group by FT-IR or the like during the reaction. According to the order of the reaction, first the tetra-salt dianhydride is reacted, then the polyfunctional phenol compound is reacted, and the tetra-salt »dianhydride and polyfunctional phenol compound are simultaneously reacted to react. How to make it bald. At the same time, it is thought that the anhydride group reacts with the isocyanate group in a woven manner and forms an imido bond fiTT. And the remaining isocyanate group reacts with the polyfunctional phenolic compound to form * S. Ability to introduce phenolic jobs.

 The functional group equivalent of the hydroxyl group of the polybutadiene polyol of the reaction component [a] is W, the functional group equivalent of the isocyanate group of the diisocyanate compound of the reaction component [b] is X, and the tetrasalt dianhydride of the reaction component [c] is When the functional group equivalent is Y and the functional group equivalent of the polyfunctional phenolic compound of reaction component [d] is Ζ, the reaction components [c] and [d] are in a ratio satisfying the relationship of Y く X—W く Y + Z. The power of use at s is preferred.

 When a polybutadiene diol having a hydroxyl group at the molecular end is used as the reaction component [a], the polyimide of component (A) in the present invention has the following formulas (1-a) and (1b).

具体的な反応条件は、 例えば、 反応成分 [a]のポリブタジエンポリオールと反応成分 [b]のジィ ソシァネート化合物の反応は、 械-赚中、 反応温度が 8 0 以下、 反応時間が通常 2〜8時間の 条件で行うこと力できる。 また必要により讓雜下に行ってもよい。 次に該反応鹿夜中に四塩基 酸二無水物及 官能フエノール化合物を添カロし、 反応温度 1 2 0〜 1 6 0 、 反応時間 5〜2 4 時間の条件で反応を行うことができる。 反応は通常触媒存在下に行われる。 また有機讓を更に添 加して行ってもよい。

The specific reaction conditions are, for example, the reaction of the polybutadiene polyol of the reaction component [a] and the diisocyanate compound of the reaction component [b], in which the reaction temperature is 80 ° C. or less and the reaction time is usually 2 to 8 You can do it under the conditions of time. You may also go to the Majesty if necessary. Next, tetrabasic dianhydride and a functional phenol compound are added to the reaction mixture, and the reaction can be performed under the conditions of a reaction temperature of 120 to 160 and a reaction time of 5 to 24 hours. The reaction is usually performed in the presence of a catalyst. An organic soot may be further added.

 In this reaction, carbon dioxide gas is generated along with imide bond formation by reaction of isocyanate group and acid anhydride group. Therefore, it was formed by measuring the amount of SS decrease after rubbing and determining the number of moles of carbon dioxide gas. It is possible to calculate the number of moles of imide groups.

 After completion of the reaction, the reaction solution may be filtered if necessary to remove insoluble matter. Thus, the polyimide resin in the present invention can be obtained in a varnish form. The amount of the solvent in the varnish can be adjusted by adjusting the amount of the solvent at the time of reaction or by increasing the intensity after the reaction. The polyimide resin in the present invention can be used for the preparation of a composition usually in the above varnish form. In a simple case, for example, the varnish obtained in methanol, which is a poor solvent, is gradually added to obtain polyimide as a solid.

Examples of organic cages used in the above reactions include N, N'-dimethylformamide, N, N'-jetylformamide, N, N'-dimethylacetamide, N, N'-jetylacetate. Amide, dimethyl sulfoxide, jetyl sulfoxide, N-methyl-2-pyrrolidone, tetramethylurea, τ-ptyrolactone, cyclohexanone, diglyme, triglyme, Calvi I ^ llucate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ester It is possible to mention the polarity of one tellate. Two or more of these solvents may be mixed and used. In addition, if necessary, it is possible to use a mixture of aromatic hydrocarbons and the like. Examples of the catalyst used in each of the above reactions include tetramethylbutanediamine, benzyldimethylamine, triethanolamine, Tertiary amines such as triethylamine, N, N′-dimethylpiperidine, en-methylpentyldimethylamine, N-methylmorpholine, triethylenediamine, dip-J-resin laurate, dimethyltin dichloride, cobalt naphthenate, And organic metal such as zinc naphthenate. These cocoons may be used in combination of two or more. As In particular, the power of using triethylenediamine is most preferred.

 Examples of the epoxy resin in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol nopolac type epoxy resin, bisphenol S type epoxy resin, alkylphenol nopolac type epoxy resin, biphenol type epoxy resin. Resin, naphthenic epoxy resin, dicyclopentene epoxy resin, epoxidized product of condensate of phenol with aromatic aldehyde having phenolic hydroxyl group, 卜 lidarididyl isocyanurate, alicyclic epoxy resin An epoxy resin having two or more functional groups in one molecule can be exemplified. These epoxy resins may be used in combination of two or more. Furthermore, it is preferable to use bisphenol A type epoxy.

 In the composition of this invention, you may mix | blend an epoxy hardening | curing agent as needed. Examples of the epoxy curing agent include an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, an acid anhydride curing agent, or epoxy epoxy or microencapsulation thereof. Can be mentioned. In particular, phenolic curing agents are preferred from the standpoint of viscosity when the resin composition is varnished. Two or more epoxy hardeners may be used in combination.

 Specific examples of the epoxy curing agent include, for example, dicyandiamide as the amine curing agent, imidazole silane as the imidazole curing agent, 2-phenyl-4-methyl-1-5-hydroxymethylimidazole, 2, 4-diamine, 6- [2'-Methylimidazolyl (Γ)] -ethyl s-triazine dissocyanuric acid 5 mouthfuls, triazine structure phenol novolac resin (for example, phenolite 7 0 5 0 series: Dainippon Ink Chemical Industry Co., Ltd. ¾S).

The polyimide resin composition of the present invention includes two or more phenols in the component (D) 1 in order to control the polyimide extension of the component (A) and the crosslinking density during curing of the epoxy resin of the component (B). It is encouraging to use a polyfunctional phenolic compound having a bivalent acid group. It is possible to increase the crosslink density of component (A) and component (B) by using component (D) together, which reduces thermal expansion in fil above the glass transition point. Noh. In order to increase the crosslink density and decrease the tension and the like, the blending ratio of the component (A), the component (B) and the component (D) in the resin composition is based on the total of 100% by weight. The component (A) is preferably 40 to 85% by weight, the component (B) is 15 to 40% by weight, and the component (D) is preferably 0 to 20% by weight. In addition, phenolic hydroxyl group (X) in component (A) and component (D) The molar ratio (x + z) / (y) of the total of phenol ft * acid groups (z) and epoxy groups (y) in component (B) is 0.7 to 1.3. s preferred.

 As an example of a polyfunctional phenol compound having two or more phenolic hydroxyl groups in 1 ^ of component (D), the same compound as the reaction component [d] can be raised.

 The composition for emphasizing the curable curable polyimide of the present invention is intensively used in combination with a curing accelerator as necessary. For example, melamine, dicyandiamide, guanamine and its derivatives, amines, phenols with one water awakening, organic phosphines, phosphonium salts, quaternary ammonium salts, polysalt »anhydride, light power thione catalyst, cyanene Compounds, isocyanate compounds, block isocyanate compounds and the like.

The woven fiber of the present invention is supplied with an inorganic filler having a specific surface area of 18 to 50 m ² , g. Examples of inorganic charges include silica, alumina, and other forces. Silica power is particularly preferable. Minoru: »^ You can use a mixture of two or more. There are no particular restrictions on the amount of content that can be used for discussion, but preferably, the resin composition can be energized in the range of 10 to 50% by mass. When the content is less than 10% by mass, the effect of the banning ratio and evening revision tends to be difficult to obtain. When it exceeds 50% by mass, not only does the laser processability worsen, but the elastic modulus of the cured product also increases, and it tends to be a hard and brittle material.

The specific surface area of the inorganic filler is in the range of 18 to 50 m ² Zg. Outside this range, there is a tendency for the filler to fall, making it difficult to keep the varnish stable for a long time. The lower limit of the specific surface area is more preferably ²⁰ m ² / g or more. The upper limit of the range of the specific surface area is preferably 40 m ² Zg force, more preferably 3 δπι ² / ^ force, and more preferably 30 m ² / g or less. For example, the range of the specific surface area is preferably from 18 to 40 m ² / g, more preferably from 18 to 35 m ² Zg, and further preferably from 20 to 30 m ² / g.

 The analysis of the ratio table can be performed by the so-called BET method, in which the portion of the adsorption-occupied male is adsorbed on the surface of the powder particle with a liquid and the ratio of the sample is determined from the amount. The most commonly used method is BET method by low-temperature, low-humidity physical adsorption of activated gas.

In the resin composition of the present invention, various emphasis additives, resin components (A) and (B) ^, and the like can be blended within the range in which the effects of the present invention are exhibited. Examples of resin glazes include thickeners such as olben and benton, silicone, fluorine or acrylic defoamers, leveling agents, imidazole, thiazole, triazol, etc. Adhesion imparting agent, surface treatment agent such as silane coupling agent, etc. Coloring agents such as guanine pull 1, phthalocyanine green, iodine green, disazo yellow, vibrant pon black, flame retardants such as phosphorus compounds, odor compounds, aluminum hydroxide, magnesium hydroxide, phosphorus antioxidants The resin composition of the present invention can be used particularly as an interlaminar layer for a multilayer flexible printed wiring board. In particular, a plastic film composed of a resin composition layer (A layer) and a supporting film (B layer) and an intention composition layer (A layer) Form of an RCC type adhesive film formed on a foil Can be used for firewood.

 For the adhesive film, according to a method known to those skilled in the art, for example, a resin varnish prepared by dissolving the curable resin of the present invention in an organic solvent is prepared, and this resin varnish is applied to the support film and copper foil. It can be produced by drying the organic solvent by heating or blowing hot air to form a curable resin composition layer.

 The support film (saddle layer) serves as a support for the adhesive film, and is finally peeled off or removed in the production of the multi-layer printing spring plate. As the support film, for example, polyethylene, polyvinyl chloride Λ / polyolefin, polyethylene terephthalate, and so on may be abbreviated as “Ρ Ε Τ”. ), Polyesters such as polyethylene naphthalate, poly force-ponates, and metal foils such as mold release copper foils. Polyimide, polyamide

It is also possible to use itif fats such as polyamide imide and liquid crystal polymer. When copper foil is used as a supporting tree film, it can be removed by etching with an etchant such as ferric chloride or cupric chloride. The support film may be subjected to a release treatment in addition to a pine treatment and a corona treatment, but it is more preferable that the release film is subjected to release treatment in consideration of peelability. The thickness of the support film is not particularly limited, but is usually from 10 to 1550 m, and preferably from 25 to 50 m.

 In the case of RCC type, the copper foil is used as a part of the multilayer printed board ^ (It is used as a part of this layer. Generally, electrolytic copper foil and rolled copper foil are mentioned, g »copper foil is used. The thickness of the copper foil is not particularly limited, but it is preferable to use an ultrathin copper foil for forming a fine pitch @a line.

Examples of organic solvents for preparing the varnish include acetone, methyl ethyl ketone, and cyclohexane. Ketones such as xanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, petroleum carbite J, etc., toluene The ability to mention aromatic hydrocarbons such as xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Two or more organic solvents may be used in combination.

 Although the drying conditions are not particularly limited, it is necessary to prevent the Mongolian curable resin composition from proceeding as far as possible to the Sengan-ji Temple in order to carry the drought ability of the adhesive film. In addition, if a large amount of organic solvent remains in the adhesive film, it may cause swelling after curing. Therefore, the content of the organic solvent in the incompressible resin composition is usually 5% by mass or less, preferably 3% by mass. Dry to: The specific drying conditions vary depending on the curability of the hatchable resin composition and the amount of organic soot in the varnish. For example, in a varnish containing 30 to 60% by mass of an organic solvent, usually 80 to : L 2 0: 3 ~; 1 Can dry for about 3 minutes. A person skilled in the art can provide suitable drying conditions by a simple experiment.

 The thickness of the resin composition layer (A layer) can usually be in the range of 5 to 500 m. The preferred category of the thickness of layer A depends on the use of the film, and when it is used for the production of multilayer printed wiring boards by the build-up method, it forms a circuit.) The thickness of this layer is usually 5-7 Since the thickness is 0 m, the thickness of the A layer corresponding to the interlayer insulation layer is in the range of 10 to 100 μπι.

 The A layer may be protected with a protective film. By protecting with a protective film, it is possible to prevent adhesion or scratches of dust or the like to the surface of the resin composition layer. The protective film is peeled off during lamination. As the protective film, the same material as the cocoon film can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 40 im.

 The adhesive film of the present invention can be suitably laminated on a circuit board by vacuum laminating overnight. Examples of the inner layer circuit board used here include inner layer circuit boards such as a polyester substrate, a polyimide substrate, a polyamide-imide substrate, and a liquid crystal polymer substrate. The adhesive film of the present invention can also be used for further multilayering of a multilayer printed sheet. It should be noted that the surface of the recovery layer should be roughened by surface treatment such as hydrogen peroxide, Z-sulfuric acid or MEC etch pond (MEC Co., Ltd.). It is preferable from the viewpoint of the adhesiveness.

Examples of commercially available vacuum laminars include, for example, Nichigo-Morton, Inc., vacuum applique Ichiichi, manufactured by Meiki Seisakusho, and Hitachi Techno Engineering. Examples thereof include a roll type dry coater manufactured by Hitachi, Ltd. and a vacuum laminator manufactured by Hitachi AI IC Co., Ltd.

In the laminate, when the adhesive film has a protective film, the protective film is removed, and then the adhesive film is pressure-bonded to the rotating plate while being heated and heated. The lamination conditions are preheated if necessary adhesion full Irumu and times plate, crimping preferably 7 0; 1 4 0, the crimping pressure preferably set to 1 to 1 1 kgf / cm ^2, air雖2 0 mmH The laminating force under reduced pressure of g or less is preferable. The laminating method may be a batch method or a continuous method using a roll. In the case of a cocoon film consisting of a measured spoilage layer (A layer) and a supporting film (B layer), the following steps are followed. After laminating the adhesive film on the circuit board, remove it near room temperature and peel it off. Next, the curable resin composition laminated on the recycle plate is calcined. In addition, the conditions of addition and 匕 are usually selected in the range of 15 0 to 2 20 0 to 20 min to 1 80 min, more preferably 3 0 to 1 2 0 at 16 0 ° C to 2 0 0 Selected in the range of minutes. In addition, when using a support film force S separation and a release layer such as silicon, the film is cured after the curing of the curable resin I, or cured and perforated. You can also

 After the formation, the circuit board is drilled by drilling, laser beam, plasma, or a combination of these as necessary to form via holes. It may be formed. In particular, drilling with a carbon dioxide laser or a YAG laser is commonly used.

 Next, the surface treatment of the insulating layer is performed. The surface treatment can adopt the method used in the desmear process, and can be performed in a form that also serves as a desmear process. The chemical used in the desmear process is oxidant power ^ HIS-like. Examples of the oxidant include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, peroxygen is elemental / sulfuric acid, nitric acid, and the like. Preferably, an alkaline permanganate solution (for example, potassium manganate, sodium permanganate sodium hydroxide deer) is used as an oxidizing agent widely used for roughening the insulating layer in the ffit of a multi-layer printed spring plate by the build-up method. It is also possible to perform the treatment with the agent J before the treatment with the oxidizing agent, and the neutralization treatment with the reducing agent is usually performed after the treatment with the apologizing agent.

The desmear process as described above increases the peel strength of the conductor layer formed by plating. It also serves the purpose of roughening the surface of the insulating layer and providing irregularities.

 After the surface treatment, form a final layer by plating on the surface of the I layer. The difficult layer can be formed by a method that combines a plating method and an electrolytic method. It is also possible to form a metal resist with a pattern opposite to that of this layer, and to form a conductor layer only with electroless plating. By conducting an annealing treatment with a conductor layer shape of 1 5 0 -2 0 0 20 to 90 minutes, the peel strength of this layer can be further improved and stabilized.

 As a method of forming a circuit by patterning the difficult layer, for example, a subtractive method, a semi-additive method, or the like can be used for those skilled in the art. In the case of the subtractive method, the thickness of the electroless copper plating layer is 0.1 to 3 mm, preferably 0.3 to 2. An electrical plating layer (panel plating layer) is formed thereon with a thickness of 3 to 35, preferably 5 to 20 xm, and then an etching resist is formed to etch ferric chloride, cupric chloride, etc. Etching with a liquid ^ (After forming this pattern, the circuit board can be obtained by removing the etching resist IT. In the case of the semi-additive method, the thickness of the electroless copper plating layer is reduced. After forming a copper plating layer at 0.1 to 3 m, preferably 0.3 to 2 m, forming a non-turn resist, and then peeling off to a mm copper plate, Can be obtained.

 In the case of R CC type soot film in which the resin integrity layer (A layer) is formed on copper foil, the following steps are followed. Laminate the adhesive film on the circuit board, and cure the water-resistant resin composition as described above. Next, drilling is performed as described above, and surface treatment of the via is performed by soft etching. Next, electroless plating is performed, and a circuit board can be obtained using the subtractive method as described above. The copper foil used is usually 1 or 2 m of 1 »copper foil. For example,“ DF F ”,“ NS-VL P ”manufactured by Mitsui Mining & Smelting Co., Ltd., Nikko Metal "JT (:"), etc. made by Co., Ltd. S. Also, ultra-thin copper foil can be used according to the requirements of fine lines. For example, "M icro Th in Ex" made by Sakurai Metal Mining Co., Ltd. And “Y SMAP” manufactured by Japan Corporation.

Example

 The contents of the present invention will be specifically described below with reference to examples, but these examples do not limit the present invention in any way.

<&mn> Polyimide resin St (Polyimide varnish A)>

«Stage #g, flask with iUJ meter and condenser were charged with 20 3.07 g of aptilolactone and 304. 60 g of Solvesso 150 as solvent, and 88.8 of isophorone diisocyanate. g (0.4 mol) and hydrogenated polybutadiene diol (hydroxy acid 48.5 KOH—mg / g, fi 313) 231.3 g (0.1 mol) and polybutadiene diol (τ acid male 52.6 KOH-mg Zg , I ^; f. 133) 213.3 g (0.1 mol) was charged and reacted at 70 at 4 hours. Next, nonylphenol nopolac resin (hydroxyl equivalent: 229.4 gZeq, average: 4.27 functional, average calculated molecular weight: 979. 5 gZ mol) 195.9 g (0.2 mol) and ethylene glycol bisanhydride trimellitate: 41. 0 g (0.1 mol) was charged, and the temperature was raised to 150 over 2 hours, followed by reaction for 12 hours.

After the reaction, it became a transparent brown liquid, and a non-volatile content of 60% and a viscosity of 15 Pa · s (polyimide resin with a viscosity of 2 was obtained. The obtained polyimide resin solution was applied to the KB Γ plate, and the solvent component was volatilized. as a result of measuring the infrared absorption scan Bae spectrum of a sample obtained by a characteristic absorption of Isoshianeto group 2270 cm- ¹ is fully extinguished, 725c πΓ ¹ and 1780c m- ¹ and 1720c m- ¹ and the imide Absorption of a ring was confirmed, and absorption of a urethane bond was observed at 1540 cm— ^1. Also, the amount of carbon dioxide generated as the imidization progressed was tracked by the change in SS charged in the flask. The functional group equivalent of the acid anhydride of ethylene glycol monobisanhydro trimellitate is 0.2 mol, and the amount of carbon dioxide generated is 0.2 mol. Anhydride power S All used for imidization, not covered with carboxylic anhydride! ^ It is.

 As a result, 0.2 mol of the isocyanate group is converted to an imide bond, and the remaining isocyanate groups are the hydroxyl groups of hydrogenated polybutadiene diol and polybutadiene diol and the phenol in the nonylphenol nopolac resin. A urethane bond was formed together with a functional hydroxyl group, and as a result, a polyurethaneimide shelf having a phenolic hydroxyl group of nonylphenol nopolac resin and a modified phenolic hydroxyl group modified with a urethane bond was obtained. It is concluded.

Row 2>

Polyimide resin M (polyimide resin varnish B)>

 m, a flask equipped with a meter and a condenser.

—Stage 292.09 g, Solvesso 150 292.09 g, Isophorone diisocyanate 88.8 g (0.4 mol) and polybutadienediol (τ acid Sffi52. 6KOH-mg / g, molecular weight 2133) 426. 6 g (0.2 mol) were charged to 70. The reaction was carried out at C for 4 hours. Next, noniphenol enonopolak resin-(7 acid group equivalent 229.4 g / eq, average 4.27 functionalities, average calculated liver mass 979. δ g / mol) 195.9 g (0.2 mol) and ethylene glycol bis-an Hydrotrimerate 41.0 g (0.1 mol) was charged, and the temperature was raised to 150 ° C. over 2 hours, followed by reaction for 12 hours.

After the reaction, a transparent brown liquid was obtained, and a non-volatile content of 56% and a viscosity of 12 Pa's (at 25) were obtained. The night of the resulting polyimide resin was painted on a KBr plate, and the infrared absorption spectrum of the sample in which the solvent component was volatilized was measured. As a result, 2270 cm- ^1, which is the characteristic absorption of the isocyanate group, disappeared completely. The absorption of the imide ring was observed at 725 cm- ¹ , 1780 cm- ^1, and 1720 cm- ¹ . Absorption of urethane bonds was observed at 1540 cm- ¹ . The amount of carbon dioxide generated with the progress of imidization was 8.8 g (0.2 mol), as monitored by the change in the weight charged to the flask. The functional group equivalent of the anhydride of ethylene glycol bisanhydrotrimellitate is 0.2 mol, the amount of carbon dioxide generated is also 0.2 mol, and all of the anhydride is used for imido formation. It is concluded that the anhydride is not. As a result, 0, 2 mol of the isocyanate group is converted to an imide bond, and the remaining isocyanate group forms a urethane bond with the hydroxyl group of polybutadiene glycol and the phenolic hydroxyl group in nonylphenol nopolac resin. Thus, it is concluded that a polyimide urethane resin having phenolic novolak resin phenolic heptaic acid groups and some phenolic hydroxyl groups modified with urethane bonds was obtained.

<Dance 1>

40 parts of polyimide varnish A obtained in Production Example 1 as component (A), diethylene glycol monoethyl ether acetate of bisphenol A nopolak type epoxy resin (hereinafter referred to as EDGAc) as component (B) and Ivzol 150 (Hanafu hydrocarbon blended rice cake: manufactured by Idemitsu Petrochemical Co., Ltd.) Mixed varnish (solid content 50%, epoxy equivalent 210, manufactured by Japan Epoxy Resin Co., Ltd. “157 S 70J” 10. 9 parts, Imidazo 1 (Part: Japan Epoxy Resin Co., Ltd. “P 2001-150 J”) 0.5 parts, spherical silica (specific surface area 80 m ² / g) 6 parts, further 10 parts toluene, 5.5 parts of absilolacton To prepare a varnish-like shelf-waste product.

<Pride 2> As component (A), 40 parts of polyimide resin varnish obtained in Production Example 1, and as component (B) bisphenol A nopolak type epoxy resin EDGAc and ibzol 150 mixed varnish (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157S70”) 10. 9 parts, Imidazoru Invitation (Japan Epoxy Resin Co., Ltd. “P200H50”) 0.5 parts, Spherical Silica (specific surface area 6.2 m ² / g) A varnish-like resin composition was prepared by adding 6 parts and further 10 parts of toluene.

 <«Example 3>

Component (A) 1 ^ Polyimide resin varnish B obtained in Example 2 40 parts, Component (B) bisphenol A nopolak type epoxy resin EDGAc and ipzol 150 mixed varnish (solid content 50%, epoxy equivalent 210 , Japan Epoxy Resin Co., Ltd. “157S70”) 10.9 parts, Imidazol Tokumoto (Japan Epoxy Resin Co., Ltd. “P200H50”) 0.5 parts, Spherical silica (Specific surface area 80m ² / g) 6 parts Further, 10 parts of toluene and 5.5 parts of butyrolactone were added to prepare a varnish-like resin composition.

<Pride 4>

40 parts of the polyimide resin varnish B obtained in Production Example 2 as component (A), bisphenol A nopolac type epoxy resin EDGAc and ibzorile 150 mixed varnish as component (B) (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157 S 70”) 10. 9 parts, Imidazol invitation (Japan (Japan Epoxy Resin Co., Ltd. “P 200H50”) 0.5 part, spherical silica (specific surface area 6.2 m ² / g) 6 parts and further 10 parts of toluene were added to prepare a varnish-like resin composition.

Fine row 1> ·

As component (A), 40 parts of polyimide resin varnish obtained in Production Example 1, and as component (B), Pisfenol A nopolak type epoxy resin EDGAc and ibzol 150 mixed varnish (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157S70”) 10. 9 parts, Imazosol Induction ^ ίmoto (Japan Epoxy Resin Co., Ltd. “Ρ200Η50”) 0.5 parts, spherical silica (specific surface area 30m ² / g) A varnish-like resin composition was prepared by pouring 6 parts, further 10 parts of toluene, and 2 parts of butyrolactone.

Difficult example 2> As component (A), 40 parts of the polyimide shelf varnish B obtained in Production Example 2, and as component (B) bisphenol A nopolak type epoxy resin EDGAc and ipzol 150 mixed varnish (solid content 50%, epoxy equivalent 210 , Japan Epoxy Resin Co., Ltd. “157 S 70”) 10.9 parts, Imidazole Induced (Japan Epoxy Resin Co., Ltd. “P200H50”) 0.5 parts, Spherical silica (specific surface area 30 m ² / g) 6 A varnish-like resin composition was prepared by mixing 10 parts of toluene, 10 parts of toluene, and 2 parts of butyrolactone.

Pain 3>

As component (A), 40 parts of polyimide resin varnish obtained in Production Example 1, and as component (B), bisphenol A nopolak type epoxy resin EDGAc and ipzol 150 mixed varnish (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157 S 70”) 10. 9 parts, Imidazoru Invitation (Japan Epoxy Resin Co., Ltd. “P200H50”) 0.5 parts, Spherical Silica (specific surface area 20 m ² / g) 6 parts, 10 parts toluene, 4 parts aptylolactone! A varnish-like resin composition was prepared.

• Difficult 4>

40 parts of polyimide resin varnish B obtained in Production Example 2 as component (A), EDGAc and ibzol 150 mixed varnish of bisphenol A nopolac type epoxy resin as component (B) (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157 S 70”) 10.9 parts, imidazole derivative (Japan Epoxy Resin Co., Ltd. “P200H50”) 0.5 parts, Spherical silica (specific surface area 20m ² Zg) 6 parts, Furthermore, 10 parts of toluene and 4 parts of butyrolactone were added to prepare a varnish-like resin composition.

Difficult example 5>

As component (A), 40 parts of polyimide resin varnish A obtained in Production Example 1, and as component (B), bisphenol A nopolak type epoxy resin EDGAc and ibzol 150 mixed varnish (solid content 50%, epoxy equivalent 210, Japan epoxy resin) ("157 S 70" manufactured by Co., Ltd.) 10. 9 parts, imidazole derivative ("P200H50" manufactured by Japan Epoxy Resin Co., Ltd.) 0.5 parts, 6 parts of spherical alumina (specific surface area 22m ² / g), and toluene A varnish-like resin composition was prepared by adding 10 parts.

<Row 6> As component (A), polyimide resin varnish B 40 obtained in Production Example 2, and as component (B) bisphenol A nopolak type epoxy resin ED GA c and ibzol 15 50 mixed varnish (solid content 50%, Epoxy equivalent 2 1 0, Japan Epoxy Resin Co., Ltd. “1 5 7 S 7 0”) 1 0.9 part, imidazole derivative (Japan Epoxy Resin Co., Ltd. “P 2 0 OH 5 0”) 0. 5 parts, spherical alumina

(Specific surface area 2 2 m ² / g) 6 parts and further 10 parts of toluene were added to prepare a varnish-like resin composition.

 Dispersibility>

 In Reference Examples 1 to 4, when the varnish was allowed to stand at room temperature for about 12 hours, the filler sheds, and the force S that separated the varnish was removed. In Examples 1 to 6, the filler force S was uniformly dispersed. Maintained.

Ring of bells 7>

 For the varnish obtained in Example 1, the release treatment polyethylene terephthalate rate is 0? 3 8 mm, hereinafter abbreviated as PET), and the resin composition has a dry odor resin thickness of 60. In this way, the coating was applied by application, and dried at 80 to 12 (TC (average at 100)) for 12 minutes to form a resin composition layer to obtain an adhesive film J-REM.

<Fine row 8>

 For the varnish obtained in Example 2, a resin yarn destruction layer was formed on PET in the same manner as in Example 7 to obtain an adhesive film.

Difficult example 9>

 For the varnish obtained in Example 3, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain an adhesive film.

<Row 1 0>

 For the varnish obtained in Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain an adhesive film.

<Row 1 1>

 What about the varnish obtained in Example 5 as in Example 7? A resin composition layer was formed on ET to obtain an adhesive film.

<Row 1 2>

For the varnish obtained in Example 6, a resin composition layer was formed on and contacted with PET in the same manner as in Example 7. A wearing film was obtained.

 The adhesive films obtained from Examples 7-12 were cured at 180 for 90 minutes. Table 1 shows the characteristics of the cured product of each resin composition. The measurement of the breaking strength of bow I tension was performed in accordance with Japanese Industrial Standard (JIS) K7127. The dielectric properties are measured by the cavity perturbation method (E 8362 B, manufactured by Agilent Technologies Corp.)! «I was jealous. The characteristic values are shown in Table 1.

Comparative Example 1>

 As a comparative card 1, a cured product obtained by allowing an epoxy resin-made interlayer adhesive material (Ajinomoto Fine Techno Co., Ltd. Ne ± SABF—G Xcode 13) to stir at 180 for 90 minutes was obtained. Similar to the above, Table 1 shows the characteristic values of the cured products.

 Table 1>

Row 13>

Adhesion with copper foil (Part 1)

The adhesive film obtained in Example 7 was applied to the S surface and M surface of copper foil (Nikko Metal Co., Ltd. JTC foil), respectively, at a temperature of 100, using a vacuum laminator manufactured by Meiki Seisakusho Co., Ltd. Lamination was performed on one side under conditions of pressure 7kgfZcm ² and pressure 5mmHg or less, and three layers of copper foil / adhesive film / PET were prepared. Next, the release-treated PET film was peeled off and laminated in the same manner on a MEC-etch pond CZ-8100 treated cocoon laminate. Then, the mixture was subjected to 120 minutes at 120 ° C. and 90 minutes at 180 ° C. When the peel strength of the interface of the resin Z copper foil was measured using the obtained substrate, the peel on the S surface was 0.66 kgf / cm, and the peel on the M surface was 1.22 kgfZcm. The peel strength was measured according to JISC 6481 and the foil thickness was 18 / im.

Fine row 14>

Adhesion with copper box (Part 2) Using the adhesive film obtained in Example 8, the peel strength at the shelf / copper foil interface was measured in the same manner as in ¾M Example 13, and the peel on the S surface was 0.73 kg f / cm, the peel on the M surface. There was 1. 05kg f / cm.

<Example 15>

Adhesion with copper foil (Part 3)

 Using the adhesive film obtained in Example 9, the peel strength at the interface of the shelf Z copper foil was measured in the same manner as in Example 13, and the peel on the S surface was 0.50 kg f / cm. The peel was 1.04 kg f / cm.

<Row 16>

Adhesion with copper foil (Part 4)

 Using the adhesive film obtained in Example 10, the peel bow at the resin / copper foil interface was measured in the same manner as in Example 13. As a result, the peel on the S surface was 0.67 kg f / cm, and the M surface was peeled off. The peel was 0.94 kg f / cm.

<Row 17>

Adhesion with copper box (5)

 Using the adhesive film obtained in Example 11 and measuring the peel bow at the interface of the resin / copper box in the same manner as in Example 13, the peel on the S surface was 0.46 kg f / cm, and the M surface was peeled off. The peel was 1.13 kg f Z cm.

<Example 18>

Adhesion with copper foil (Part 6)

 Using the adhesive film obtained in Example 12, the peel of the resin / copper foil interface was measured in the same manner as in Example 13. As a result, the peel on the S surface was 0.44 kg iZcm, and the peel on the M surface was 1. 06 kgf / cm. ·

<Comparative Example 2>

 Using an interlayer resin material made of epoxy resin (ABF—GXCode 13 manufactured by Ajinomoto Fine Techno Co., Ltd.), the peel bow at the interface of the resin Z copper foil was measured in the same manner as in Difficult Example 13. The peel was 0.29 kg f / cm, and the peel on the M surface was 1.44 kgf Zcm.

The results of Examples 13-18 and Comparative Example 2 are summarized in Table 2. Example ¾ «Smooth like S side of foil It also has the power to show good adhesion to the surface.

 Table 2>

 <Challenge 19>

 About Metsukipireire (Part 1)

Adhesive film obtained by the MEC etch pounds CZ- 8100 processing雜同clad laminate on Corporation Meiki Tsurusora laminator in Example 8, temperature 100, pressure 7 kgf / cm ^2, pressure 5 negation Hg or less Laminated on both sides under the conditions of Mold release treatment The PET film was then peeled off, and cured with 18 O for 30 minutes to form an insulating layer. For the surface treatment process of the soot layer that also served as the desmear process, the following chemicals manufactured by Wattec Japan Co., Ltd. were used. Swelling agent “Swelling Dip Securiganth P”, oxidizing agent “Concentrat e Compact CP” (alkali permanganate, reducing agent “Reduction” Chillon 'Sekiyuri Sword (Reduction solution Securiganth P- 500) "

Surface treatment was carried out with a swelling agent solution at a temperature of 80 ° C. for 5 minutes, followed by surface treatment with an oxidizing agent at a temperature of 801: for 5 minutes, and finally neutralization treatment with a reducing agent solution at 40 for 5 minutes. Next, the electroless copper plating catalyst was applied to the surface of the insulating layer and then immersed in an electroless copper plating solution at 32 X: for 30 minutes to form a 1.5 m electroless copper plating film. . This was dried and acid-washed at 150 for 30 minutes, and the copper-containing film was formed by performing electrolytic copper plating for 12 minutes with a flow density of 2. OAZdm ² using a phosphorus-containing copper plate as the anode. Thereafter, annealing was further performed at 180 for 30 minutes. The peel strength of the obtained conductor layer was 0.71 kg f / cm. The peel measurement was performed in accordance with JIS C6481, and the thickness of the ί book was about 25 m.

 <Comparative Example 3>

 An end layer was formed in the same manner as in Example 19 using an epoxy resin-made interlayer paper sheet material (ABF-GXCcode 13 manufactured by Ajinomoto Fine Techno Co., Ltd.). Surface treatment was similarly performed using a chemical solution manufactured by Atotech Japan.

Surface treatment with swelling agent solution at temperature 60 for 5 minutes, then at temperature 80 ° C: 15 minutes with oxidizing agent Finally, neutralization was performed with a reducing agent solution at 40 for 5 minutes. The peel strength of the obtained conductor layer was 0.6 kg f / cm.

<Row 3>

Wire of modified polyimide resin (Linear modified polyimide resin varnish C)>

G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average: ^ amount = 5047 (GPC method), hydroxyl group equivalent = 1798 g / e q., Solid content 100w%: Nippon Soda Co., Ltd. 50 g), ibusol 150 23.5 g, and dibutyltin laurate 0.005 g were mixed and dissolved uniformly. When it became uniform, it was displayed on 5 O: and further, while adding toluene, 2, 4-disisocene (isocyanate group equivalent = 87.08 g / eq.), 4.8 g was added and reacted for about 3 hours. Went. Next, the reaction product was cooled to room temperature, and then benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161 · 1 g / eq.) 8.96 g, triethylenediamine 0 07 g and 40.4 g of ethyl diglycol acetate (manufactured by Daicel Chemical Industries, Ltd.) were added, the temperature was raised to 130 with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm- ¹ was confirmed by FT-IR. Upon confirming the disappearance of the NCO peak, the reaction was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain a linear modified polyimide resin (linear modified polyimide, Kitsuki varnish C).

Properties of linear modified polyimide resin varnish A: Viscosity = 7.5 Pa · s (25 ° C, E-type viscometer) Acid value = 16.9 mgKOH / g

Solid content = 50w%

<Example 5>

 35 parts of polyimide resin varnish C obtained in Production Example 3 as component (A), bisphenol A nopolak type epoxy resin EDGAc and ibzol 150 mixed varnish as component (B) (solid content 50%, epoxy equivalent 210, Japan Epoxy Resin Co., Ltd. “157 S 70”) 10. 9 parts, phenol nopolak (Dainippon Ink Chemical Co., Ltd. “TD2090-60M”) 4. 5 parts, spherical silica (specific surface area 4 lmVg) 6 parts, and further 10 parts of toluene and 2 parts of butyrolactone were added to prepare a varnish-like resin composition.

Dispersibility>

In Comparative Example 4, the filler force was uniformly dispersed even when the varnish was allowed to stand at room temperature for about 12 hours. Maintained 31.

Property values>

 For the varnish obtained in Comparative Example 4, a resin composition layer was formed on PET in the same manner as in Example 7 to obtain an adhesive film, which was cured at 180 for 90 minutes. Table 3 shows the characteristic values of the cured product. Further, when the peel strength of the resin / copper foil interface was measured in the same manner as in Example 13 using the adhesive film obtained from Comparative Example 4, the peel on the S surface was 0.5 5 kgf / cm, M The peel on the surface was 0.67 7 kg ί cm.

Table 3

Claims

The scope of the claims  [1] Multilayer printed wiring board interlayer resin containing a component (A), (B) and (C)  (A) a polyimide resin having a polybutadiene β, urethane «t, imide structure and a phenol structure in the liver,  (B) epoxy resin, (C) Ratio table noble 18-50 m ² / g inorganic filler.  [2] Resin waste for interlayer insulation of multilayer printed wiring boards containing the following components (A), (B) and (C):  (A) [a] a polybutadiene polyol compound having two or more alcoholic hydroxyl groups in one molecule, and [b] a disozone mono-compound to react with each other. A polyimide having a phenol structure at the end of the liver, obtained by reacting [c] tetrasalt am dianhydride, and a polyfunctional phenolic compound having two or more phenolic hydroxyl groups in [d] resin, (B) epoxy resin, (C) A male filler having a ratio of specific surface drawing of 18 to 50 m ² / g. [3] The resin composition according to claim 1 or 2, wherein the inorganic filler of component (C) has a specific surface area of 18 to 40 m ² / g. [4] The resin composition according to claim 1 or 2, wherein the inorganic filler of component (C) has a specific surface area of 18 to 35 m ² / g. [5] The resin composition according to claim 1 or 2, wherein the inorganic filler of component (C) has a specific surface area of 20 to 30 m ² / g.  [6] The resin composition according to claim 1 or 2, wherein the male filler is silica.  [7] The resin composition according to claim 1 or 2, wherein the phenolic compound is a phenol nopolac resin.  [8] The effect composition according to claim 1 or 2, which is a polybutadienepolyol compound-added polybutadienepolyol compound. [9] In the component (A) polyimide resin, the reaction component [a] 1; two or more alcohol hydroxyl groups in ^: the reaction component [b] diisocyanate to the hydroxyl group of polybutadiene polyol The resin composition according to claim 2, wherein Mi: の of the isocyanate group of the compound is reacted at a ratio of 1: 1.5 to 1: 2.5. ,  [10] The resin m ^ product according to claim 1 or 2, further comprising component [D]: a polyfunctional phenol compound having two or more phenolic hydroxyl groups in one liver.  [11] Component (A) is 40 to 85% by weight with respect to the total of 100% by weight of the component (A) polyimide resin, the component (B) epoxy resin and the component (D) polyphenol compound. 11. The resin composition according to claim 10, wherein (B) is contained in an amount of 15 to 40% by weight and component (D) force ¾0 to 20% by weight.  [12] An adhesive film for forming an interlayer insulating layer of a multilayer printed wiring board in which the resin composition according to claim 1 or 2 is formed on a substrate.  [13] A multilayer printed wiring board in which an interlayer insulating layer is formed from the resin composition according to claim 1 or 2.