JP5245526B2 - Insulating resin composition and insulating film with support - Google Patents

Description

  The present invention relates to an insulating resin composition and an insulating film with a support. More specifically, the present invention relates to an insulating resin composition having a low thermal expansion coefficient and excellent adhesive strength with copper, and an insulating film with a support.

As a general method for manufacturing a multilayer wiring board, a material (prepreg) made by impregnating a glass cloth with an epoxy resin and semi-cured on an insulating substrate having an inner layer circuit formed on one side or both sides is laminated with a copper foil. Integrate the layers by hot pressing, then drill holes called through holes for interlayer connection, perform electroless plating on the inner walls of the through holes and the copper foil surface, and if necessary, perform further electrolytic plating A method of manufacturing a multilayer wiring board by removing unnecessary copper after making the thickness necessary as a circuit conductor is mentioned.
However, in recent years, electronic devices have been further reduced in size, weight, and functionality, and accordingly, the integration of LSIs and chip parts has been increased, and the form has rapidly increased in number and size. (See Non-Patent Document 1). For this reason, in order to improve the mounting density of electronic components, development of a fine wiring of a multilayer wiring board is advanced. As a manufacturing method of multilayer wiring boards that meet these requirements, build-up that uses insulating resin that does not contain glass cloth as an insulating layer instead of prepreg, and forms a wiring layer while connecting only necessary parts with via holes Multilayer wiring boards having a structure are becoming mainstream as methods suitable for weight reduction, miniaturization, and miniaturization.

Further, in the multilayer substrate having the build-up structure, as the number of layers increases, the via portion is filled and stacked (see Non-Patent Document 2).
However, insulation resin layers that do not contain glass cloth tend to have a large coefficient of thermal expansion for thinner multilayer wiring boards, so the difference in thermal expansion coefficient between copper in filled and stacked vias is a reliable connection. It has a great influence on reliability and has become a concern for reliability.
As described above, a material having a low thermal expansion coefficient has been required for the insulating resin. In addition, since the contact area between the resin and the metal decreases with the fine wiring, it is necessary to increase the adhesion of the resin-metal interface.

Conventionally, eutectic solder using lead-tin has been used for soldering printed wiring boards used in electronic devices. However, with increasing environmental problems, lead removal is rapidly progressing in consideration of the effects of lead on the human body and the environment.
Generally, the melting temperature of lead-free solder is higher than that of the conventional lead-tin system (210 to 230 ° C.). For this reason, the printed wiring board material (FR-4) that has been generally used conventionally has a problem that the substrate is swollen during the reflow process or the insulation reliability is lowered.
For this reason, a technique has been adopted in which the glass transition temperature (Tg) of the resin used for the substrate is increased, or a large amount of filler is added while preventing aggregation of the filler (see Patent Document 1).
However, with conventional high Tg substrates, there is a problem that blistering occurs in a reflow test at around 260 ° C., or when a high-hardness filler typified by silica is highly filled, the punching processability deteriorates. There was a problem.

2005 Japan Packaging Technology Roadmap, Japan Electronics and Information Technology Industries Association, pp168-169 Journal of Japan Institute of Electronics Packaging, vol.10, No.5, pp342-343, (2007) JP 2002-80624 A

  An object of the present invention is to provide an insulating resin composition having a low coefficient of thermal expansion and excellent adhesion to copper, and an insulating film with a support formed by forming a semi-cured product thereof on the surface of the support. To do.

  As a result of advancing research to solve such problems, the present inventors have found that as an insulating resin composition, an epoxy resin, a phenolic hydroxyl group-containing polyamideimide having a low thermal expansion coefficient, and a highly adhesive phenoxy resin And it discovered that high adhesiveness and a low thermal expansion coefficient were securable by including an inorganic filler as an essential.

That is, the gist of the present invention is as follows.
1. An insulating resin composition comprising (A) an epoxy resin, (B) a phenolic hydroxyl group-containing polyamideimide, (C) a phenoxy resin, and (D) an inorganic filler.
2. As content in the total solid of the said insulating resin composition, (A) epoxy resin is 10-30 mass%, (B) phenolic hydroxyl group containing polyamideimide is 35-65 mass%, (C) phenoxy resin is 3 The insulating resin composition according to 1 above, wherein ˜20 mass% and (D) the inorganic filler is 5-38 mass%.
3. 3. The insulating resin composition according to 1 or 2, wherein the insulating resin composition further contains (E) crosslinked rubber particles.
4). (A) The insulating resin composition as described in 3 above, wherein the solid content mass ratio between the epoxy resin and the (E) crosslinked rubber particles is 80/20 to 98/2.
5. An insulating film with a support, wherein a semi-cured film of the insulating resin composition according to any one of 1 to 4 is formed on the surface of the support.

  According to the present invention, it is possible to provide an insulating resin composition having a low coefficient of thermal expansion and excellent adhesion to copper, and an insulating film with a support formed by forming a semi-cured product thereof on the surface of the support. it can.

First, the insulating resin composition in the present invention will be described.
The present invention is an insulating resin composition containing (A) an epoxy resin, (B) a phenolic hydroxyl group-containing polyamideimide, (C) a phenoxy resin, and (D) an inorganic filler.
Here, the epoxy resin that is the component (A) is an epoxy resin having one or more epoxy groups in the molecule, and examples thereof include 2-functional polyepoxy resins.
Among these, the polyfunctional epoxy resin having 5 or more functional groups includes a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a phenol biphenylene novolac type epoxy resin, a bisphenol A novolac type epoxy resin, and an aralkyl type epoxy resin. Examples of the epoxy resin include tetraglycidyl metaxylenediamine type epoxy resin and tetrakishydroxyphenylethane type epoxy resin. Examples of the trifunctional epoxy resin include triglycidyl isocyanurate or triphenylglycidyl ether methane type epoxy resin. As the bifunctional epoxy resin, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane [bisphenol F], Bisphenol AD having an intermediate character of fine both like.
The epoxy resin is not limited to the above, and several types may be used simultaneously.
It is preferable that the compounding quantity of the said epoxy resin is 10-30 mass% in the ratio in the total solid of the insulating resin composition except a solvent. By setting it as 10 mass% or more, the adhesive strength with a required metal is obtained, and a low thermal expansion coefficient can be maintained by setting it as 30 mass% or less.

(B) The phenolic hydroxyl group-containing polyamideimide is a polymer having a phenolic hydroxyl group reactive with an epoxy resin in addition to an amide group and an imide group in the molecular structure.
Polyamideimide resin has low thermal expansion and high glass transition temperature (Tg) due to imide ring, high adhesion to metals due to amide group, and is soluble in solvent A lot of research has been done. As a method for producing a polyamideimide resin, for example, a so-called isocyanate method is known which includes a step of reacting trimellitic anhydride and aromatic diisocyanate. As an application example of this isocyanate method, as described in Japanese Patent No. 2897186 and JP-A-4-182466, an aromatic tricarboxylic acid anhydride and an aromatic diamine are reacted under diamine excess conditions, and then a diisocyanate is reacted. There is a way to make it.
(B) The phenolic hydroxyl group-containing polyamideimide is a compound in which a phenolic hydroxyl group capable of reacting with an epoxy resin is further introduced without impairing the properties of the general polyamideimide produced by the above method. As a method for introducing a phenolic hydroxyl group, for example, in the method described in the above-mentioned publication, an aromatic tricarboxylic acid anhydride and an aromatic diamine are reacted under an excess condition of the diamine and then reacted with a diisocyanate. And a method of copolymerizing an aromatic dicarboxylic acid having a functional hydroxyl group, such as hydroxyisophthalic acid.
(B) The content of the phenolic hydroxyl group-containing polyamideimide is preferably 35 to 65% by mass in the total solid content of the insulating resin composition excluding the solvent. It is because the thermal expansion coefficient of resin can be kept low by setting it as 35 mass% or more, and a precise roughened shape can be maintained at the time of metal plating by setting it as 65 mass% or less.

(C) The phenoxy resin is a high molecular weight resin having a phenoxy group in the molecular structure and a molecular weight of 10,000 or more, synthesized from bisphenol A and epichlorohydrin, or diglycidyl ether, and similar in structure to other epoxy resins. Therefore, the compatibility is good and the adhesiveness is also good.
(C) It is preferable to make content of a phenoxy resin into 3-20 mass% in the total solid of an insulating resin composition except a solvent. By making it 3% by mass or more, it becomes possible to contribute to high adhesion to metal, and by making it 20% by mass or less, a low thermal expansion coefficient can be maintained and high tensile strength can be kept. is there.

Examples of the (D) inorganic filler include silica, fused silica, talc, alumina, aluminum hydroxide, barium sulfate, calcium hydroxide, aerosil, and calcium carbonate. These may be used alone or in combination. In view of flame retardancy and low thermal expansion, aluminum hydroxide or silica is preferably used alone or in combination. These inorganic fillers may be surface-treated with a coupling agent for the purpose of enhancing dispersibility, or may be dispersed by a known kneading method such as a kneader, ball mill, bead mill, or three rolls.
Among these, examples of the coupling agent include silane coupling agents, and specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyl (methyl) dimethoxysilane. , Epoxy group-containing silane such as 2- (2,3-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- An amino group-containing silane such as (2-aminoethyl) -3-aminopropyl (methyl) dimethoxysilane; a cationic silane such as 3- (trimethoxylyl) propyltetramethylammonium chloride; such as vinyltriethoxysilane Vinyl group-containing silane; 3-methacryloxypropylto Acryl group-containing silanes such as methoxy silane; and mercapto group-containing silane such as and 3-mercaptopropyl trimethoxysilane.
(D) It is preferable to make content of an inorganic filler into 5-38 mass% in the total solid of an insulating resin composition except a solvent. More preferably, it is 30 to 38% by mass, and if it is 5% by mass or more, the effect of low thermal expansion is increased. It does not become a shape, the resin elongation rate decreases, and the adhesive strength with the metal does not weaken. Moreover, the handleability of the semi-cured resin is improved.

Next, in the present invention, it is desirable to further blend (E) crosslinked rubber particles. Such a crosslinked rubber has the effect of toughening the insulating resin after curing and improving the contact strength with the wiring formed by plating. Moreover, since such a crosslinked rubber particle contributes also to the improvement of the bending resistance of a semi-hardened film, there exists an advantage which a handleability improves.
Examples of (E) crosslinked rubber particles include copolymers of acrylonitrile and butadiene, specifically, acrylonitrile butadiene rubber particles (NBR) obtained by copolymerization of acrylonitrile and butadiene, and carboxylic acids such as acrylonitrile, butadiene, and acrylic acid. Copolymerized carboxylic acid-modified acrylonitrile butadiene rubber particles, polybutadiene or NBR as a core, acrylic acid derivative as a shell, butadiene rubber-acrylic resin core-shell particles, and ethylene and an α-olefin having 3 to 20 carbon atoms Crosslinkable rubber-like polymer particles containing an ethylene / α-olefin copolymer consisting of can be used.
The content of the (E) crosslinked rubber particles is preferably such that (A) the epoxy resin and (E) the solid content blending ratio (mass ratio, hereinafter the same) of the crosslinked rubber is 80/20 to 98/2.
By setting the solid content ratio to 80/20 or more, necessary solder heat resistance can be obtained, and a low thermal expansion coefficient can be maintained. Moreover, the toughness of insulation resin hardened | cured material can be maintained by setting it as 98/2 or less.

In the insulating resin composition used in the present invention, (B) the phenolic hydroxyl group-containing polyamideimide acts as a curing agent for the (A) epoxy resin, but if necessary, other curing agents may be added. it can. As other curing agents, various phenol resins, acid anhydrides, amines, hydragits and the like can be used.
As phenolic resins, bifunctional phenolic resin, novolac type phenolic resin, cresol novolac type phenolic resin, etc. can be used. As acid anhydrides, phthalic anhydride, benzophenone tetracarboxylic dianhydride, methyl hymic acid Examples of amines include primary to tertiary amines, and examples of primary amines include dicyandiamide, diaminodiphenylmethane, and guanylurea. Secondary amines include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiomorpholine, etc. Is mentioned.
Examples of the tertiary amine include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and the like.
Among these, dicyandiamide is preferable from the viewpoint of adhesion to the circuit conductor, and it is more preferable to use dicyandiamide and novolak phenol in consideration of heat resistance and insulation.
It is preferable that the usage-amount of a hardening | curing agent is 0.5-1.5 equivalent with respect to the epoxy group of (A) epoxy resin as a total amount including (B) phenolic hydroxyl group containing polyamideimide. By setting it to 0.5 equivalent or more with respect to the epoxy group, a low coefficient of thermal expansion can be maintained, and by setting it to 1.5 equivalent or less, the unevenness after roughening is reduced, which is suitable for forming fine wiring. is there.

Moreover, in the insulating resin composition used by this invention, a reaction accelerator can be added as needed other than a hardening | curing agent. As the reaction accelerator, various imidazoles and BF ₃ amine complexes which are latent thermosetting agents can be used.
Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-hepta. Decylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4- Examples include methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline.
Among these, preferably, from the viewpoint of storage stability of the insulating resin composition, handling property of the B-stage (semi-cured) insulating resin composition, and solder heat resistance, 2-phenylimidazole and 2- Ethyl-4-methylimidazole is preferable, and the blending amount is optimally about 0.2 to 0.6% by mass with respect to the blending amount of the epoxy resin. By setting it to 0.2% by mass or more, it is possible to increase the degree of curing and maintain a low coefficient of thermal expansion, and it is suitable for forming fine wiring by suppressing the amount of roughening to be 0.6% by mass or less. As a result, the storage stability of the insulating resin composition and the handleability of the semi-cured insulating resin composition are good.

  In addition to the essential and optional components, the insulating resin composition in the present invention includes various additions such as a thixotropic agent, a surfactant, and a coupling agent that are used in ordinary multilayer printed wiring board resin compositions. An agent can be appropriately blended. When using the additive, after sufficiently stirring, the insulating resin composition can be obtained by standing until the bubbles disappear.

When using the insulating resin composition in the present invention, it is preferable from the viewpoint of workability to mix in a solvent and dilute or disperse to form a varnish. Examples of the solvent include methyl ethyl ketone, xylene, toluene, acetone, ethylene glycol monoethyl ether, cyclohexanone, ethyl ethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like. Can be used. These solvents may be used alone or in a mixed system.
What is necessary is just to adjust the usage-amount of a solvent according to the installation of the said coating film formation of the said resin composition. For example, when the insulating resin composition varnish is applied to a carrier film or a metal foil with a comma coater, the amount of the solvent used is preferably adjusted so that the solid content concentration in the varnish is 30 to 60% by mass.

Next, the insulating film with a support of the present invention is obtained by forming a semi-cured film (hereinafter referred to as “semi-cured film”) of the above-mentioned insulating resin composition on the surface of the support.
Examples of the support on which a semi-cured film is formed include, for example, polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and release paper and copper foil. A metal foil such as an aluminum foil can be used. The support may be subjected to corona treatment or mold release treatment. The thickness of a support body is 10-150 micrometers normally, Preferably it is 25-50 micrometers.

  In order to obtain an insulating film with a support, for example, a method in which a varnish of an insulating resin composition is prepared as described above, the varnish is applied on a support, and dried to be semi-cured. Moreover, when apply | coating a varnish on a support body, a comma coater, a bar coater, a kiss coater, a roll coater, etc. are used suitably by application | coating thickness. The coating thickness, drying conditions after coating, and the like are appropriately selected according to the purpose of use and are not particularly limited. However, it is generally preferable that the solvent used in the varnish volatilizes 80% by mass or more.

  The thermal expansion coefficient of the insulating resin layer in the present invention is preferably 40 ppm / K or less. The lower limit is not particularly limited as long as other characteristics are not hindered. If it is higher than 40 ppm / K, there is a tendency that cracks are likely to occur in the insulating resin and cracks in the plated copper in the via due to the difference in thermal expansion coefficient with copper due to temperature changes such as thermal cycle tests. This greatly affects connection reliability.

EXAMPLES Next, although an Example demonstrates this invention further in detail, the scope of the present invention is not restrict | limited to these Examples.
About the hardened | cured material of the insulating resin composition and the insulating film with a support body which were produced by the Example and the comparative example, the thermal expansion coefficient, the adhesive strength, the 288 degreeC solder heat resistance test, and the tension test were implemented with the following method.

(1) Thermal expansion coefficient The insulating film with a support obtained in each Example and Comparative Example was laminated on copper foil, dried at 180 ° C. for 1 hour, and then the copper foil was removed to prepare a test piece. Was measured. The measurement is performed using a TMA2940 thermomechanical analyzer (trade name, manufactured by TA Instruments Co., Ltd.), cutting the sample into a width of 3 mm, and pulling the sample under the conditions of a heating rate of 10 ° C./min, a measurement length of 8 mm, and a load of 5 g. Measured by the method. At that time, the first run was heated to 250 ° C. to remove the distortion of the cured product, cooled to −30 ° C., and then heated again to 300 ° C. From the amount of thermal expansion and the length of the test piece, A thermal expansion coefficient of ˜120 ° C. was calculated.
(2) Resin-metal bond strength (peel strength)
Form a portion of width 10 mm and length 100 mm on a part of the plating surface layer of the resin-coated laminate produced in each Example and Comparative Example, peel off one end at the plated copper layer / resin interface and grab it with a gripping tool. The load when peeled off at a pulling speed of about 50 mm / min in the vertical direction at room temperature was measured.
(3) 288 ° C. solder heat resistance The BF plate with resin produced in each example and comparative example was cut into 25 mm squares, floated in a solder bath adjusted to 288 ± 2 ° C., and the time until blistering was examined. .
(4) Tensile test The cured resin films produced in each of the examples and comparative examples were cut into a width of 10 mm and a length of 80 mm, and both ends were clamped with a jig, and a toughness tester (manufactured by Shimadzu Corporation, trade name: Auto) Graph AG-100C) was used to examine the elongation of the resin.

Production Example 1 (Production of phenolic hydroxyl group-containing polyamideimide A)
In a 2 L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer in a nitrogen atmosphere, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, which is an aromatic diamine compound (product) Name, BAPP, manufactured by Wakayama Seika Kogyo Co., Ltd.) 30.8 g, trimellitic anhydride (TMA) 28.9 g, and aprotic polar solvent N-methyl-2-pyrrolidone (NMP) 230 g The reaction solution was stirred at 80 ° C. for 30 minutes and dissolved in the solvent.
Subsequently, 200 mL of toluene which is an aromatic hydrocarbon azeotropic with water was added to the reaction solution, and the mixture was refluxed at 160 ° C. for 2 hours. After confirming that the theoretical amount of water has accumulated in the moisture determination receiver and that no water has flowed out, remove the water and toluene in the moisture determination receiver and raise the temperature of the reaction solution to 180 ° C. Then, toluene in the reaction solution was removed.
Then, after cooling the reaction solution to room temperature, 9.1 g of 5-hydroxyisophthalic acid, 7.1 g of 2,4-dihydroxybenzoic acid, and 37.6 g of 4,4′-diphenylmethane diisocyanate (MDI) which is a diisocyanate were added. In addition, the reaction solution was raised to 170 ° C. and reacted for 2 hours to obtain an NMP solution of a phenolic hydroxyl group-containing polyamideimide resin A. When the Mw of the obtained phenolic hydroxyl group-containing polyamideimide resin A was measured by gel permeation chromatography (GPC) under the conditions described in Table 1, Mw was 22,000 and the theoretical phenol equivalent was 654. It was.

Production Example 2 (Production of phenolic hydroxyl group-free polyamideimide B)
In a 2 L separable flask equipped with a Dean-Stark reflux condenser, thermometer, and stirrer, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, an aromatic diamine compound] [Wakayama Seika Kogyo Co., Ltd.] Co., Ltd., trade name: BAPP] 30.8 g, trimellitic anhydride (TMA) 28.9 g and aprotic polar solvent N-methyl-2-pyrrolidone (NMP) 230 g And stirred at 80 ° C. for 30 minutes.
Subsequently, 200 mL of toluene which is an aromatic hydrocarbon azeotropic with water was added to the reaction solution, and the mixture was refluxed at 160 ° C. for 2 hours. After confirming that the theoretical amount of water was obtained in the moisture determination receiver and that no water flow was observed, water and toluene in the moisture determination receiver were removed, and the temperature of the reaction solution was further increased to 190 ° C. The toluene in the reaction solution was removed.
Then, after cooling the reaction solution to room temperature, 22.5 g of 4,4′-diphenylmethane diisocyanate (MDI), which is a diisocyanate, is added and the reaction solution is heated to 170 ° C. for 2 hours to contain a phenolic hydroxyl group. An NMP solution of polyamideimide resin A was obtained. The molecular weight (Mw) in the gel permeation chromatography (GPC) of the obtained phenolic hydroxyl group-containing polyamideimide resin A was 25,000.

Example 1
(1) Etching is performed on one side of a glass cloth base epoxy resin double-sided copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name MCL-E-67) having a substrate thickness of 0.8 mm and a copper thickness of 18 μm. A substrate having an inner layer circuit was prepared.
(2) A varnish of an insulating resin composition having the following composition was prepared. The insulating resin composition varnish was coated on a PET film (support) and dried at 130 ° C. for 5 minutes to prepare a roll of an insulating film with a support having a thickness of 40 ± 3 μm. Further, this insulating film with support and the circuit board are stacked with the semi-cured film on the surface side in contact with the inner layer circuit of the circuit board, and a batch type vacuum pressure laminator (trade name: MVLP-500, manufactured by Meiki Co., Ltd.). ).
[composition]
-(A) 25 parts by mass of an epoxy resin having a biphenyl structure and a novolac structure (Nippon Kayaku Co., Ltd., trade name: NC3000S-H)-(B) NMP solution of a phenolic hydroxyl group-containing polyamideimide resin A (solid 54 parts by mass) (C) Phenoxy resin: (manufactured by Toto Kasei, trade name: FX-293) 5 parts by mass. (D) Inorganic filler: spherical silica (manufactured by Admatechs Co., Ltd., trade name:
Admafine SO-25R) 80 parts by mass / reaction accelerator: 2-phenylimidazole (trade name 2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) 0.2 parts by mass / curing agent: aminotriazine novolac type phenol (Dainippon Ink & Chemicals, Inc.) Product name: LA3018) 2 parts by mass / solvent: 25 parts by mass of N-methylpyrrolidone

(3) Next, after peeling off the PET film of the support, the semi-cured film was cured under a curing condition of 180 minutes at 180 ° C. to obtain an insulating layer.
(4) In order to chemically roughen the insulating layer, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L, NaOH: 5 g / L was prepared as a swelling liquid, heated to 70 ° C. and immersed for 5 minutes. Next, an aqueous solution of KMnO ₄ : 60 g / L and NaOH: 40 g / L was prepared as a roughening solution, heated to 80 ° C. and immersed for 10 minutes. Subsequently, it was neutralized by immersing in an aqueous solution of a neutralizing solution (SnCl ₂ : 30 g / L, HCl: 300 ml / L) at room temperature for 5 minutes.
(5) In order to form a plating layer on the surface of the insulating layer, first, an electroless plating catalyst containing palladium chloride (PdCl ₂ ) (trade name: HS-202B, manufactured by Hitachi Chemical Co., Ltd.) is used at room temperature. Immersion treatment was performed for a minute, washed with water, and immersed in a plating solution (trade name: CUST-201, manufactured by Hitachi Chemical Co., Ltd.) for electroless copper plating for 15 minutes at room temperature, and further copper sulfate electrolytic plating was performed. Thereafter, annealing was performed at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 25 μm on the surface of the insulating layer. Table 2 shows the performance evaluation results for the cured product of the obtained insulating resin composition.

Example 2
In Example 1, Example 1 except that 20 parts by mass of epoxy resin (NC-3000S-H) and 5 parts by mass of bisphenol F type epoxy resin (trade name: JER-806, manufactured by Japan Epoxy Resin Co., Ltd.) were used. And performed in the same manner.
The performance evaluation results are shown in Table 2.

Example 3
In Example 1, 1 part by mass of (E) particulate NBR (JSR Corporation, trade name: XER-91) was added with the same blending amount. Others were performed in the same manner as in Example 1. The performance evaluation results are shown in Table 2.

Example 4
In Example 1, the amount of (C) phenoxy resin was replaced with FX-280 (trade name, manufactured by Tohto Kasei Co., Ltd.) while maintaining the same blending amount. Others were performed in the same manner as in Example 1. The performance evaluation results are shown in Table 2.

Example 5
In Example 3, the component (E) was replaced with a butadiene-acrylic resin core-shell rubber (EXL-2655, manufactured by Rohm & Haas Japan Co., Ltd., trade name) while maintaining the same blending amount. Others were performed in the same manner as in Example 3. The performance evaluation results are shown in Table 2.

Comparative Example 1
In Example 1, instead of (B) the phenolic hydroxyl group-containing polyamideimide resin A, 54 parts by mass of the phenolic hydroxyl group-free polyamideimide resin B was used. Others were performed in the same manner as in Example 1. The performance evaluation results are shown in Table 2.

Comparative Example 2
In Example 1, the same procedure as in Example 1 was performed except that (D) the inorganic filler was not added. The performance evaluation results are shown in Table 2.

Comparative Example 3
In Example 5, it carried out similarly to Example 5 except not adding (C) phenoxy resin. The performance evaluation results are shown in Table 2.

From Table 2, the characteristics of the laminated sheet with plated copper using the insulating resin composition of the present invention were such that, as shown in Examples 1 to 5, the coefficient of thermal expansion was low, the adhesiveness was excellent, and the tensile strength was also good. Indicates. It also has excellent 288 ° C. solder heat resistance, and it is possible to manufacture a multilayer wiring board that is environmentally friendly.
On the other hand, the multilayer wiring board shown in Comparative Example 1-3 that does not contain any of the essential components of the insulating resin composition of the present invention has a tendency to deteriorate the thermal expansion coefficient, adhesive strength, solder heat resistance, and tensile strength. It is done.

  Since the insulating resin composition and the insulating film with a support of the present invention have a low coefficient of thermal expansion, excellent adhesion to copper, and good tensile strength, they can be used as materials for semiconductor miniaturization and densification. can do.

Claims (4)

(A) an epoxy resin having a biphenyl structure and a novolak structure, (B) a phenolic hydroxyl group-containing polyamideimide, (C) a phenoxy resin, and (D) an inorganic filler , each content of the insulating resin composition As content in the total solid content, (A) 10-30 mass% of epoxy resin having biphenyl structure and novolac structure, (B) 35-65 mass% of phenolic hydroxyl group-containing polyamideimide, (C) phenoxy resin 3 to 20% by mass, and (D) an insulating resin composition having an inorganic filler content of 5 to 38% by mass,
(B) A phenolic hydroxyl group-containing polyamideimide is obtained by reacting an aromatic tricarboxylic acid with an aromatic diamine and then reacting with a diisocyanate, and simultaneously copolymerizing an aromatic dicarboxylic acid having a phenolic hydroxyl group. An insulating resin composition, which is a polyamideimide . The insulating resin composition according to claim 1, wherein the insulating resin composition further contains (E) crosslinked rubber particles. (A) epoxy resin and (E) an insulating resin composition according to claim 2 solid weight ratio of 80/20 to 98/2 of the crosslinked rubber particles. A semi-cured film of the insulating resin composition according to any one of claims 1 to 3 is formed on the surface of the support.