TW201412864A - Thermosetting resin compositions, resin films in B-stage, metal foils, copper clad boards and multi-layer build-up boards - Google Patents

Abstract

To provide an epoxy-based thermosetting resin, which has flexibility and allows film insulation, has reliability and processability to be matched with halogen-free FR-4, and has less resin flow during vacuum lamination. A thermosetting resin composition contains (a1) a liquid epoxy resin, (a2) a solid epoxy resin, (b) an aromatic diamine compound containing an ether group, (c) a solvent-soluble polyimide resin with its weight average molecular weight below 50000, and (d) a phenoxy resin. Based on the total amount of (a1) the liquid epoxy resin, (a2) the solid epoxy resin, and (b) the diamine compound as 100 weight parts, the total amount of (c) the solvent-soluble polyimide resin and (d) the phenoxy resin is above 15 weight parts and below 100 weight parts.

Description

Thermosetting resin composition, B-stage (semi-hardened stage) resin film, metal foil, copper clad laminate, and multilayer build-up substrate Field of invention

The present invention relates to a thermosetting resin composition having a small resin flow, a B-staged resin film produced using the same, a B-staged copper foil coated with a B-stage on one side of a metal foil, and A copper-clad laminate or the like, the thermosetting resin composition can be used as an adhesive, a prepreg, a paint, or the like, and a base material for a flexible substrate or a build-up substrate mainly composed of a flexible substrate can be produced. And a metal base substrate as a base such as aluminum, and the present invention can be used in a high-density flexible build-up printed wiring board which is bendable and has high heat resistance, high adhesion strength, high reliability, primary molding substrate use, and heat release substrate. For use, etc., the printed wiring board produced by the same can be used in portable devices, LED substrates, module substrates, and the like.

Background of the invention

In recent years, as in the high-performance of portable devices and the thinness represented by liquid crystal televisions, the printed wiring boards and module substrates used in such devices are required to be thinner and more highly functional. It is known that some of these printed wiring boards are using flexible printed wiring boards.

Conventionally, a material for a flexible substrate having a bendable and substrate-free material is generally modified by using a carboxyl-modified rubber or a thermoplastic resin or a phenoxy resin in addition to a polyimide-based material. An epoxy resin based adhesive for the material. These are also used in copper clad laminates and coatings. However, these materials generally have less resin flow after forming, but have a low Tg and are less reliable than rigid materials.

In the patent document 1 (Japanese Patent Application No. 2011-170165), the present applicant discloses a thermosetting resin composition containing a liquid epoxy resin, a solid epoxy resin having a softening point of 130 ° C or less, and a benzoic acid ester. An aromatic diamine compound having a polymethylene group in the main chain, a solvent-soluble polyimine resin having a Tg of 200 ° C or higher and a weight average molecular weight Mw of 50,000 or less, and a phenoxy resin having a Tg of 130 ° C or more .

Prior technical literature Patent literature

Patent Document 1: Special Wish 2011-170165

Summary of invention

However, since the melt viscosity of the B-staged resin film on the material is low, the resin flow is increased in the vacuum press molding, and it is difficult to control the plate thickness precision.

Moreover, even in the all-polyimine flexible wiring board, there is no suitable layering material suitable for use.

Therefore, there is currently no material that fully satisfies these requirements, especially The flexibility of the material for a flexible substrate and the thin film insulating layer have an epoxy-based flexible substrate material which is comparable to the reliability and processing characteristics of the halogen-free FR-4 and has a small resin flow. The processing characteristics referred to herein are, for example, laser through hole workability, desmearing etchability, and the like.

An object of the present invention is to provide an epoxy-based thermosetting resin which has a certain degree of flexibility and a thin film insulating layer, and which has reliability and processing characteristics comparable to that of halogen-free FR-4 and which has little resin flow during vacuum pressing.

Further, an object of the present invention is to provide a flexible substrate material using the above-mentioned thermosetting resin, and to provide an adhesive material for a heat radiation substrate which is excellent in adhesion strength to a metal such as pure aluminum. Further, an object of the present invention is to provide a high-density flexible build-up printed wiring board, a module substrate, and a heat radiation substrate using the above.

The thermosetting resin composition of the present invention is characterized by comprising (a1) a liquid epoxy resin, (a2) a solid epoxy resin, (b) an aromatic diamine compound having an ether group, and (c) a weight average molecular weight. a solvent-soluble polyimine resin having a Mw of 50,000 or less and (d) a phenoxy resin; and the liquid epoxy resin (a1), the solid epoxy resin (a2), and the (b) diamine compound When the total amount is 100 parts by weight, the total amount of the solvent-soluble polyimine resin (c) and the (d) phenoxy resin is 15 parts by weight or more and 100 parts by weight or less.

Further, the present invention relates to a B-staged resin film produced from the above thermosetting resin composition.

Moreover, the present invention relates to a thin resin provided with a B-stage Metal foil and copper clad laminate for film.

Further, the present invention relates to a multilayer build-up substrate produced by using the above-described thermosetting resin composition as an interlayer insulating material.

In the past, there has been no material which can completely satisfy the flexibility, the reliability, the workability, and the fluidity after vacuum pressing in the material for a flexible substrate having no substrate.

In the present invention, it has been found that the flexibility of the epoxy resin can be improved without lowering the reliability and the workability, and it can be achieved by using a phenoxy resin and a soluble polyimide resin in combination.

Further, in order to reduce the fluidity after vacuum pressing, hydrogen bonding between the secondary hydroxyl group obtained by the reaction of the epoxy resin and the aromatic diamine compound and the ether group in the aromatic diamine compound, and the aromatic ring The π-π electron interaction enhances the intermolecular force, and the apparent molecular weight of the resin composition increases and the melt viscosity increases.

Form for implementing the invention

((a1) liquid epoxy resin and (a2) solid epoxy resin)

In the present invention, (a1) the liquid epoxy resin is a liquid epoxy resin at 25 ° C, and the (a2) solid epoxy resin is a solid epoxy resin at 25 ° C.

As long as both are epoxy resins having two or more epoxy propyl groups, they can be appropriately selected according to the purpose. Ideally, as a liquid epoxy resin, it can be mentioned as double A Type epoxy resin, double F type epoxy resin, phenolic phenol type epoxy resin, and naphthalene type epoxy resin. Further, examples of the solid epoxy resin include a phenol phenol type epoxy resin, a bisphenol type epoxy resin, a naphthalene type epoxy resin, and a dicyclopentadiene type epoxy resin. These may be used alone or in combination of two or more.

Further, in the case of using a liquid epoxy resin or a solid epoxy resin, it is preferable to use a solid epoxy resin so that the cured physical properties are close to the FR-4 resin, but it is difficult to uniformly melt the entire resin composition during curing. status. Thus, the melting is continuously carried out by using an epoxy resin which is still liquid at normal temperature to achieve the above object.

The viscosity of the liquid epoxy resin is preferably 1.0 to 120 Pa‧s at 25 ° C, more preferably 1.2 to 100 Pa‧ s. However, the viscosity is defined using the value measured by an E-type viscometer.

The ratio of the liquid epoxy resin to the solid epoxy resin is preferably determined from the viewpoint of desired properties and flexibility in a semi-hardened state. Therefore, the optimal combination ratio does not necessarily have to be limited. However, when the total amount of the two is 100 parts by weight, the ratio of the liquid epoxy resin is preferably from 20 to 50 parts by weight.

((b) an aromatic diamine compound having an ether group)

The aromatic diamine-based curing agent having an ether group is excellent in adhesion strength to a metal substrate such as a polyimide film or aluminum, and the secondary hydroxyl group and the aromatic diamine obtained by reacting an epoxy resin and an aromatic diamine compound The hydrogen bonding between the ether groups in the compound and the π-π electron interaction of the aromatic ring enhance the intermolecular force, and the resin composition increases the molecular weight and increases the melt viscosity, thereby reducing the fluidity after vacuum pressing. .

Specifically, the hardener is 1,3-bis(4-aminophenoxybenzene), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4'-diaminodiphenyl ether.

In the composition of the present invention, when the total number of epoxy equivalents of (a1) liquid epoxy resin and the number of epoxy equivalents of (a2) solid epoxy resin are 1, the active hydrogen equivalent number is used. The amount of the aromatic diamine compound (b) is preferably 0.95 to 1.50.

Here, the epoxy equivalent number of each epoxy resin is as follows: the number of equivalent epoxy groups of each epoxy resin = (the weight of each epoxy resin in the composition (solid component weight)) / (each epoxy resin) Each epoxy equivalent).

The active hydrogen equivalent number of the (b) aromatic diamine compound is as follows: (b) The number of active hydrogen equivalents of the aromatic diamine compound = (weight of the diamine compound in the composition) / (active hydrogen equivalent of the diamine compound).

When the number of epoxy equivalents (total value) of the epoxy resin is 1, the ratio of the number of active hydrogen equivalents of the aromatic diamine compound is the ratio of the two (unknown number), so the following formula is calculated: (aromatic diamine compound) The number of active hydrogen equivalents) / (the number of epoxy equivalents of the epoxy resin (total value)).

These may be used singly or in combination of two or more kinds, or in combination with other diamine hardeners.

((c) Solvent-soluble polyimine resin)

(c) Solvent-soluble polyimine resin A polyimine resin which is soluble in an organic solvent used in the production of the composition. (c) The solvent-soluble polyimine resin is preferably one having a high Tg, a low C.T.E, excellent film properties, and excellent adhesion properties. In terms of molecular weight, from the viewpoint of compatibility when making varnish Preferably, the weight average molecular weight (Mw) is preferably 50,000 or less, more preferably 35,000 or less. Further, the weight average molecular weight (Mw) is preferably 20,000 or more, more preferably 25,000 or more.

(c) The solvent-soluble polyimine resin preferably has a phenyl decane structure. Further, a fully fluorinated soluble polyimine resin obtained by reacting a diaminotrialkylnonane with a tetracarboxylic dianhydride or a derivative thereof is preferred. Here, examples of the diaminotrialkyl decane include diaminotrimethylnonane and diaminotriethyl decane; and derivatives of tetracarboxylic dianhydride include diphenyl. Ketone tetracarboxylic dianhydride.

A fully fluorinated soluble polyimine resin obtained by reacting diaminotrimethylphenylnonane with diphenyl ketone tetracarboxylic dianhydride is shown in (Formula 1). Further, a fully fluorinated soluble polyimine resin obtained by reacting diaminotrimethylphenylnonane with a tetracarboxylic dianhydride is also preferred.

The solvent-soluble polyimine resin is particularly excellent in adhesion strength to a resin having a phenyl decane structure, a copper, a ruthenium film, or a pure aluminum. Further, by incorporating the soluble polyimine resin into the resin composition, the Tg can be improved, which is more preferable in terms of ensuring the reliability of the FR-4 grade.

((d) phenoxy resin)

Since the phenoxy resin often has an epoxy group at the end, it is also hard and hard. The possibility of the reaction of the chemical agent, due to the molecular chain length, often exhibits a plasticizer behavior, and the bending property is good when the cured product is formed. Further, similarly to the epoxy resin, there is hydrogen bonding between the secondary hydroxyl group contained in the phenoxy resin and the ether group in the aromatic diamine compound, and the π-π electronic interaction of the aromatic ring. The effect of enhancing the intermolecular force and increasing the molecular weight of the resin composition and increasing the melt viscosity to reduce the fluidity after vacuum pressing.

The phenoxy resin must be uniformly melted at the time of hardening, and therefore it is preferable to have a Tg of a molding temperature or lower. The molding temperature is not necessarily limited. However, since it is an epoxy resin composition, it is usually a molding temperature of 180 ° C or lower. At this time, the Tg of the phenoxy resin is preferably 180 ° C or less.

A phenoxy resin can also be used, for example, YL6954BH30 (manufactured by Mitsubishi Chemical Corporation, Tg130°C), PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg146°C), and PHENOTOHTO YP-70 (Nippon Steel) Chemical company, Tg84 ° C).

(c) solvent-soluble polyimine resin and (d) benzene when the total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin, and (b) aromatic diamine compound is 100 parts by weight The total amount of the oxyresin may be selected in the range of 15 parts by weight or more. This is because when the amount is less than 15 parts by weight, the effect of the adhesive strength and flexibility of the composition is small, so it is set to 15 parts by weight or more. From this point of view, it is more preferably 25 parts by weight or more. Moreover, when it exceeds 100 parts by weight, the breaking strength of the film is lowered, so it is preferably 100 parts by weight or less, more preferably 50 parts by weight or less.

The ratio of the (c) solvent-soluble polyimine resin and (d) phenoxy resin is not particularly limited. However, (c) solvent-soluble polyimine resin and (d) When the total amount of the phenoxy resin is 100 parts by weight, from the viewpoint of hardening all the constituent components of the solvent-soluble polyimide resin in a (imaginary) compatible state, (d) phenoxy resin The amount is preferably 30 parts by weight or more, more preferably 50 parts by weight or more, and most preferably 60 parts by weight or more. Further, from the viewpoint of exerting the action of the (c) solvent-soluble polyimine resin, the amount of the (d) phenoxy resin is preferably 95 parts by weight or less, more preferably 90 parts by weight or less.

((e) filler)

The filler may or may not be added depending on the physical properties required for the composition. In terms of the filler, specifically, alumina (thermal conductivity: 32 W/mK), aluminum nitride (thermal conductivity: 150 W/mK), boron nitride (thermal conductivity: 33-55 W/mK), and tantalum nitride (thermal conductivity: 20 W) /mK) is suitable. However, for the purpose of exothermicity of the film thickness, although the thermal conductivity of the monomer is low, cerium oxide (thermal conductivity: 1.3 W/mK) or aluminum hydroxide (thermal conductivity: 7.1 W/mK) may be used.

The main purpose of the addition of the filler is to increase the thermal conductivity when used as an adhesive for a heat-releasing substrate, so that the selection of such fillers is quite suitable.

The total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin, (b) aromatic diamine compound, (c) solvent-soluble polyimine resin, and (d) phenoxy resin is 100. In the case of parts by volume, the amount of (e) filler may be determined in accordance with the desired physical properties such as thermal conductivity. In general, the amount of the filler is not particularly limited, but it is preferably 1% by volume or more from the viewpoint of exerting physical properties of the filler. Further, from the viewpoint of maintaining the physical properties of the composition, the amount of the filler is preferably 200% by volume or less. Moreover, the exothermic characteristics are related to the thermal conductivity and the thickness, so it is preferable to determine the amount of addition by considering two factors. In terms of specific thermal conductivity, organic The thermal material is required to be more than 2 W/mK, and therefore, the amount of the filler is preferably 100 parts by volume or more.

(additive)

Further, the composition of the present invention can be used in combination with a hardening accelerator. As the hardening accelerator, various general articles such as imidazoles can be used. Mainly from the point of view of the reaction rate and pot life.

For example: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole , 1-Benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole , 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2 '-Methylimidazolyl-(1')]-ethyl symmetry III 2,4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl symmetrical three 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl symmetrical three Iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole, 4,4'-methylenebis(2-ethyl-5-methylimidazole), TPP, etc. .

Further, the composition of the present invention may be added with a flame retardant for the purpose of imparting flame retardancy. For halogen-free flame retardants, there are condensed phosphates, phosphazenes, polyphosphates, and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxidation The derivative or the like is not particularly limited.

The solvent to be used in the thermosetting resin composition of the present invention is not particularly limited, and a high boiling point solvent such as NMP (N-methylpyrrolidone) or γ-butyrolactone is used together with cyclohexanone and MEK (methyl group B). Medium and low boiling solvents The combination is especially good. Further, DMF (dimethylformamide) or DMAC (dimethylacetamide) can be mentioned.

A resin film can be obtained by subjecting the thermosetting resin composition of the present invention to a B-stage. That is, the resin composition of the present invention described above can be made into a varnish by a general method such as dilution with a suitable mixed organic solvent, and coated to a demolded polymer by a die coater or the like as required. A polyethylene terephthalate film (PET film) was dried and a B-state thermosetting resin film was produced. The B stage is a state in which the resin composition is semi-hardened.

Further, by applying the thermosetting resin composition of the present invention to a metal foil, a metal foil with an adhesive can be produced. As the metal foil, a copper foil or an aluminum foil which is roughened by a surface may be mentioned, and copper foil is especially preferable.

The resin film and the RCC of the present invention can also be used as a printed wiring board having a non-through via such as a laser via hole as an HDI material having a build-up multilayer board having a rigid core or an FPC core.

Example

The invention is illustrated by the following examples.

(Example 1)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR-0163 ( PI Technology Research Institute, 20% by weight of resin solids, 367 parts by weight A mixture of phenoxy resin PHENOTOHTO ERF-001M30 (30% by weight of resin solid content, manufactured by Nippon Steel Chemical Co., Ltd.) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) was adjusted to 40% by weight of the resin solid content. Resin varnish.

(Example 2)

105 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 105 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 115 parts by weight of 2,2-bis[4-(4-aminophenoxy)phenyl]propane BAPP (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR -0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content), 367 parts by weight of PHENOTOHTO phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., 30% by weight of resin solid content), and 25 parts by weight A mixture of HCA (manufactured by Sanko Co., Ltd.) was adjusted to a resin varnish having a resin solid content of 40% by weight.

(Example 3)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR-0163 (PI a mixture of phenolic resin PHENOTOHTO YP-70 (manufactured by Nippon Steel Chemical Co., Ltd.) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.), 110 parts by weight of the resin company's resin solid content) , adjust the resin solid 40% by weight of resin varnish.

(Example 4)

110 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), 110 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (made by DIC Corporation, epoxy resin) Base equivalent: 188), 50 parts by weight of 2,2-bis[4-(4-aminophenoxy)phenyl]propane BAPP (manufactured by SEIKA), 55 parts by weight of trimethylene double (4-amino group) Benzene ester) CUA-4 (manufactured by IHARA Chemical Industry Co., Ltd.), 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content), and 367 parts by weight a mixture of phenoxy resin PHENOTOHTO ERF-001M30 (30% by weight of resin solid content, manufactured by Nippon Steel Chemical Co., Ltd.) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) was adjusted to 40% by weight of the resin solid content. Resin varnish.

(Example 5)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR-0163 (PI Phenocene resin PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., resin solid content: 30% by weight), and 200 parts by weight of aluminum hydroxide HIGILITE, manufactured by the Institute of Technology, 20% by weight of resin solids, 367 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 A mixture of H-42M (manufactured by Showa Denko Co., Ltd.) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) was adjusted to have a resin solid content of 40% by weight. Resin varnish.

(Comparative Example 1)

235 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), 90 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE- R (manufactured by SEIKA Co., Ltd.), 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content), and 367 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 A resin varnish having a resin solid content of 40% by weight was adjusted to a mixture of 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) and a mixture of 25 parts by weight of a resin solid content (manufactured by Nippon Steel Chemical Co., Ltd.).

(Comparative Example 2)

Manufactured from 235 parts by weight of a phenol novolak type epoxy resin EPICLON N-770 (manufactured by DIC, epoxy equivalent 188), 90 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA Co., Ltd.), 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content), and 367 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 ( A mixture of HCA (manufactured by Sanko Co., Ltd.) of 25 parts by weight of a resin solid content (manufactured by Nippon Steel Chemical Co., Ltd.) and a resin varnish having a resin solid content of 40% by weight was adjusted.

(Comparative Example 3)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of trimethylene bis(4-aminobenzoic acid) Ester) CUA-4 (manufactured by IHARA Chemical Industry Co., Ltd.), 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content), and 367 parts by weight of phenoxy A resin varnish having a resin solid content of 40% by weight was prepared by blending a mixture of a base resin, PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., 30% by weight of a resin solid component), and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.).

(Comparative Example 4)

100 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), 100 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 135 parts by weight of melamine-modified phenol novolac resin (manufactured by DIC Corporation), and 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content) 367 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., 30% by weight of resin solids) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) to adjust the solid content of the resin 40% by weight of resin varnish.

(Comparative Example 5)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA Co., Ltd.), 500 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 (Nippon Steel Chemical Co., Ltd. A mixture of 30% by weight of a resin solid content of the company and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) A resin varnish having a resin solid content of 40% by weight was prepared.

(Comparative Example 6)

115 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 115 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 95 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR-0163 (PI a mixture of 110 parts by weight of NIPOL 1072 (manufactured by Nippon Zeon Co., Ltd.) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.), and a resin solid content of 40% by weight. Resin varnish.

(Comparative Example 7)

85 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 85 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 65 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 325 parts by weight of soluble polyimine resin Q-VR-0163 (PI Pharmaceutical company, 20% by weight of resin solid content), 583 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., 30% by weight of resin solids), and 25 parts by weight of HCA (three light) A mixture of the resin solids was adjusted to a resin varnish of 40% by weight of the resin solid content.

(Comparative Example 8)

Modulated by 100 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC Corporation, epoxy equivalent 188), 100 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC, epoxy equivalent 188), 125 parts by weight of 1,3-double (4-Aminophenoxybenzene) TPE-R (manufactured by SEIKA Co., Ltd.), 200 parts by weight of soluble polyimine resin Q-VR-0163 (manufactured by PI Institute of Technology, 20% by weight of resin solid content) 367 parts by weight of phenoxy resin PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., 30% by weight of resin solids) and 25 parts by weight of HCA (manufactured by Sanko Co., Ltd.) to adjust the resin solid content 40% by weight of resin varnish.

(Comparative Example 9)

120 parts by weight of bisphenol A type epoxy resin EPICLON 850-S (manufactured by DIC, epoxy equivalent 188), and 120 parts by weight of phenol novolac type epoxy resin EPICLON N-770 (manufactured by DIC Corporation, epoxy resin) Base equivalent: 188), 85 parts by weight of 1,3-bis(4-aminophenoxybenzene) TPE-R (manufactured by SEIKA), 200 parts by weight of soluble polyimide resin Q-VR-0163 (PI Phenocene resin PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., resin solid content: 30% by weight) and 25 parts by weight of HCA (three light), 367 parts by weight of phenolic resin, PHENOTOHTO ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd.) A mixture of the resin solids was adjusted to a resin varnish of 40% by weight of the resin solid content.

Regarding the filler-containing material and the rubber-containing material in the resin varnish of each of the above examples, the three-roller was uniformly dispersed. These were coated on a release-treated 25 μm polyethylene terephthalate film (PET film) by a die coater, and dried at a temperature of 120 ° C to produce a B state having a thickness of 51 μm. hot Curable resin film (A). The volatiles were adjusted to 5 wt%. Further, as a protective film, a polyethylene film (PE film) was laminated.

It was cut into 300 mm × 300 mm, overlapped with 18 μm of the surface-free copper foil, fed into a vacuum press, and heated at 180 ° C × 120 min and 1 MPa, and pressed (vacuum 5 torr) to form (formed product ( 1)).

In the same manner, it was superposed on the copper foil with the pins, and fed to a vacuum press, and heated at 180 ° C × 120 minutes and 1 MPa, and pressed (vacuum 5 torr) to form (molded product (2)).

On the other hand, a 25 μm thick plyimide copper clad laminate (copper foil 18 μm) was formed into a circuit and perforated, and after the conductor was subjected to black copper oxide treatment, the film (A) was peeled off from the protective film and Lay on both sides. Further, the copper foil was superposed on both sides, fed into a vacuum press, and heated at 180 ° C × 90 min and 1 MPa, and pressed (vacuum degree 1 torr). After cooling and taking out, a concealed interlayer of a predetermined aperture is formed by a CO2 laser using a conformal mask method.

The surface was roughened with a permanganate degumming solution, and the residual resin at the bottom of the well was also dissolved and removed. To this, 0.5 μm of electroless copper plating and 20 μm of electroplated copper were added, and baking was performed after 180° C.×30 minutes. Here, circuit formation was carried out, and a four-layer build-up multilayer printed wiring board (PWB (I)) having one layer on the build-up layer side was produced.

PWB (II) is a test pattern substrate of JPCA-HD01 manufactured according to the manufacturing method of PWB (I).

Insulation reliability: high temperature and high humidity offset test 85 ° C × 85% RH, DC = 30V, 10E6Ω or more

The parameters of the above examples are shown in Tables 1 and 2. Also, each case The results of the characteristic evaluation are shown in Tables 3 and 4.

Resin flow amount: The copper foil of the molded product (1) was etched, and the maximum value of the resin layer which was increased from the original size was measured.

Laser processing property: Determination of the pore diameter, top diameter/bottom diameter, and residual resin content of the interlayer resin after CO2 laser processing.

Desmear etching property: Residual resin content and surface roughness and rough surface uniformity after permanganic acid degumming.

(Example 6)

The test was carried out in the same manner as in Example 1. However, when the total amount of the (a1) liquid epoxy resin, the (a2) solid epoxy resin, and the (b) diamine compound is 100 parts by weight, (c) the solvent-soluble polyimine resin and (d) benzene The total amount of the oxyresin is 15 parts by weight. That is, in Example 1, (c) the amount of the solvent-soluble polyimine resin was 14 parts by weight and the amount of (d) the phenoxy resin was 35 parts by weight. As a result, in the same manner as in Example 1, the resin flow amount, the laser processability, and the desmear etching property were excellent. The results are shown in Tables 5 and 6.

(Example 7)

The test was carried out in the same manner as in Example 1. However, when the total amount of the (a1) liquid epoxy resin, the (a2) solid epoxy resin, and the (b) diamine compound is 100 parts by weight, (c) the solvent-soluble polyimine resin and (d) benzene The total amount of the oxyresin is 100 parts by weight. That is, in Example 1, (c) the amount of the solvent-soluble polyimide resin was 86 parts by weight and the amount of the (d) phenoxy resin was 238 parts by weight. As a result, in the same manner as in the first embodiment, the resin flow amount, the laser processability, and the desmear etching property were excellent.

(Example 8)

The test was carried out in the same manner as in Example 1. However, when the total amount of the solvent-soluble polyimine resin (c) and the (d) phenoxy resin is 100 parts by weight, the amount of the (d) phenoxy resin is 30 parts by weight. That is, in Example 1, (c) the amount of the solvent-soluble polyimide resin was 105 parts by weight and the amount of (d) the phenoxy resin was 45 parts by weight. As a result, in the same manner as in the first embodiment, the resin flow amount, the laser processability, and the desmear etching property were excellent.

(Example 9)

The test was carried out in the same manner as in Example 1. However, when the total amount of the solvent-soluble polyimine resin (c) and the (d) phenoxy resin is 100 parts by weight, the amount of the (d) phenoxy resin is 95 parts by weight. That is, in Example 1, (c) the amount of the solvent-soluble polyimide resin was 8 parts by weight and the amount of (d) the phenoxy resin was 142 parts by weight. As a result, in the same manner as in the first embodiment, the resin flow amount, the laser processability, and the desmear etching property were excellent.

(Embodiment 10)

The test was carried out in the same manner as in Example 1. However, when the total number of epoxy equivalents of (a1) liquid epoxy resin and the number of epoxy equivalents of (a2) solid epoxy resin are 1, the (b) aromatic is used in terms of the number of active hydrogen equivalents. The amount of the group diamine compound was determined to be 0.95. As a result, in the same manner as in the first embodiment, the resin flow amount, the laser processability, and the desmear etching property were excellent.

(Example 11)

The test was carried out in the same manner as in Example 1. However, when the total number of epoxy equivalents of (a1) liquid epoxy resin and the number of epoxy equivalents of (a2) solid epoxy resin are 1, the (b) aromatic is used in terms of the number of active hydrogen equivalents. The amount of the family diamine compound was set to 1.50. As a result, in the same manner as in the first embodiment, the resin flow amount, the laser processability, and the desmear etching property were excellent.

As described above, according to the present invention, it can be used as a high-density flexible build-up wiring board, high-density thin-layer stacking printing, which has low resin flow, bendability, high heat resistance, high adhesion strength, and high reliability in vacuum pressing. The wiring board and the heat-dissipating substrate are used, and the printed wiring board produced by the same can be used in a portable machine, an LED substrate, or the like.

Claims (7)

A thermosetting resin composition comprising (a1) a liquid epoxy resin, (a2) a solid epoxy resin, (b) an aromatic diamine compound having an ether group, and (c) a weight average molecular weight Mw a solvent-soluble polyimine resin of 50,000 or less and (d) a phenoxy resin; and a total amount of the liquid epoxy resin (a1), the solid epoxy resin (a2), and the (b) diamine compound When the amount is 100 parts by weight, the total amount of the solvent-soluble polyimine resin (c) and the (d) phenoxy resin is 15 parts by weight or more and 100 parts by weight or less. The composition of claim 1, wherein the (c) solvent-soluble polyimine resin is a fully fluorinated soluble polyimine resin having a phenyl decane moiety. The composition of claim 1 or 2, further comprising (e) a filler, wherein the (e) filler is selected from the group consisting of alumina, aluminum nitride, boron nitride, cerium oxide, and aluminum hydroxide. One or more materials are used. A B-staged resin film produced by the composition according to any one of claims 1 to 3. A metal foil provided with a B-staged resin film as claimed in claim 4. A copper clad laminate provided with a B-staged resin film as claimed in claim 4. A multilayer build-up substrate comprising an interlayer insulating material, the interlayer insulating material being the thermosetting resin composition according to any one of claims 1 to 3. Composition.