JP2013035881A - Thermosetting resin composition, b-staged resin film, metal foil, copper-clad sheet, and multilayer build-up substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy-based thermosetting resin which exhibits a certain level of flexibility, can be formed into a thin insulating layer, and has reliability and workability comparable to those of halogen-free FR-4.SOLUTION: A thermosetting resin composition comprises (a1) a liquid epoxy resin, (a2) a solid epoxy resin having a softening point of ≤125°C, (b) an aromatic diamine compound having a benzoate group, and a polymethylene group in a main chain, (c) a solvent-soluble polyimide resin having a Tg of ≥200°C and a weight average molecular weight Mw of ≤50,000, and (d) a phenoxy resin having a Tg of ≥130°C, wherein when the total amount of (a1) the liquid epoxy resin, (a2) the solid epoxy resin and (b) the aromatic diamine compound is 100 pts.wt., the total amount of (c) the solvent-soluble polyimide and (d) the phenoxy resin is 15-150 pts.wt.

Description

  The present invention is used for adhesives, prepregs, paints, etc., and can also be used to produce base materials for flexible substrates, build-up substrates mainly made of flexible base materials, and metal base substrates based on aluminum, etc. Resin composition and B-staged resin film produced using this, applied to one side of metal foil and B-staged, such as copper foil with adhesive and copper-clad plate, etc., can be bent High heat resistance, high adhesive strength, high reliability for high-density flexible build-up printed wiring boards, batch-formed boards, heat dissipation boards, etc. The printed wiring boards obtained are portable devices, LED boards, and module boards. Used for etc.

  In recent years, printed wiring boards and module boards used in such devices are required to have high functionality in addition to thinning, as seen in higher functionality of portable devices and thinning such as LCD televisions. ing. Conventionally, flexible printed wiring boards have been used for some of these printed wiring boards.

  Conventionally, flexible substrate materials that can be bent and have no base material, other than polyimide-based materials, are generally epoxy resin-based adhesives that are modified with carboxyl group-modified rubber, thermoplastic resin, phenoxy resin, or the like. Used for bonding sheets. These were also used for copper-clad plates and coverlays. However, these materials generally have low Tg, and their reliability is not as good as that of rigid materials.

  In addition, these adhesives are often excellent in adhesive strength with different materials, and thus have been used as adhesives for metal base substrates. However, this metal does not contain pure aluminum, and there is a problem that an alumite treatment must be performed for the bonding. Since pure aluminum is excellent in flexibility, it is suitable for a metal base substrate that can be bent.

  Therefore, to increase the density and thinness of flexible printed wiring boards, the double-sided FPC and double-sided FPC, single-sided FPC are different from the prepreg, resin film, and RCC that make rigid materials multilayer and build-up substrates. There are many examples that are multilayered by the combination of FPC and single-sided FPC, or single-sided FPC and double-sided FPC, and examples that are supported by the structure and manufacturing method, and there are things that improve the characteristics with materials, but processing Improvements including reliability and reliability have not been achieved. For example, specific examples can be found in the following Patent Documents 1 to 7. One reason for this is that there is no material equivalent to build-up materials such as resin films and RCC on rigid substrates.

  In addition, in the patent document 8, the present applicant disclosed a thermosetting resin composition containing a liquid epoxy resin, a solid epoxy resin, a triazine-modified phenol novolac resin curing agent and a solvent-soluble polyimide resin mainly as a rigid material application. In addition, the present applicant mainly disclosed in Patent Document 9 as a rigid material application, a liquid epoxy resin, a solid epoxy resin, a triazine-modified phenol novolac resin, a benzoxazine resin, and a thermosetting containing a phenoxy resin having a Tg of 120 ° C. or higher. A resin composition has been disclosed.

WO2007 / 46459 Patent No. 4237726 JP2005-126543 JP2005-347414 JP 2006-299209 JP2006-179679 JP2011-40607 JP2007-224242A JP2008-037957

  In this way, materials other than all-polyimide copper-clad plates have characteristics, workability, and reliability sufficient to meet these requirements except for bending characteristics, thickness reduction, and weight reduction. There wasn't.

  Further, even in all polyimide flexible wiring boards, there is currently no suitable build-up material suitable for them.

  Therefore, there are currently no materials that satisfy these requirements. Epoxy-based flexible materials that have the flexibility and thin film insulating layers that are the characteristics of flexible substrate materials, as well as the reliability and processing characteristics comparable to halogen-free FR-4. There was no substrate material. The processing characteristics referred to here are, for example, laser via processability, desmear etching property, etc., which are essential for high-density mounting substrates and build-up substrates.

  That is, there is a need for a flexible substrate material that can be bent and does not have a base material that is comparable to FR-4 and halogen-free FR-4 prepregs in properties other than variations in flexibility and thickness as a single material.

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

  Moreover, the subject of this invention is providing the flexible substrate material using such a thermosetting resin, and providing the adhesive material for heat sinks which is excellent in adhesive strength with metals, such as a pure aluminum. Furthermore, it is providing the high-density flexible buildup printed wiring board using these, a module substrate, and a heat sink.

  The thermosetting resin composition according to the present invention includes (a1) a liquid epoxy resin, (a2) a solid epoxy resin having a softening point of 125 ° C. or lower, (b) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain. (C) a solvent-soluble polyimide resin having a Tg of 200 ° C. or more and a weight average molecular weight Mw of 50,000 or less, and (d) a phenoxy resin having a Tg of 130 ° C. or more, (a1) the liquid epoxy resin, When the total amount of a2) the solid epoxy resin and (b) the aromatic diamine compound is 100 parts by weight, the total amount of (c) the solvent-soluble polyimide resin and (d) the phenoxy resin is 15 parts by weight or more. 150 parts by weight or less.

  The present invention also relates to a B-staged resin film prepared from the thermosetting resin composition.

  The present invention also relates to a metal foil and a copper-clad plate provided with a B-staged resin film.

  Furthermore, this invention relates to the multilayer buildup board | substrate manufactured using the said thermosetting resin composition as an interlayer insulation material.

  Conventionally, improvement of the flexibility of an epoxy resin has been realized by using a phenoxy resin, a thermoplastic resin, a carboxyl-modified rubber or the like as a modifying material. However, with these methods alone, it was very difficult to achieve the same reliability and workability as halogen-free FR-4.

  In the present invention, in order to improve the flexibility of the epoxy resin without reducing the reliability and workability, the heat-resistant curing agent has a certain degree of flexibility, We have discovered that this is possible by using a combination of phenoxy resin and soluble polyimide resin.

  Also, in order to develop the characteristics of these resins as a resin composition, it was also discovered that the compatible state of the resin at the time of curing is important, and the melting of each resin component (including the apparent molten state) We have also found that this can be achieved by selecting the continuation to occur continuously.

  Furthermore, the composition of the present invention is based on improving the adhesion performance to imide film, copper, metal base substrate material (especially pure aluminum), etc., but this function is cured by aromatic diamine having benzoate group. It has also been discovered that it can be realized by a synergistic effect of the combined use of an agent and a soluble polyimide, and the present invention has been achieved.

((A1) Liquid epoxy resin and (a2) Solid epoxy resin with a softening point of 125 ° C or lower)
Any of the epoxy resins having two or more glycidyl groups can be appropriately selected depending on the purpose, but preferably, a liquid epoxy resin is a bis A type epoxy resin, a bis F type epoxy resin, or a novolac phenol type epoxy. Examples thereof include a resin and a naphthalene type epoxy resin. Examples of the solid epoxy resin include novolak phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin and the like. These can be used alone or in combination of two or more.

  The reason why the softening point of the solid epoxy resin is set to 125 ° C. or lower is that the Tg of the phenoxy resin used as the modifying material is limited to Tg 130 ° C. or higher. The definition of softening point is difficult to apply to the polymer phenoxy resin, but it has been experimentally shown that Tg is an alternative property. The purpose is to make the cured resin layer uniform because the epoxy resin is melted before the phenoxy resin layer is melted when cured as a composition.

  In addition, the liquid epoxy resin and the solid epoxy resin are used in combination so that the cured epoxy resin may be used in order to bring the cured properties close to those of the FR-4 resin. Difficult to melt. Therefore, the melting is continuously caused by using an epoxy resin that is liquid even at room temperature, thereby enabling it.

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

  The softening point of the solid epoxy resin is 125 ° C. or lower, but from the viewpoint of the present invention, 100 ° C. or lower is preferable. However, the softening point is preferably 50 ° C. or higher from the viewpoint of exhibiting the above-described effects of the solid epoxy resin when mixed with the liquid epoxy resin.

  The ratio between the liquid epoxy resin and the solid epoxy resin is preferably determined from the viewpoints of desired characteristics and melting control. Therefore, this optimal combination ratio is not necessarily limited. However, when the total amount of both is 100 parts by weight, the ratio of the liquid epoxy resin is preferably 20 to 50 parts by weight.

((b) Aromatic diamine compound having a benzoate group and a polymethylene group in the main chain)
Aromatic diamine-based curing agents with ester bonds are excellent in adhesive strength with metal bases such as polyimide film and aluminum, and by introducing a polymethylene structure into the skeleton, heat resistance as well as in the epoxy resin skeleton It can have a certain degree of flexibility.

  Here, the number of methylene groups contained in the polymethylene group provided in the main chain is preferably 3 or more, and more preferably 16 or less.

  Specifically, this curing agent is trimethylene-bis (4-aminobenzoate) [melting point: 122 ° C.] or poly (tetra / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate)) [liquid] And polytetramethylene oxide-di-p-aminobenzoate) [melting point: 15 to 60 ° C.].

 For the same reason as (a2) the solid epoxy resin, the melting point of this curing agent is preferably 125 ° C. or lower.

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

Here, the number of epoxy equivalents of each epoxy resin is as follows.
Each epoxy equivalent number of each epoxy resin =
(Weight of each epoxy resin in the composition (solid content weight)) / (Each epoxy equivalent of each epoxy resin)
(b)
The number of active hydrogen equivalents of the aromatic diamine compound is as follows.
(b)
Number of active hydrogen equivalents of aromatic diamine compound =
(Weight of aromatic diamine compound in composition) /
(Active hydrogen equivalent of aromatic diamine compound)

The number of active hydrogen equivalents of the aromatic diamine compound when the number of epoxy equivalents (total value) of the epoxy resin is 1, is the ratio of both (nameless number), and is calculated by the following formula.
(Number of active hydrogen equivalents of aromatic diamine compound) /
(Epoxy equivalent number of epoxy resin (total value))

((C) Solvent-soluble polyimide resin having a Tg of 200 ° C. or higher and a weight average molecular weight Mw of 50,000 or less)
(c) A solvent-soluble polyimide resin is a polyimide resin that is soluble in an organic solvent used in the production of the composition. (c) A solvent-soluble polyimide resin having high Tg, low CTE, excellent film properties, and excellent adhesion performance is preferable. The molecular weight is preferably 50000 or less in weight average molecular weight (Mw), more preferably 35000 or less. The weight average molecular weight (Mw) is preferably 20000 or more, and more preferably 25000 or more.

  (c) The solvent-soluble polyimide resin preferably has a phenylindane structure. Furthermore, a completely imidized soluble polyimide resin obtained by reacting diaminotrialkylindane with tetracarboxylic dianhydride or a derivative thereof is preferable. Here, examples of the diaminotrialkylindane include diaminotrimethylindane and diaminotriethylindane, and examples of the tetracarboxylic dianhydride derivative include benzophenonetetracarboxylic dianhydride.

  A completely imidized soluble polyimide resin obtained by reacting diaminotrimethylphenylindane and benzophenonetetracarboxylic dianhydride is shown in (Formula 1). A completely imidized soluble polyimide resin obtained by reacting diaminotrimethylphenylindane and tetracarboxylic dianhydride is also preferable.

  A solvent-soluble polyimide resin, particularly a resin having a phenylindane structure, is excellent in adhesive strength with copper, imide film, pure aluminum and the like. In addition, by incorporating this soluble polyimide resin into the resin composition, Tg can be improved, which is more preferable for ensuring reliability at the FR-4 level.

 The composition of the present invention is basically based on improving the adhesion performance to imide film, copper, metal base substrate material (especially pure aluminum), but this action is aromatic with benzoate group. It is established by the synergistic effect of including a diamine curing agent and soluble polyimide as constituent components.

((D) Phenoxy resin with Tg of 130 ° C or higher)
Here, the reason for limiting to the phenoxy resin having a Tg of 130 ° C. or more is to set the connection reliability to the FR-4 level. That is, the connection reliability of FR-4 boards is often judged by a thermal cycle test between 125 ° C. and −65 ° C. The phenoxy resin often leaves an epoxy group at the terminal and may react with the curing agent, but often exhibits a plasticizer behavior due to the long molecular chain. Therefore, the T g becomes the boundary of viscoelastic behavior. Therefore, Tg of 130 ° C. or higher is a necessary condition for improving connection reliability. That is, the CTE, which is one element of connection reliability, changes greatly before and after Tg, so that the influence is reduced.

  Tg (glass transition temperature) of phenoxy resin is measured by DSC method. The type of phenoxy resin is not limited, but as the resin skeleton, BPA / BPS type, BP / BPS type, BP type, BPS type and the like having a heat resistant skeleton are preferable. Further, the weight average molecular weight Mw of the phenoxy resin is preferably 10,000 or more.

  Since the phenoxy resin needs to be uniformly melted at the time of curing, the Tg is preferably equal to or lower than the molding temperature. The molding temperature is not necessarily limited, but is usually a molding temperature of 180 ° C. or less because of the epoxy resin composition. In this case, the T g of the phenoxy resin is desirably 180 ° C. or lower.

  A commercially available phenoxy resin may be used. ° C) and the like.

  In addition, phenoxy resin with a Tg of 130 ° C or higher is used in combination with the solvent-soluble polyimide resin, but because the softening point of the solvent-soluble polyimide resin is high, softening does not occur in the resin melting process at the time of curing (during molding). Because it was found that the compatibility with other components was difficult to be uniform, it was also found that it was effective at the time of molding and was effective in curing all components including the solvent-soluble polyimide resin in a pseudo-compatible state. . This makes the cured physical properties after curing uniform.

  This uniform cured product is also effective in improving the processing characteristics. In other words, the unevenness of laser processing and the roughness variation of the roughened surface of the desmear surface in the desmear etching process, which are found in the conventional resin composition imparted with flexibility, can be greatly improved, and as a result, the reliability is improved. .

  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 (c) solvent-soluble polyimide resin and (d) phenoxy resin is It is selected in the range of 15 parts by weight or more and 150 parts by weight or less. If the amount is less than 15 parts by weight, the effect of the adhesive strength and flexibility of the composition is small. From this viewpoint, the amount is more preferably 25 parts by weight or more. Further, if this exceeds 150 parts by weight, the breaking strength as a film is lowered, so that it is 150 parts by weight or less, preferably 100 parts by weight or less, more preferably 50 parts by weight or less, 30 Most preferably, it is at most parts by weight.

The ratio of (c) solvent-soluble polyimide resin and (d) phenoxy resin is not particularly limited. However, when the total amount of (c) the solvent-soluble polyimide resin and (d) the phenoxy resin is 100 parts by weight, the amount of (d) the phenoxy resin includes all the components including the solvent-soluble polyimide resin described above ( From the viewpoint of curing in a (pseudo) compatible state, 60 parts by weight or more is preferable. Further, from the viewpoint of exerting the action of (c) the solvent-soluble polyimide resin, the amount of (d) phenoxy resin is preferably 95 parts by weight or less.

((E) Filler)
The filler may or may not be added depending on the physical properties required for the composition. Specific fillers include alumina (thermal conductivity 32W / mK), aluminum nitride (thermal conductivity 150W / mK), boron nitride (thermal conductivity 33-55W / mK), silicon nitride (thermal conductivity 20W). / mK) is preferred. However, for heat dissipation with thin film thickness, the thermal conductivity of the single substance is low, but silica (thermal conductivity 1.3W / mK), aluminum hydroxide (thermal conductivity 7.1W / mK), etc. Can also be used.
Since this filler addition is mainly for the purpose of improving the thermal conductivity when used as an adhesive for a heat dissipation substrate, the selection of these fillers is suitable.

  When the total amount of (a1) liquid epoxy resin, (a2) solid epoxy resin, (b) aromatic diamine compound, (c) solvent-soluble polyimide resin, and (d) phenoxy resin is 100 parts by volume, (e) The amount of filler is determined by the desired physical properties, for example, thermal conductivity. In general, there is no particular lower limit on the amount of filler, but from the viewpoint of exhibiting the physical properties of the filler, it is preferably 5 parts by volume or more, and more preferably 50 parts by volume or more. From the viewpoint of maintaining the physical properties of the composition, the amount of filler is preferably 200 parts by volume or less. In addition, since the heat dissipation characteristics are related to the thermal conductivity and the thickness, it is preferable to determine the addition amount in consideration of both factors. As a specific thermal conductivity, 2 W / mK or more is often required as an organic heat dissipation material. From this viewpoint, the amount of filler is preferably 100 parts by volume or more.

(Additive)
Moreover, a hardening accelerator can be used together with the composition of this invention as needed. As the curing accelerator, common ones such as various imidazoles can be used. Select mainly from the viewpoint of reaction speed 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-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid addition 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 4,4'-methylenebis (2- Ethyl-5-methylimidazole) and TPP.

  Furthermore, a flame retardant can be added to the component of the present invention for imparting flame retardancy. Halogen-free flame retardants include condensed phosphate esters, phosphazenes, polyphosphates, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivatives, aluminum hydroxide, etc. There is no particular limitation.

  Although the solvent which can be used for the thermosetting resin composition of the present invention is not particularly limited, a high boiling point solvent such as NMP (N-methylpyrrolidone) or γ-butyrolactone and a low boiling point solvent such as cyclohexanone or MEK (methyl ethyl ketone). Is particularly preferred. Furthermore, DMF (dimethylformamide) and DMAC (dimethylacetamide) can be exemplified.

 A resin film can be obtained by converting the thermosetting resin composition of the present invention into a B-stage. That is, the resin composition of the present invention described above is diluted with a suitable mixed organic solvent to form a varnish, and a die coater is formed on a polyethylene terephthalate film (PET film) which has been subjected to a release treatment if necessary. A thermosetting resin film in a B state can be produced by the usual method of applying and drying. The B stage refers to a state in which the resin composition is semi-cured.

 Moreover, the metal foil with an adhesive agent can be manufactured by applying the thermosetting resin composition of the present invention to a metal foil. Examples of the metal foil include a roughened copper foil and an aluminum foil, and a copper foil is particularly preferable.

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

Hereinafter, the present invention will be described by way of examples.
(Example 1)
98 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 126 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) manufactured by Ihara Chemical Co., Ltd., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q-VR- X0163 (manufactured by PI Engineering Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg 146 ° C, resin solid content 30% by weight)) Then, a mixture composed of 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Example 2)
111 parts by weight of bisphenol A type epoxy resin Epicron 850-S (Dainippon Ink and Chemicals, epoxy equivalent 188), 167 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 92 parts by weight of CUA-4 (trimethylenebis (4-aminobenzoate, melting point 122 ° C)
Ihara Chemical Co., Ltd.), 100 parts by weight of soluble polyimide resin Q-VR-X0163 (PI Technology Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (new day) A mixture made of Sakai Chemical Co., Ltd., Tg 146 ° C., resin solid content 30 wt%)), 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40 wt%.

(Example 3)
98 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 126 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) manufactured by Ihara Chemical Co., Ltd., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q-VR- X0163 (PII Research Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin YL6954BH30 (JER, Tg 130 ° C, resin solids 30% by weight)), 18 parts by weight A mixture comprising HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Example 4)
98 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 126 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) manufactured by Ihara Chemical Co., Ltd., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q-VR- X0163 (manufactured by PI Engineering Laboratory, Tg 246 ° C., resin solid content 20% by weight), 303 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER, Tg 150 ° C., resin solid content 30% by weight)), 18 parts by weight A mixture comprising HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Example 5)
98 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 126 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) manufactured by Ihara Chemical Co., Ltd., melting point 60 ° C), 100 parts by weight of soluble polyimide resin Q-VR- X0163 (manufactured by PI Engineering Laboratory, Tg 246 ° C., resin solid content 20% by weight), 303 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER, Tg 150 ° C., resin solid content 30% by weight)), 18 parts by weight A mixture of HCA and 1600 parts by weight of surface-treated spherical alumina was prepared to prepare a resin varnish having a resin solid content of 75% by weight.

(Comparative Example 1)
103 parts by weight of bisphenol A type epoxy resin Epicron 850-S (Dainippon Ink and Chemicals, epoxy equivalent 188), 155 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C.), 112 parts by weight of BAPP (2,2-bis [4- (4-aminophenoxy) phenyl] propane manufactured by Wakayama Seika Kogyo Co., Ltd., melting point 128 ° C.), 100 parts by weight of soluble polyimide Resin Q-VR-X0163 (PII Research Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (Nippon Steel Chemical Co., Tg 146 ° C, resin solid content 30 wt%)) and 18 parts by weight of HCA were prepared to prepare a resin varnish having a resin solid content of 40 wt%.

(Comparative Example 2)
97 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 213 parts by weight of melamine-modified phenol novolac resin LA-7054 (manufactured by Dainippon Ink and Chemicals, hydroxyl value 125, resin solid content 60% by weight), 100 parts by weight of soluble polyimide resin Q -VR-X0163 (manufactured by PI Engineering Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight of phenoxy resin ERF-001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg 146 ° C, resin solid content 30% by weight) %)), A mixture of 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Comparative Example 3)
237 parts by weight of cresol novolac type epoxy resin N-695 (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 215, softening point 98 ° C.), 134 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) ) 100 parts by weight soluble polyimide resin Q-VR-X0163 (manufactured by PI Engineering Laboratory, Tg 246 ° C, resin solid content 20% by weight), 303 parts by weight phenoxy resin ERF -001M30 (manufactured by Nippon Steel Chemical Co., Ltd., Tg 146 ° C., resin solid content 30% by weight)) and 18 parts by weight of HCA were prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Comparative Example 4)
98 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 147 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C), 126 parts by weight of elastomer 250P (polytetramethylene oxide-di-p-aminobenzoate) Ihara Chemical Co., melting point 60 ° C), 370 parts by weight of phenoxy resin YX8100BH30 (manufactured by JER) , Tg 150 ° C., resin solid content 30 wt%)), and a mixture of 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40 wt%.

(Comparative Example 5)
97 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C.), 213 parts by weight of melamine-modified phenol novolac resin LA-7054 (Dainippon Ink and Chemicals, hydroxyl value 125, resin solid content 60% by weight), 111 parts by weight of carboxy-containing acrylonitrile butadiene A mixture comprising rubber, Nipol 1072 (manufactured by Nippon Zeon Co., Ltd.) and 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Comparative Example 6)
97 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C.), 213 parts by weight of melamine-modified phenol novolak resin LA-7054 (Dainippon Ink & Chemicals, hydroxyl value 125, resin solid content 60% by weight), 111 parts by weight of phenoxy resin YP- A mixture consisting of 55 (Tg 84 ° C., manufactured by Tohto Kasei Co., Ltd.) and 18 parts by weight of HCA was prepared to prepare a resin varnish having a resin solid content of 40% by weight.

(Comparative Example 7)
97 parts by weight of bisphenol A type epoxy resin Epicron 850-S (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 188), 145 parts by weight of dicyclopentadiene type epoxy resin HP-7200H (manufactured by Dainippon Ink and Chemicals, epoxy Equivalent 283, softening point 83 ° C.), 213 parts by weight of melamine-modified phenol novolac resin LA-7054 (Dainippon Ink Chemical Co., Ltd., hydroxyl value 125, resin solid content 60% by weight, 100 parts by weight of soluble polyimide resin Q- VR-X0163 (PI Engineering Laboratory, Tg 246 ° C, resin solid content 20 wt%), 303 parts by weight of phenoxy resin YX8100BH30 (JER, Tg 150 ° C, resin solid content 30 wt%)), 18 wt A mixture of 1 part by weight of HCA and 1600 parts by weight of surface-treated spherical alumina was prepared to prepare a resin varnish having a resin solid content of 75% by weight.

Of the resin varnishes in each of the above examples, the filler-containing product and the rubber-containing product were well dispersed with three rolls. These were coated on a 25 μm polyethylene terephthalate film (PET film) subjected to mold release treatment with a die coater and dried at a temperature of 120 ° C. to produce a thermosetting resin film (A) in a B state having a thickness of 51 μm. Volatiles were adjusted to 0.5 wt%. Further, a polyethylene film (PE film) was laminated as a protective film.
This was overlaid with a 18 μm surface-treated copper foil, placed in a vacuum press, and molded at 180 ° C. for 120 minutes and heated and pressurized (vacuum degree 5 torr) at 1 MPa. (Molded product (1))

  Similarly, it was overlapped with a copper foil with a treated foot, charged into a vacuum press and molded at 180 ° C. for 120 minutes at 1 MPa with heating and pressurization (vacuum degree 5 torr). (Molded product (2))

  On the other hand, a circuit and through-holes are formed in a 25 μm thick all-polyimide copper-clad plate (copper foil 18 μm), and after the black copper oxide treatment on the conductor, the above film (A) is peeled off on this surface and the laminate is double-sided. To do. Further, copper foil is superimposed on both sides, and this is charged into a vacuum press and molded at 180 ° C. for 90 minutes at 1 MPa with heating and pressurization (vacuum degree 1 torr). After cooling and taking out, blind vias having a predetermined hole diameter were formed with a CO2 laser by a conformal mask method.

 Surface roughening was performed with a permanganate desmear solution, and the residual resin at the bottom of the hole was dissolved and removed. Electroless copper plating 0.5 μm and electrolytic copper plating 20 μm were applied to this, and after baking was performed at 180 ° C. for 30 minutes. A circuit was formed on this, and a four-layer build-up multilayer printed wiring board (PWB (I)) having one build-up layer on one side was produced.

  Tables 1 and 2 show the parameters of the above examples. Tables 3 and 4 show the characteristic evaluation results of each example.

Note that PWB (II) in Table 2 is a test pattern substrate of JPCA-HD01 manufactured in accordance with the manufacturing method of PWB (I).
PWB (II)
: JPCA-HD01 test pattern board manufactured according to the PWB (I) manufacturing method.
* 1) AL1060 is used instead of the copper foil of the molded product (2)
* 2) A polyimide film is used instead of the copper foil in the molded product (2).

Reliability: According to JPCA-BU01.
(a) Thermal shock test 125 ℃ × 30min ← → −65 ℃ × 30min
(1 cycle)
(b) High temperature and high humidity bias test 85 ℃ × 85% RH, DC = 30V
Laser workability: Judged from the hole diameter, top diameter / bottom diameter, and via bottom residual resin amount after CO2 laser processing.
Desmear etching property: Judged from the amount of residual resin after permanganate desmear, surface roughness and rough surface uniformity.

  As described above, according to the present invention, bending, high heat resistance, high adhesive strength, and high reliability for high-density flexible build-up printed wiring boards, high-density thin build-up printed wiring boards, and heat dissipation boards The obtained printed wiring board can be used for portable devices and LED substrates.

  For reference, the reliability in the table for FR-4 base material and FR-4 resin is “(a)> 500” and “(b)> 1,000”, which is equivalent to the embodiment of the present invention. I understand that there is.

Claims (7)

  (a1) liquid epoxy resin, (a2) solid epoxy resin having a softening point of 125 ° C. or lower, (b) an aromatic diamine compound having a benzoate group and a polymethylene group in the main chain, (c) Tg is 200 ° C. or higher, A solvent-soluble polyimide resin having a weight average molecular weight Mw of 50,000 or less, and (d) a phenoxy resin having a Tg of 130 ° C. or higher, (a1) the liquid epoxy resin, (a2) the solid epoxy resin, and (b) the fragrance. When the total amount of the group diamine compound is 100 parts by weight, the total amount of (c) the solvent-soluble polyimide resin and (d) the phenoxy resin is 15 parts by weight or more and 150 parts by weight or less. , Thermosetting resin composition.  2. The composition according to claim 1, wherein the solvent-soluble polyimide resin is a completely imidized soluble polyimide resin having a phenylindane structure.  (E) further containing a filler, wherein the (e) filler is made of one or more materials selected from the group consisting of alumina, aluminum nitride, boron nitride, silica and aluminum hydroxide, The composition according to claim 1 or 2.   A B-staged resin film prepared from the composition according to any one of claims 1 to 3.   A metal foil having the B-staged resin film layer according to claim 4.   A copper-clad plate obtained by molding and curing the B-staged resin film and copper foil according to claim 4.   The multilayer buildup board | substrate containing the interlayer insulation material which consists of a thermosetting resin composition as described in any one of Claims 1-3.