JP2008037957A - Thermosetting resin composition, b-stage resin film and multilayer build-up substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition having heat resistance, a low expansion coefficient, excellent peeling strength in a place with small surface roughness (Ra≤0.3 μm) after roughened so as to be suitable for a (semi)additive method, excellent desmearing performance at an extra small laser via bottom, and a good balance of resin physical properties such as an elastic modulus, breaking strength and breaking elongation. <P>SOLUTION: This thermosetting resin composition comprises an epoxy resin (a) containing a liquid epoxy resin of 20-70 wt.% with viscosity of 1.0-120 Pa s at 25°C, a triazine-modified phenolic novolac and a benzoxazine resin (b), and a phenoxy resin (c) with a Tg (glass transition temperature: DSC method) of 120°C or higher, wherein an amount of the phenoxy resin (c) is ≤10 pts.wt. based on the total amount of 100 pts.wt. of the epoxy resin (a), the triazine-modified phenolic novolac and the benzoxazine resin (b). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a B-staged resin film, and is used for a high-density build-up printed wiring board having a low expansion coefficient, low roughness-high adhesive strength, high heat resistance, and high reliability. Here, the B stage refers to a state in which the resin composition is semi-cured.

  In recent years, package substrates for MPUs and ASICs are required to have finer lines, smaller pad pitches, multilayers, shorter connections, lower transmission loss, and the like. For this purpose, a high-density build-up substrate or a high-density batch-molded substrate is required in terms of the substrate structure. Needs to be made with a small-diameter laser via, and the connection in the thickness direction also requires a stack via. For this reason, the main characteristics required for the substrate material need to correspond to laser drilling and (semi) additive methods for thinning and diameter reduction. Laser processability with small diameter, high peel strength with low roughness, and smear removal at laser via bottom. Further, there are low expansion coefficient and elastic modulus for improving reliability, dimensional accuracy and positional accuracy, balanced resin properties such as breaking strength and breaking elongation, and electrical characteristics such as low dielectric constant and low dielectric loss tangent. Among them, the importance of low dielectric constant and low dielectric loss tangent has decreased slightly because the MPU performance improvement method has shifted from higher frequency to higher parallelism.

  However, there is currently no material that sufficiently satisfies the above-mentioned requirements, and this is particularly remarkable for an interlayer insulating material for a build-up substrate. In other words, it has high heat resistance, low expansion coefficient, excellent peeling strength when the surface roughness after roughening is small, suitable for the (semi) additive method, and removal of smear at the bottom of laser vias under low roughening conditions A thermosetting resin composition having excellent physical properties and balanced resin properties such as elastic modulus, breaking strength and breaking elongation is desired.

In the patent documents 1 to 3, the present applicant has disclosed a composition for solving this problem.
JP-A-2005-248164 JP-A-2005-272722 JP 2005-281673 A

  A low expansion coefficient can be realized to some extent by adding an inorganic filler on the premise of a low expansion coefficient in the base resin, but there is a limit unless a reduction in the thermal expansion coefficient of the base resin itself is realized. In order to reduce the thermal expansion coefficient of the epoxy resin, selection of a curing agent is important. In addition, certain polymer compounds (such as soluble polyimides and siloxane-modified polyamideimides) can improve film properties without lowering thermal expansion coefficient, low roughening adhesive strength, flexibility, and Tg. It was possible (Patent Document 1).

  However, it has been found that the resin modification as described in Patent Document 1 has a disadvantage that the smear removability of the bottom of the small-diameter laser via under low roughening conditions is inferior when the modification amount increases. Residual smear tends to deteriorate connection reliability.

  The problems of the present invention are high heat resistance (Tg: 150 ° C. or more), low expansion coefficient (40 ppm / ° C. or less at 25 ° C. to 150 ° C.), and surface roughness after roughening that is compatible with the (semi) additive method. Excellent peel strength at small (Ra 0.3μm or less), excellent smear removal at the bottom of the small diameter laser via, and balanced resin properties such as elastic modulus, breaking strength, breaking elongation It is to provide a thermosetting resin composition.

  Moreover, the subject of this invention is providing the high-density buildup printed wiring board manufactured using such a thermosetting resin composition as an interlayer insulation material.

The thermosetting resin composition according to the present invention is:
(a) an epoxy resin containing 20 to 70% by weight of a liquid epoxy resin having a viscosity at 25 ° C. of 1.0 to 120 Pa · s,
(b) a triazine-modified phenol novolac resin and a benzoxazine resin, and
(c) includes a phenoxy resin having a Tg (glass transition temperature: DSC method) of 120 ° C. or higher,
When the total amount of (a) epoxy resin and (b) triazine-modified phenol novolac resin and benzoxazine resin is 100 parts by weight, the amount of phenoxy resin is 10 parts by weight or less.

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

Moreover, this invention relates to the multilayer buildup board | substrate characterized by including the said resin film.

  The present inventor has formulated a suitable blend of a triazine-modified phenol novolac resin and a benzoxazine resin as a curing agent and limits the amount of the polymer compound, thereby reducing the low thermal expansion coefficient, low roughening adhesive strength, It has been found that the film properties can be improved without significantly reducing the flexibility and Tg, and the smear removability at the bottom of the small-diameter laser via can be improved under low roughening conditions.

((A) Epoxy resin containing 20 to 70% by weight of liquid epoxy resin with a viscosity of 1.0 to 120 Pa · s at 25 ° C)
The reason why 20 to 70% by weight of “liquid epoxy resin having a viscosity at 25 ° C. of 1.0 to 120 Pa · s” is used is as follows. In order to support thinning, specifically L / S is 20 / 20μm or less, the sub-tra method is shifted to the (semi) additive method, and low peel (0.3μm or less) and high peel strength (0.7kN / m) The above is an essential condition. This is because the flatness of the insulating layer when entering the roughening step in this (semi) additive step also has a great influence on this. That is, the surface irregularities before the roughening step affect the Ra on the low roughness surface.

  In order to prevent this, it is necessary that the surface is flattened before the roughening step, that is, after the vacuum lamination-planarization and the initial curing step. The standard for this flattening varies depending on various process conditions, but in our experiment, the surface unevenness is 1.5 μm or less due to the difference (step) between each pattern top and its etched surface top regardless of the pattern density. It has been proven necessary. In order to realize this, in addition to the optimization of each process condition, it is necessary to have a proper fluidity at the time of the vacuum laminating-flattening process and the initial curing.

From this point of view, it has been found that it is most effective to use 20 to 70% by weight of a liquid epoxy resin having a viscosity at 25 ° C. of 1.0 to 120 Pa · s in the resin system of the present invention. By making this amount 20% by weight or more, the above effect is remarkably improved. Even a liquid epoxy resin having a viscosity at 25 ° C. of 120 Pa · s or more has an effect on the flatness, but the effect is remarkably reduced. Furthermore, no liquid epoxy resin having a viscosity at 25 ° C. of less than 1.0 Pa · s satisfies the heat resistance. On the other hand, the viscosity at 25 ° C. is 1.0 to 120 Pa · s
If the amount of the liquid epoxy resin exceeds 70% by weight, the target thermal expansion coefficient and Tg cannot be obtained.

  The amount of “liquid epoxy resin having a viscosity at 25 ° C. of 1.0 to 120 Pa · s” is preferably 30% by weight or more, and more preferably 60% by weight or less.

  “Liquid epoxy resin with a viscosity of 1.0 to 120 Pa · s at 25 ° C.” includes bis A type epoxy resin, bis F type epoxy resin, hydrogenated bis A type epoxy resin, novolac phenol type epoxy resin, naphthalene type epoxy resin And tertiary butyl catechol type epoxy resins. These can be used alone or in combination of two or more. Preferably, the viscosity is 1.2 Pa · s to 100 Pa · s. This viscosity is defined by a value measured using an E-type viscometer.

  (A) In the epoxy resin, the epoxy resin other than the liquid epoxy resin is one excluding an epoxy resin having a viscosity at 25 ° C. of 1.0 Pa · s or more, and excluding (c) a phenoxy resin described later. is there.

Such an epoxy resin can be used as long as it is an epoxy resin having two or more glycidyl groups, but in order to obtain a cured product having a Tg (glass transition temperature: TMA method) of 150 ° C. or higher, A novolak phenol type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthol aralkyl type epoxy resin, and the like are suitable, and these can be used alone or in combination of two or more.

  Among various curing agents, triazine-modified novolak resin produces a cured product with low dielectric constant, low dielectric loss tangent and excellent flame resistance compared with conventional novolak resin, and benzoxazine compound has low dielectric constant, low dielectric loss tangent, low A cured product having an expansion coefficient can be produced. However, since the benzoxazine compound alone is inferior in reactivity with the epoxy resin and causes ring-opening polymerization, it has been found that the combined curing agent with the triazine-modified novolak resin according to the present invention exhibits the most excellent cured product properties. .

  In the present invention, (b) the triazine-modified phenol novolak resin curing agent is benzoguanamine-modified bisphenol A type novolak resin, benzoguanamine modified cresol novolak type phenol resin, benzoguanamine modified phenol novolak type phenol resin, melamine modified bisphenol A type novolak resin, melamine modified. There are cresol novolac type phenol resins, melamine-modified phenol novolac type phenol resins and the like.

  In a preferred embodiment, when (a) the epoxy equivalent number of the epoxy resin is 1, (b) the hydroxyl equivalent number of the triazine-modified phenol novolak resin is 0.5 to 1.0. By setting this to 0.5 or more, an appropriate thermal expansion coefficient can be obtained. By making this 1.0 or less, a well-balanced breaking strength and breaking elongation can be obtained.

Here, the number of epoxy equivalents of (a) epoxy resin is as follows.
Epoxy equivalent number of epoxy resin =
(Weight of epoxy resin in composition (solid content weight)) / (Epoxy equivalent of epoxy resin)
(b) The number of hydroxyl equivalents of the triazine-modified phenol novolac resin is as follows.
(b) Number of hydroxyl equivalents of triazine-modified phenol novolac resin =
(Weight of triazine-modified phenol novolac resin in the composition) /
(Hydroxyl equivalent of triazine-modified phenol novolac resin)

When the number of epoxy equivalents of the (a) epoxy resin is 1, the number of hydroxyl equivalents of the (b) triazine-modified phenol novolac resin curing agent is the ratio (anonymous number) of both, and is calculated by the following formula.
(Number of hydroxyl equivalents of triazine-modified phenol novolac resin) /
(Epoxy equivalent number of epoxy resin)

  (b) The benzoxazine compound used as a curing agent is not particularly limited. Preferably, it is a compound represented by the general formula (formula 1) or (formula 2), an isomer of this compound, or an oligomer of this compound, and generates a phenolic hydroxyl group and a tertiary amine by ring opening by heat. . For this reason, the effect | action as a hardening | curing agent of an epoxy resin can also be anticipated. However, since benzoxazine compounds can be self-condensed by heat, there are restrictions on the structures that can be used for such applications, and those capable of ring-opening polymerization at low temperatures are not suitable. From this viewpoint, a compound capable of ring-opening polymerization by heat at 100 ° C. or higher is suitable.

  In a preferred embodiment, when (a) the number of epoxy equivalents of the epoxy resin is 1, the number of hydroxyl equivalents after thermal decomposition of the benzoxazine compound is 0.1 or more and 0.5 or less. By setting this to 0.1 or more, the effect of lowering the dielectric constant / dielectric loss tangent and the coefficient of expansion of the resin is enhanced. If this exceeds 0.5, the curing time is significantly delayed, so it is preferably 0.5 or less, and more preferably 0.3 or less.

(b) The number of hydroxyl equivalents after thermal decomposition of the benzoxazine compound is as follows.
(b) Number of hydroxyl equivalents after thermal decomposition of benzoxazine compound =
(Weight of benzoxazine compound in composition) /
(Hydroxyl equivalent after thermal decomposition of benzoxazine compound)

(a) When the number of epoxy equivalents of the epoxy resin is 1, (b) The number of hydroxyl equivalents after the thermal decomposition of the benzoxazine compound is the ratio (anonymous number) of both, and is calculated by the following formula.
((B) Number of hydroxyl equivalents after thermal decomposition of benzoxazine compound) /
(Epoxy equivalent number of epoxy resin)

  From the viewpoint of the effect obtained by using the two kinds of curing agents, it is more effective to control the total equivalent ratio. Specifically, when (a) the number of equivalents of the epoxy resin is 1, (b) the number of hydroxyl equivalents of the triazine-modified phenol novolac resin curing agent and (b) the number of hydroxyl equivalents after thermal decomposition of the benzoxazine resin. More preferably, the total is 0.6 to 1.2.

 (c) The phenoxy resin is contained in the polymer epoxy resin and has a molecular weight (Mw) of 10,000 or more. The type of phenoxy resin is not limited, but the resin skeleton is BPA / BPS type, BP / BPS type, BP type, BPS type, etc., and Tg (DSC) method is 120 ° C or higher (more preferably 130 ° C). Those having a heat-resistant skeleton as described above are suitable.

  (C) When phenoxy resin is used, it is slightly inferior in terms of thermal expansion coefficient, adhesive strength at low roughness, and Tg compared to the case of using siloxane-modified polyamideimide resin or solvent-soluble polyimide resin. However, the effect is reduced by limiting the addition amount. And, regarding smear removability, it is superior to siloxane-modified polyamideimide resin or solvent-soluble polyimide resin.

  (C) By reducing the amount of phenoxy resin used to 10 parts by weight or less (preferably 9 parts by weight or less, more preferably 8 parts by weight or less), the smear removability of the bottom of a small-diameter laser via under low roughening conditions is remarkably increased improves. Moreover, the effect of adhesiveness and flexibility is improved by setting this to 1 part by weight or more.

  In the composition of the present invention, (d) a filler can be added. Specifically, the filler (d) is preferably silica, alumina, aluminum nitride, boron nitride, magnesium oxide or the like.

  Further, when the total amount of (a) epoxy resin, (b) curing agent, and (c) phenoxy resin is 100 parts by weight, the amount of (d) filler is preferably 40 to 100 parts by weight. When a low expansion coefficient is taken into consideration, silica is preferred. In this case, silica that has been surface-treated (epoxysilane treatment, aminosilane treatment, vinylsilane treatment, etc.) may be used. Further, as the particle size, spherical particles having an average particle size of 0.5 μm or less are desirable from the viewpoint of narrow pitch (L / S ≦ 20/20 μm) and reduction of surface roughness (Ra ≦ 0.3 μm). In order to obtain a peel strength of 0.5 kN / m or more with Ra ≦ 0.3 μm and C.T.E to be 40 ppm / ° C. or less, it is preferable to add 40 parts by weight or more of silica. However, since addition of 100 parts by weight or more deteriorates workability such as laser processability and peel strength, it is preferably 100 parts by weight or less.

  As other fillers, fillers such as alumina, aluminum nitride, boron nitride, and magnesium oxide can be similarly used.

  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 and organic phosphine compounds can be used. Select mainly from the viewpoint of reaction rate (curing 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-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.

  A flame retardant can be added to the composition of the present invention for imparting flame retardancy. In particular, as halogen-free flame retardants, condensed phosphate esters, phosphazenes, polyphosphates, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivatives, etc. are good. is there.

  Although the solvent which can be used for the thermosetting resin composition of the present invention is not particularly limited, it is particularly preferable to combine a high boiling point solvent such as NMP and diethylene glycol monomethyl ether acetate with a low boiling point solvent among cyclohexanone and MEK.

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 can be obtained by using NMP, diethylene glycol monomethyl ether acetate / MEK, if necessary.
, Varnish by diluting with a suitable mixed organic solvent such as cyclohexanone, etc., by applying a die coater etc. on a polyethylene terephthalate film (PET film) that has been subjected to mold release treatment if necessary, and then heating A thermosetting resin film in a B state can be produced.

  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 with a die coater or the like. Examples of the metal foil include a roughened copper foil and an aluminum foil, and a copper foil is particularly preferable.

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

(Example 1)
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 283, resin solid content 80% by weight), 98 parts by weight of “EPICLON
730A "(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850dPa · s (8.50 Pa · s) / 25 ° C), 157 parts by weight of melamine-modified cresol novolac resin" EXB-9854 "(Dainippon Ink Chemical Co., Ltd.) Made by the company, hydroxyl value 151, resin solid content 80% by weight), 42 parts by weight of benzoxazine resin “F-a” (manufactured by Shikoku Kasei Co., Ltd., hydroxyl value 217), 110 parts by weight of phenoxy resin “YL6954BH30” (Japan epoxy) Resin, Mw = about 39,000, resin solid content 30% by weight), 27 parts by weight of phosphazene compound “SPB-100” (manufactured by Otsuka Chemical), 0.7 parts by weight of 2-ethyl-4 methylimidazole, 272 parts by weight Epoxy silane-treated silica (average particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

(Example 2)
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 283, resin solid content 80% by weight), 98 parts by weight of “EPICLON
730A ”(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850 dPa · s / 25 ° C.), 157 parts by weight of melamine-modified cresol novolac resin“ EXB-9854 ”(Dainippon Ink Chemical Co., Ltd., hydroxyl value 151 Resin solid content 80 wt%), 42 parts by weight of benzoxazine resin “F-a” (manufactured by Shikoku Kasei Co., Ltd., hydroxyl value 217), 83 parts by weight of phenoxy resin “FX280AXM40” (manufactured by Toto Kasei Co., Ltd., Mw = about 45,000, resin solid content 40% by weight), 27 parts by weight of phosphazene compound `` SPB-100 '' (manufactured by Otsuka Chemical), 0.7 parts by weight of 2-ethyl-4methylimidazole, 272 parts by weight of epoxysilane-treated silica (average) Particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

(Example 3)
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (manufactured by Dainippon Ink and Chemicals, epoxy equivalent 283, resin solid content 80% by weight), 98 parts by weight of “EPICLON
730A ”(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850 dPa · s / 25 ° C.), 157 parts by weight of melamine-modified cresol novolac resin“ EXB-9854 ”(Dainippon Ink Chemical Co., Ltd., hydroxyl value 151 , Resin solid content 80% by weight), 42 parts by weight of benzoxazine resin “F-a” (manufactured by Shikoku Kasei Co., Ltd., hydroxyl value 217), 83 parts by weight of phenoxy resin “FX293AXM40” (manufactured by Toto Kasei Co., Ltd., Mw = about 43,000, resin solid content 40% by weight), 27 parts by weight of phosphazene compound `` SPB-100 '' (manufactured by Otsuka Chemical), 0.7 parts by weight of 2-ethyl-4methylimidazole, 272 parts by weight of epoxysilane-treated silica (average) Particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

Example 4
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 283, resin solid content 80% by weight), 98 parts by weight of “EPICLON
730A ”(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850 dPa · s / 25 ° C.), 157 parts by weight of melamine-modified cresol novolac resin“ EXB-9854 ”(Dainippon Ink Chemical Co., Ltd., hydroxyl value 151 , Resin solid content 80% by weight), 42 parts by weight of benzoxazine resin “F-a” (manufactured by Shikoku Chemicals, hydroxyl value 217), 110 parts by weight of phenoxy resin “YX8100BH30” (manufactured by Japan Epoxy Resin, Mw = About 38,000, resin solid content 30% by weight), 27 parts by weight of phosphazene compound `` SPB-100 '' (manufactured by Otsuka Chemical Co., Ltd.), 0.7 parts by weight of 2-ethyl-4methylimidazole, 272 parts by weight of epoxysilane-treated silica ( Average particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

(Comparative Example 1)
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (Dainippon Ink and Chemicals, Epoxy equivalent 283, resin solid content 80% by weight), 57 parts by weight of “EPICLON”
730A "(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850dPa.s / 25 ° C), 110 parts by weight of melamine-modified cresol novolac resin" EXB-9854 "(Dainippon Ink Chemical Co., Ltd., hydroxyl value 151 , Resin solid content 80% by weight), 60 parts by weight of benzoxazine resin `` Fa '' (manufactured by Shikoku Chemicals, hydroxyl value 217), 216 parts by weight of siloxane-modified polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., amide equivalent 620, Mw = about 80,000, resin solid content 28% by weight), 15 parts by weight of condensed phosphate ester “PX-200” (manufactured by Daihachi Chemical Co., Ltd.), 0.7 parts by weight of 2-ethyl-4methylimidazole, 120 parts by weight Epoxy silane-treated silica (average particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

(Comparative Example 2)
362 parts by weight of biphenyl type epoxy resin `` NC-3000H '' (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 275, resin solid content 80% by weight), 177 parts by weight of melamine-modified phenol novolac resin `` LA-7054 '' (Dainippon Ink Chemical Industry Co., Ltd., hydroxyl value 125, resin solid content 60% by weight), 60 parts by weight of benzoxazine resin `` Fa '' (manufactured by Shikoku Kasei Co., Ltd., hydroxyl value 217), 302 parts by weight of soluble polyimide resin `` Q-VR- X0163 '' (manufactured by PI Engineering Laboratory, Mw≈25,000, resin solid content 20% by weight), 25 parts by weight of condensed phosphate ester PX-200 (manufactured by Daihachi Chemical Co., Ltd.), 1.0 part by weight of 1-cyano- 2-Undecylimidazole, 120 parts by weight of epoxysilane-treated silica (average particle size
To the mixture of 0.3 μm), an NMP / MEK mixed solvent was added as a solvent to prepare a resin varnish having a resin solid content of 55% by weight.

(Comparative Example 3)
260 parts by weight of dicyclopentadiene type epoxy resin “HP-7200H” (Dainippon Ink Chemical Co., Ltd., epoxy equivalent 283, resin solid content 80% by weight), 98 parts by weight of “EPICLON
730A "(Dainippon Ink Chemical Co., Ltd., epoxy equivalent 180, viscosity 850dPa · s / 25 ° C), 157 parts by weight of melamine-modified cresol novolak resin" EXB-9854 "(Dainippon Ink Chemical Co., Ltd., hydroxyl value 151 , Resin solid content 80% by weight), 42 parts by weight of benzoxazine resin `` Fa '' (manufactured by Shikoku Chemicals, hydroxyl value 217), 118 parts by weight of siloxane-modified polyamideimide resin (manufactured by Hitachi Chemical Co., Ltd., amide equivalent 620, Mw = about 80,000, resin solid content 28% by weight), 27 parts by weight of phosphazene compound “SPB-100” (manufactured by Otsuka Chemical Co., Ltd.), 0.7 parts by weight of 2-ethyl-4methylimidazole, 272 parts by weight of epoxysilane treatment Silica (average particle size
A resin varnish having a resin solid content of 60% by weight was prepared by adding an NMP / MEK mixed solvent as a solvent to a mixture of 0.3 μm).

  The resin varnish of each example was well dispersed using a three roll. This was coated with a die coater on a 25 μm polyethylene terephthalate film (PET film) that had been subjected to a release treatment if necessary, and dried at a temperature of 120 ° C. to produce a thermosetting resin film (A) in a B state having a thickness of 40 μm. . Volatiles were adjusted to 3.0 wt%. Further, a polyethylene film (PE film) was laminated as a protective film.

This was overlapped with 18μm surface-treated copper foil, placed in a vacuum press and molded at 180 ° C for 120 minutes, heated and pressurized (vacuum degree 5 torr) at 0.65 MPa (molded product (1))
Similarly, it was overlapped with a copper foil with processing feet, charged in a vacuum press and molded at 180 ° C. for 120 minutes and heated and pressurized at 0.65 MPa (vacuum degree 5 torr). (Molded product (2))

On the other hand, a circuit was formed on a 0.6mm thick high-Tg halogen-free FR-4 double-sided copper-clad laminate (copper foil 18μm) [trade name TLC-W-552Y, manufactured by Kyocera Chemical Co., Ltd.], and the conductor was treated with black copper oxide Later, with a vacuum laminator, the protective film is peeled off from the above film A, lamination is performed on both surfaces, and flattening is performed through a flattening press step. This is first heated and cured in a tunnel drying furnace at 190 ° C for 30 minutes. After cooling and taking out, blind vias having predetermined hole diameters (60 μm, 100 μm) were formed with a CO 2 laser.
Surface roughening was performed with a permanganate desmear solution, and at the same time, residual resin at the bottom of the hole was dissolved and removed. Electroless copper plating 0.8 μm and electrolytic copper plating 20 μm were applied to this, and after baking was performed at 190 ° C. for 60 minutes. By repeating this, a 6-layer build-up multilayer printed wiring board (I) having two build-up layers on one side was produced (the built-up pattern was not formed, but there was a solid copper part capable of peel measurement).

  Table 1 summarizes the parameters of the above examples. In addition, Table 2 and Table 3 show the results of characteristic evaluation of each example. PWB (II) in Tables 2 and 3 is a JPCA-HD01 test pattern substrate manufactured in accordance with the manufacturing method of PWB (I).

(Flatness): PWB (II) surface unevenness after flattening press, the difference between each pattern top and its etched surface top
(Step); (by laser microscope)
(LVH via bottom smear removability): Determine visually by SEM secondary electron image (× 1,000) of via bottom after desmear.
(Surface roughness): According to a laser microscope.
(PWB (II)): JPCA-HD01-compliant test pattern substrate fabricated in accordance with the PWB (I) manufacturing method.
(Film physical properties): According to autograph.
(Reliability): According to JPCA-BU01.
(a) Thermal shock test: 150 ℃ × 30min and −65 ℃ × 30min (1 cycle)
Judgment criteria: 10% change in conduction resistance
(b) High temperature and high humidity bias test 85 ℃ × 85% RH, DC = 30V L / S = 30 / 30μm
Judgment criteria: Insulation resistance 1 × 107Ω or more (measurement in the tank)
PWB (III): Substrate in which a film is laminated on each side of a 0.1 mm thick core with two layers on each side.

  As described above, according to the present invention, a resin composition for a high-density build-up printed wiring board having a low expansion coefficient, low roughness-high adhesive strength, high heat resistance, high reliability, and high smear removability is provided. Can be provided. And the printed wiring board which provided such various characteristics can be used for semiconductor plastic packages.

Claims (7)

(a) an epoxy resin containing 20 to 70% by weight of a liquid epoxy resin having a viscosity at 25 ° C. of 1.0 to 120 Pa · s,
(b) a triazine-modified phenol novolac resin and a benzoxazine resin, and
(c) includes a phenoxy resin having a Tg (glass transition temperature: DSC method) of 120 ° C. or higher,
The amount of the (c) phenoxy resin when the total amount of the (a) epoxy resin and the (b) triazine-modified phenol novolac resin and the benzoxazine resin is 100 parts by weight is 10 parts by weight or less. A thermosetting resin composition.   Furthermore, when (d) filler is included, the total amount of (a) epoxy resin, (b) triazine-modified phenol novolac resin and benzoxazine resin, and (c) phenoxy resin is 100 parts by weight. The composition according to claim 1, wherein the amount of filler is 40 parts by weight or more. When the epoxy equivalent number of the (a) epoxy resin is 1, the hydroxyl equivalent number of the (b) triazine-modified phenol novolac resin curing agent is 0.5 to 1.0,
The hydroxyl equivalent number after thermal decomposition of the (b) benzoxazine resin is 0.1 to 0.5,
The sum of the number of hydroxyl equivalents of the (b) triazine-modified phenol novolak resin and the number of hydroxyl equivalents after thermal decomposition of the (b) benzoxazine resin is 0.6 to 1.2. The composition as described.   The (b) triazine-modified phenol novolak resin curing agent is selected from the group consisting of a melamine-modified phenol novolak resin, a melamine-modified cresol novolak resin, a benzoguanamine-modified phenol novolak resin, and a benzoguanamine-modified cresol novolak resin. The composition according to any one of claims 1 to 3.   The composition according to any one of claims 2 to 4, wherein the filler (d) is selected from the group consisting of silica, alumina, aluminum nitride, boron nitride, and magnesium oxide. .   A B-staged resin film prepared from the composition according to any one of claims 1 to 5.   A multilayer buildup substrate comprising the resin film according to claim 6.