JP6123152B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition for solder resist. Furthermore, it is related with the circuit board containing the said resin composition.

In the solder resist of a printed wiring board, the color tone is generally green that is gentle to the eyes of the operator and has high design properties. With the recent increase in environmental awareness, there is a demand for reduction of halogen compounds that generate toxic gases and dioxins during combustion. Therefore, Patent Document 1 only describes a very common technique in which a halogen-free green solder resist resin composition for printed wiring boards is obtained by blending a plurality of colorants with a photocurable resin composition.

JP2000-7974

The problem to be solved by the present invention is to provide a halogen-free resin composition for a solder resist that has a low surface roughness after desmearing of a cured product of the resin composition and exhibits a green color regardless of only the pigment. It is.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention with a resin composition containing a naphthol resin and a blue colorant. That is, the present invention includes the following contents.
[1] A solder resist resin composition comprising (A) a naphthol resin and (B) a blue colorant.
[2] The resin composition according to [1] above, wherein the b * value of the L * a * b * display system of the cured product of the resin composition is −25 or more and 40 or less.
[3] The resin composition according to [1] or [2] above, wherein the a * value of the L * a * b * display system of the cured product of the resin composition is −60 or more and 55 or less. .
[4] The above [1] to [3], wherein the content of (A) naphthol resin is 0.001 to 30% by mass when the nonvolatile content in the resin composition is 100% by mass. The resin composition in any one of.
[5] The above-mentioned [1] to [4], wherein the content of the (B) blue colorant is 0.001 to 10% by mass when the nonvolatile content in the resin composition is 100% by mass. ] The resin composition in any one of.
[6] The composition according to any one of [1] to [5], wherein the blending amount of the (B) blue colorant is 0.01 to 1000000 mass% with respect to 100 mass% of (A) naphthol resin. Resin composition.
[7] The resin composition as described in any one of [1] to [6] above, wherein the (A) naphthol resin is a naphthol aralkyl resin.
[8] The resin composition according to any one of the above [1] to [7], further comprising (C) an epoxy resin.
[9] The resin composition according to any one of the above [1] to [8], further comprising (D) an inorganic filler.
[10] The resin composition as described in any one of [1] to [9] above, further comprising (E) a curing agent (excluding (B) naphthol resin).
[11] The resin composition according to any one of [1] to [10] above, wherein the Munsell color system display of the cured product of the resin composition is in a range of GY to BG.
[12] The resin composition according to any one of [1] to [11] above, wherein the surface roughness (Ra value) after desmearing of the cured product of the resin composition is 10 to 550 nm.
[13] An adhesive film in which the resin composition according to any one of [1] to [12] is layered on a support.
[14] A multilayer printed wiring board in which an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [12].
[15] A semiconductor device using the multilayer printed wiring board according to [14].
[16] A multilayer printed wiring board characterized in that 97% by mass or more of the nonvolatile components in the resin composition of the solder resist layer and the nonvolatile components in the resin composition of the build-up layer are the same component.
[17] The multilayer printed wiring as described in [16] above, wherein the content of silica is 40 to 85% by mass when the nonvolatile content in the resin composition of the solder resist layer is 100% by mass. Board.
[18] The linear thermal expansion coefficient a (ppm) of 25 to 150 ° C. of the solder resist layer and the linear thermal expansion coefficient b (ppm) of 25 to 150 ° C. of the buildup layer are 12 ≦ a ≦ (b + 5 ) ≦ 30, and the elastic modulus of the solder resist layer at 23 ° C. is 7 GPa or more, the multilayer printed wiring board according to the above [16] or [17].
[19] The multilayer printed wiring board according to [18], wherein the linear thermal expansion coefficient a (ppm) is 25 or less.
[20] The adhesive strength of the solder resist layer and the copper foil after the high-temperature and high-humidity test is 0.4 kgf / cm or more and 10 kgf / cm or less, according to any one of the above [16] to [19] The multilayer printed wiring board as described.

The resin composition containing the naphthol resin and the blue colorant of the present invention has a low surface roughness after desmearing of a cured product of the resin composition, and is a halogen-free resin for solder resist that exhibits a green color independently of the pigment. A composition can now be provided.

6 is a conceptual diagram for illustrating a design of a double-sided copper-clad laminate of Example 5. FIG. 10 is a cross-sectional view of a core substrate of Example 5. FIG. FIG. 10 is a cross-sectional view of the core substrate after the buildup layer lamination of Example 5. FIG. 10 is a top view of the core substrate after the buildup layer is laminated in Example 5. It is sectional drawing of the core board | substrate after the soldering resist layer lamination | stacking of Example 5. FIG.

The present invention relates to a resin composition for a solder resist, which contains (A) a naphthol resin and (B) a blue colorant. The resin composition for solder resist may be a photocurable resin composition or a thermosetting resin composition. Among these, a thermosetting resin composition is preferable from the viewpoint of excellent heat resistance, reliability, and adhesion.

<(A) Naphthol resin>
The naphthol resin used in the present invention is a compound containing a naphtholic hydroxyl group such as a naphthol novolak resin or a naphthol aralkyl type resin, and has a curing action of an epoxy resin. These may be used alone or in combination of two or more. Among these, naphthol aralkyl type resins are preferred from the viewpoint of improving desmear resistance, reducing roughness after desmearing, reducing bleeding of the underfill material, and facilitating adjustment of the color exhibited by the cured product, among these, What is represented by following formula (1) is more preferable, and what is represented by following formula (2) is still more preferable. One or more naphthol resins may be used in view of the balance of the properties of the curing agent. Specifically, SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.) and the like are listed as naphthol aralkyl type resins.

(In the formula, m is 1 to 2. n is 1 to 15.)

(In the formula, m is 1 to 2. n is 1 to 15.)

In the resin composition of the present invention, the content of the naphthol resin in the resin composition is not particularly limited, but from the viewpoint of suppressing an increase in the viscosity of the varnish and preventing the cured product from becoming brittle, 30 mass% or less is preferable with respect to 100 mass% of non volatile matters in a resin composition, 25 mass% or less is more preferable, 20 mass% or less is further more preferable, 18 mass% or less is still more preferable, 15 mass% or less is 15 mass% or less. Particularly preferred is 13% by weight or less, particularly preferred is 10% by weight. Further, from the viewpoint of improving desmear resistance and exhibiting a green color, 0.001% by mass or more is preferable, 0.01% by mass or more is more preferable with respect to 100% by mass of the nonvolatile content in the resin composition, and 0.1% % By mass is further preferred, 0.3% by mass is still more preferred, 0.5% by mass or more is particularly preferred, 1% by mass or more is particularly preferred, and 2% by mass is particularly preferred.

<(B) Blue colorant>
The blue colorant used in the present invention is not particularly limited as long as it exhibits a blue color, and examples thereof include pigments, dyes, and blue materials. Although it does not specifically limit as a pigment, For example, copper phthalocyanine blue (Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6), Metal-free phthalocyanine blue (Pigment Blue 16), indanthrone (Pigment Blue 60), titanyl phthalocyanine blue, iron phthalocyanine blue, nickel phthalocyanine blue, aluminum phthalocyanine blue, tin phthalocyanine blue, alkali blue (Pigment Blue 1,2,3,10 , 14,18,19,24,56,57,61), sulfonated CuPc (Pigment Blue 17), bitumen (PigmentBlue 27), ultramarine blue (Pigment Blue 29), cobalt blue (Pigment Blue28), sky blue ( Pigment Blue 35), Co (Al, Cr) 2 O4 (Pigment Blue 36), Disazo (Pigment Blue 25,26), Indigo (Pigment Blue 63,66), Cobalt phthalocyanine (Pigment Blue 75), etc. are used. Door can be. Of these, copper phthalocyanine blue is preferable from the viewpoint of versatility. Examples of the dye include, but are not limited to, for example, Solvent Blue 35, Solvent Blue 45, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 101 Solvent Blue 104, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, and the like can be used. The blue colorant may be used alone or in combination of two or more. As a blue material, it is a component which can be normally used for a resin composition, Comprising: You may use what exhibits blue.

The content of the blue colorant is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 4% by mass with respect to 100% by mass of the non-volatile content in the resin composition from the viewpoints of improving design properties and improving cured properties. % Or less is more preferable, 3% by mass or less is further more preferable, 2% by mass or less is particularly preferable, and 1% by mass or less is particularly preferable. Moreover, from a viewpoint of performing shielding improvement and sufficient coloring, 0.001 mass% or more is preferable with respect to 100 mass% of non volatile matters in a resin composition, 0.01 mass% or more is more preferable. 02% by mass or more is more preferable, 0.05% by mass or more is further more preferable, 0.08% by mass or more is particularly preferable, and 0.1% by mass or more is particularly preferable.

The mass ratio of (A) naphthol resin and (B) blue colorant is not particularly limited as long as it exhibits a green color, but the blending amount of (B) blue colorant relative to 100% by mass of (A) naphthol resin. Is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, still more preferably 0.5% by weight or more, still more preferably 1% by weight or more, and even more preferably 1.5% by weight or more. 2 mass% or more is especially preferable, and 3 mass% or more is especially preferable. Further, the blending amount of the (B) blue colorant with respect to 100% by mass of (A) naphthol resin is preferably 1000000% by mass or less, more preferably 100000% by mass or less, further preferably 10000% by mass or less, and 150% by mass or less. Even more preferred is 100% by weight or less, particularly preferred is 80% by weight or less, and particularly preferred is 60% by weight or less.

The surface roughness (Ra value) of the cured product of the resin composition of the present invention is preferably 590 nm or less from the viewpoint of preventing bleeding of the underfill material and preventing contamination of the nickel-gold plating solution. Is more preferably 510 nm or less, still more preferably 470 nm or less, still more preferably 460 nm or less, particularly preferably 450 nm or less. Also, from the viewpoint of efficiently removing smear after laser drilling and obtaining adhesion strength with the underfill after curing, 10 nm or more is preferable, 30 nm or more is more preferable, and 50 nm or more is even more preferable.

The method for identifying the green color of the cured product of the resin composition of the present invention is not particularly limited as long as it is recognized, judged, and confirmed as green, but specifically, it can be visually judged or mechanically measured L * a. * B * display or Munsell color system display can be selected. As a method for specifying the green color of the cured product of the resin composition of the present invention, when the L * a * b * display is measured mechanically, the b * display affects the color tone of blue, green, and yellow. It is preferable to specify. From the viewpoint that it can be recognized as green, the b * value lower limit value is preferably −25 or more, more preferably −23 or more, still more preferably −21 or more, still more preferably −19 or more, and even more preferably −17 or more, -15 or more is particularly preferable. Also, from the viewpoint that it can be recognized as green, the b * value upper limit value is preferably 40 or less, more preferably 30 or less, still more preferably 25 or less, still more preferably 20 or less, even more preferably 15 or less, and even more preferably 10 or less. Particularly preferred. The L * value is not particularly limited, but is preferably 1 to 99, more preferably 5 to 90, still more preferably 10 to 80, still more preferably 15 to 70, still more preferably 20 to 60, and particularly preferably 25 to 55. . The a * value is not particularly limited, but is preferably −60 to 55, preferably −55 to 45, more preferably −50 to 35, still more preferably −45 to 25, and particularly preferably −40 to 15. −35 to 5 is particularly preferable, and −30 to 0 is particularly preferable. However, the L * a * b color system here is a display method described in JIS Z 8729. JIS Z 8729 is defined in 4 of Publication CIE No. 15.2 (1986) COLORIMETRY, SECOND EDITION.

As the method for specifying the green color of the cured product of the resin composition of the present invention, when selecting Munsell color system display, it is preferable that the color tone is specified from the viewpoint that the color tone can be specified. The range of the hue which is green is preferably GY to BG, more preferably 0.5 GY to 10 BG, still more preferably 5 GY to 10 BG, and even more preferably 10 GY to 10 BG. The lightness is not particularly limited as long as it does not affect the color determination, but is preferably 1 to 10, more preferably 2 to 9, and still more preferably 3 to 8. The saturation is not particularly limited as long as it does not affect the color determination, but is preferably 1 to 10, and more preferably 3 to 9. The Munsell color system referred to here is a display method described in JIS Z 8721.

<(C) Epoxy resin>
When the resin composition of the present invention further contains (C) an epoxy resin, the mechanical properties of the insulating layer obtained from the resin composition can be improved. The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidyl Amine type epoxy resin, cresol novolak type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, epoxy resin having butadiene structure, linear aliphatic epoxy resin, alicyclic type Examples thereof include an epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin, a cyclohexanedimethanol type epoxy resin, and a trimethylol type epoxy resin. These may be used alone or in combination of two or more. In particular, when two or more kinds are used in combination, the crystallinity of the resin composition is suppressed as compared with the case of using alone, and a cured product having a good balance such as heat resistance is obtained, which is particularly preferable.

Among these, epoxy resins are bisphenol A type epoxy resins and naphthol aralkyl type epoxies from the viewpoints of improving heat resistance, improving insulation reliability, improving adhesion to the conductor layer, and facilitating adjustment of the color of the cured product. Resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and epoxy resins having a butadiene structure are preferable, and naphthol aralkyl type epoxy resins and naphthalene type epoxy resins are more preferable. Specifically, liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by DIC Corporation), naphthalene type tetrafunctional Epoxy resins (“HP4700” and “HP4710” manufactured by Dainippon Ink and Chemicals, Inc.), naphthol type epoxy resins (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), and epoxy resins having a butadiene structure (Daicel Chemical) "PB-3600" manufactured by Kogyo Co., Ltd.), epoxy resins having a biphenyl structure ("NC3000H", "NC3000L" manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Mitsubishi Chemical Corporation)) and the like.

In the resin composition of the present invention, the content of the epoxy resin in the resin composition is not particularly limited, but the glass transition temperature of the cured product of the resin composition is improved and the linear thermal expansion coefficient is reduced. From the viewpoint, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less with respect to 100% by mass of the nonvolatile content in the resin composition. Further, from the viewpoint of improving the adhesion strength with the underlying conductor layer, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more with respect to 100% by mass of the nonvolatile content in the resin composition. preferable.

<(D) Inorganic filler>
By further including (D) an inorganic filler in the resin composition of the present invention, the coefficient of thermal expansion of the insulating layer obtained from the resin composition can be further reduced. The inorganic filler is not particularly limited, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is preferable from the viewpoint of further reducing the thermal expansion coefficient and improving the elastic modulus. The silica is preferably spherical. These may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is not particularly limited, but is preferably 3 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and 0.7 μm from the viewpoint of improving the insulation reliability. The following is even more preferable. Moreover, 0.05 micrometer or more is preferable from a viewpoint of preventing the raise of the viscosity of a varnish at the time of using a resin composition as a resin varnish, and preventing a handleability falling. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

Although content in particular of an inorganic filler is not restrict | limited, From a viewpoint of preventing that the flexibility of a resin composition film falls, 85 mass% or less with respect to 100 mass% of non volatile matters in a resin composition. It is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass or less, and particularly preferably 60% by mass or less. Further, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer, it is preferably 20% by mass or more, more preferably 25% by mass or more, and further preferably 30% by mass or more with respect to 100% by mass of the nonvolatile content in the resin composition. Preferably, 35 mass% or more is still more preferable.

Inorganic fillers include silane coupling agents, acrylate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, mercapto silane coupling agents, styryl silane coupling agents, and isocyanate silane coupling agents. Surface treatment with a surface treatment agent such as an agent, organosilazane compound, epoxysilane coupling agent, aminosilane coupling agent, ureidosilane coupling agent, titanate coupling agent, etc. to improve its moisture resistance and dispersibility Are preferred. These may be used alone or in combination of two or more. Specifically, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane Aminosilane coupling agents such as N-2 (-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-ureidopropyltriethoxysilane, etc. Ureidosilane coupling agent, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane Epoxysilane coupling agents such as glycidylbutyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyl Mercaptosilane-based coupling agents such as dimethoxysilane and 11-mercaptoundecyltrimethoxysilane, methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, t- Silane coupling agents such as butyltrimethoxysilane, vinylsilane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldiethoxysilane. Ring agent, styrylsilane coupling agent such as p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltri Acrylate silane coupling agents such as ethoxysilane and 3-methacryloxypropyldiethoxysilane, isocyanate silane coupling agents such as 3-isocyanatopropyltrimethoxysilane, bis (triethoxysilylpropyl) disulfide, bis (triethoxysilyl) Propyl) sulfide silane coupling agents such as tetrasulfide, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, hexaphenyl Silazane, trisilazane, cyclotrisilazane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, hexabutyldisilazane, hexaoctyldisilazane, 1,3-diethyltetramethyldi Silazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3-diethyltetramethyldisilazane, 1,1, Organosilazane compounds such as 3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, dimethylaminotrimethylsilazane, tetramethyldisilazane, tetra-n -Butyl titanate dimer, titanium-i-propo Xyloctylene glycolate, tetra-n-butyl titanate, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate , Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis ( Ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite Isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl And titanate coupling agents such as tris (dioctylpyrophosphate) titanate and isopropyltri (N-amidoethyl / aminoethyl) titanate. Of these, aminosilane coupling agents are preferred because of their excellent moisture resistance, dispersibility, and properties of cured products.

<(E) Curing agent (excluding naphthol resin)>
The resin composition of the present invention may further contain (E) a curing agent (excluding naphthol resin). Although there is no restriction | limiting in particular in these hardening | curing agents, A phenol type hardening | curing agent, an active ester type hardening | curing agent, a cyanate ester type hardening | curing agent etc. are mentioned.

From the viewpoint of obtaining a cured product in which the crystallinity of the resin composition is suppressed and the balance of heat resistance is improved, a phenol-based curing agent is preferable. Specific examples include compounds containing a phenol skeleton such as a phenol novolak resin, an alkylphenol novolak resin, an aminotriazine structure-containing novolak resin, a bisphenol A type novolak resin, a zyloc type phenol resin, a terpene-modified phenol resin, and a biphenyl type resin. Of these, phenol novolak resins and aminotriazine structure-containing novolak resins are preferred, and aminotriazine structure-containing novolak resins are more preferred. Commercially available phenolic curing agents include MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.) as allylphenol resins, and NHN, CBN, GPH (Nippon Kayaku (manufactured by Meiwa Kasei Co., Ltd.)). As an aminotriazine structure-containing novolak resin, LA7052, LA7054 (manufactured by DIC Corporation) can be mentioned.

In the resin composition of the present invention, the content of the (E) curing agent (excluding the naphthol resin) in the resin composition is not particularly limited, but from the viewpoint of improving the thermal expansion coefficient of the cured product, 15 mass% or less is preferable with respect to 100 mass% of non volatile matters in a resin composition, 13 mass% or less is more preferable, and 11 mass% or less is still more preferable. Moreover, from the viewpoint of obtaining the effect of blending these, the content is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more with respect to 100% by mass of the nonvolatile content in the resin composition.

The ratio of the number of epoxy groups of (C) epoxy resin in the resin composition of the present invention to the total number of active hydrogen groups of (A) naphthol resin and (E) curing agent (excluding naphthol resin) is a cured product. From the viewpoint of preventing a decrease in mechanical strength and water resistance, a range of 1: 0.2 to 2 is preferable, a range of 1: 0.3 to 1.5 is more preferable, and 1: 0.4 to A range of 1 is more preferred.

<(F) Thermoplastic resin>
When the resin composition of the present invention further contains (F) a thermoplastic resin, the viscosity of the resin varnish obtained from the resin composition and the flexibility of the cured product can be increased. The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyamide resin, polyethersulfone resin, polysulfone resin, polybutadiene resin, and ABS resin. Of these, phenoxy resins and polyvinyl acetal resins are preferred, and phenoxy resins are more preferred from the viewpoint of enhancing the flexibility of the cured product and contributing to adhesion. These may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.

The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 800,000, more preferably in the range of 10,000 to 200,000, still more preferably in the range of 15,000 to 150,000, and in the range of 20,000 to 100,000. Is even more preferred. If it is smaller than this range, the effects of improving the film forming ability and the mechanical strength tend not to be sufficiently exhibited. If it is larger than this range, the compatibility with the epoxy resin tends to be lowered. In addition, the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. Two or more phenoxy resins may be mixed and used. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Examples of commercially available products include 1256, 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation, and YX6954 (bisphenol manufactured by Mitsubishi Chemical Corporation). Acetophenone skeleton-containing phenoxy resin), FX280, FX293 manufactured by Nippon Steel Chemical Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 manufactured by Japan Epoxy Resin Co., Ltd., and the like.

Specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, and Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series and the like. Specific examples of the polyimide resin include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Also, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A 2006-37083), a polysiloxane skeleton-containing polyimide (JP 2002-2002). And modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386. Specific examples of the polyamideimide resin include polyamideimides “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. In addition, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned. Specific examples of the polyethersulfone resin include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.

The content of the thermoplastic resin is not particularly limited, but from the viewpoint of preventing the resin composition film from increasing in viscosity and becoming difficult to embed the wiring pattern on the substrate, the nonvolatile content in the resin composition is not limited. 30 mass% or less is preferable with respect to 100 mass% of minutes, 20 mass% or less is more preferable, and 10 mass% or less is still more preferable. Further, from the viewpoint of improving the flexibility of the cured product and adjusting the viscosity of the varnish, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 3% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. % Or more is more preferable.

<(G) Curing accelerator>
When the resin composition of the present invention further contains (G) a curing accelerator, the resin composition can be efficiently cured. Although it does not specifically limit as a hardening accelerator, An imidazole type hardening accelerator, an amine type hardening accelerator, an organic phosphine compound, an organic phosphonium salt compound, etc. are mentioned. These may be used alone or in combination of two or more.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Feni Louis imidazolium 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′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-be Examples thereof include imidazole compounds such as benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. These may be used alone or in combination of two or more.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5 , 4, 0) -undecene (hereinafter abbreviated as DBU) and the like. These may be used alone or in combination of two or more.

Examples of organic phosphine compounds and organic phosphonium salt compounds include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (trade name of Hokuko Chemical Co., Ltd.). . These may be used alone or in combination of two or more.

The content of the curing accelerator is not particularly limited, and depends on the epoxy resin and phenolic curing agent to be used, but from the viewpoint of improving the storage stability, with respect to 100% by mass of the nonvolatile content in the resin composition, 3 mass% or less is preferable and 2 mass% or less is more preferable. Moreover, 0.01 mass% or more is preferable with respect to 100 mass% of non volatile matters in a resin composition from a viewpoint of shortening hardening time and reducing hardening temperature.

<(H) Flame retardant>
When the resin composition of the present invention further contains (H) a flame retardant, the resin composition can be made flame retardant and safety can be enhanced. As the flame retardant, an organophosphorus flame retardant is preferable from the viewpoint that it does not contain a halogen atom and has high flame retardancy. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno. Reefos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Hokuko Chemical Co., Ltd., Clariant Phosphorus ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 manufactured by Toto Kasei Co., Ltd., and FX310, and phosphorus-containing phenoxy such as ERF001 manufactured by Toto Kasei Co., Ltd. Examples thereof include resins.

<Other ingredients>
The resin composition of the present invention can optionally contain various resin additives other than those described above within the range where the effects of the present invention are exhibited. Examples of resin additives include colorants other than blue colorants, organic fillers such as silicon powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, and polymer-based antifoaming agents. Agents or leveling agents, silane coupling agents, triazole compounds, thiazole compounds, triazine compounds, porphyrin compounds and other adhesion-imparting agents, rubber particles, maleimide compounds, bisallyl nadiimide compounds, vinyl benzyl resins, vinyl benzyl ether resins, etc. Can be mentioned.

The resin composition of the present invention is preferably used as a resin composition for a solder resist, but has a wide range of prepregs, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-filling resins, etc. Can be used for

The resin composition of the present invention may be applied as an ink to a circuit board or may be used as a dry film.

<Ink>
When using as an ink, a resin composition can be apply | coated to a circuit board using a method well-known to those skilled in the art. For example, by applying ink to a predetermined portion of the circuit board and drying the coated surface, a circuit board having the entire surface or a part of the surface protected with ink can be obtained. The drying conditions can be set as appropriate by those skilled in the art depending on the type of ink to be used, but at least the conditions under which the organic solvent constituting the ink is sufficiently dried and the resin composition is sufficiently heat-cured. It is necessary to be. It is preferable to dry at 100 to 200 ° C. for 1 to 120 minutes. Although the thickness of the surface protective film formed is not specifically limited, 5-100 micrometers is preferable. The type of circuit board whose surface is protected by the resin composition of the present invention is not particularly limited.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (hereinafter referred to as MEK), cyclohexanone, acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and cellosolve. Carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These may be used alone or in combination of two or more.

<Dry film>
When used as a dry film, the resin composition is made into an adhesive film using a method known to those skilled in the art. For example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied to a support using a die coater, and the organic solvent is further dried by heating or hot air blowing. It can manufacture by forming a resin composition layer.

Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, and more preferably 5% by mass or less. As drying conditions, suitable drying conditions can be appropriately set by simple experiments. Although depending on the amount of the organic solvent in the varnish, it is preferable to dry the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for 3 to 10 minutes.

The thickness of the resin composition layer formed in the adhesive film is preferably 1 to 90 μm, more preferably 3 to 80 μm, still more preferably 5 to 70 μm, still more preferably 10 to 60 μm, and still more preferably 15 to 55 μm, 20-50 micrometers is especially preferable and 25-45 micrometers is especially preferable.

Examples of the support used for the adhesive film of the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. The plastic film is mentioned. As the plastic film, PET is particularly preferable. A metal foil such as a copper foil or an aluminum foil can be used as a support, and an adhesive film with a metal foil can be obtained. Further, the support may be subjected to a release treatment in addition to the mat treatment and the corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

The support in the present invention is peeled off after being laminated on an inner layer circuit board or the like, or after forming an insulating layer by heat curing. If the support is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing step can be prevented, and the surface smoothness of the insulating layer after curing can be improved. In the case of peeling after curing, the support is preferably subjected to a release treatment in advance. The resin composition layer formed on the support is preferably formed so that the area of the resin composition layer is smaller than the area of the support.

A plastic film similar to the support can be further laminated as a protective film on the surface of the resin composition layer on which the support is not in close contact. The protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. Although the thickness of a protective film is not specifically limited, 1-40 micrometers is preferable. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be wound and stored in a roll.

The adhesive film of the present invention can also be used as a prepreg by impregnating the resin composition of the present invention into a sheet-like reinforcing substrate by a hot melt method or a solvent method and heating and semi-curing it. As the sheet-like reinforcing substrate, it is preferable to use a material made of fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers.

In the hot melt method, without dissolving the resin in an organic solvent, the resin is once coated on the resin and a coated paper having good releasability, and then laminated on a sheet-like fiber substrate, or directly applied by a die coater. Thus, a prepreg is manufactured. Similarly to the adhesive film, the solvent method is a method in which a sheet-like fiber base material is immersed in a resin varnish obtained by dissolving a resin in an organic solvent, the resin varnish is impregnated into the sheet-like fiber base material, and then dried.

After forming the insulating layer, the surface of the insulating layer is irradiated with a laser beam to form a via hole for establishing conduction between the layers. The size of the opening of the via hole is selected depending on the fineness of the component to be mounted, but the top diameter is preferably in the range of 30 to 500 μm. Examples of the laser light source include a carbon dioxide laser, a YAG laser, and an excimer laser, and a carbon dioxide laser is particularly preferable from the viewpoint of processing speed and cost. After the via hole is formed, a desmear process is performed for the purpose of removing the via bottom smear. The desmear treatment in the present invention can be carried out by various known methods, and examples thereof include a dry method using plasma and a wet method using an oxidant solution. In particular, a wet method using an oxidant solution is preferable because of its versatility and high throughput. When performing desmear treatment with an oxidant solution, it is preferable to perform a swelling treatment with a swelling solution, an oxidation treatment with an oxidant solution, and a neutralization treatment with a neutralization solution in this order. Examples of the swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth SBU) and Swelling Dip Securiganth SBU (manufactured by Atotech Japan Co., Ltd.). The swelling treatment is preferably performed by attaching the insulating layer to the swelling liquid heated to 60 to 80 ° C. for 5 to 10 minutes. The oxidant solution is preferably an aqueous alkaline permanganate solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with the alkaline permanganate aqueous solution is preferably performed at 60 to 80 ° C. for 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include “Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd., “Dosing Solution Securigans P”, and the like. Neutralization treatment with a neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

<Multilayer printed wiring board>
Especially the adhesive film of this invention can be used suitably for manufacture of a multilayer printed wiring board. Specifically, first, the adhesive film of the present invention is bonded to one side or both sides of a circuit board prepared in advance using a method such as lamination with a vacuum laminator or press lamination with a metal plate. Subsequently, the support is peeled off, the exposed resin composition layer is cured, and finally, a multilayer printed wiring board can be obtained by obtaining conduction between the layers by forming via holes. The pressure bonding conditions at this time can be easily set as appropriate by those skilled in the art depending on the type of adhesive film used. Lamination is preferably performed under reduced pressure at a temperature of 100 to 200 ° C., a pressure of 1 to 40 kgf / cm ² , a time of 10 seconds to 3 minutes, and an air pressure of 20 mmHg or less. The laminating method may be a batch method or a continuous method using a roll. The curing conditions can be appropriately set by those skilled in the art as appropriate depending on the type of the resin composition layer to be used. However, it is necessary that at least the resin composition is sufficiently heat-cured. It is preferable to cure at ~ 200 ° C for 1 to 120 minutes. The same operation can be repeated. In addition, the circuit board to be used can be a single-sided circuit board or a double-sided circuit board that can be combined at the same time. Furthermore, a rigid circuit board using a glass epoxy board or the like and a flexible circuit board are combined to manufacture a flex-rigid circuit board. You can also.

<Semiconductor device>
Furthermore, the semiconductor device of the present invention can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device is manufactured by bonding a semiconductor element to the connection electrode portion on the multilayer printed wiring board. The mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like.

In addition, multilayer printed wiring boards used in semiconductor packages are produced by alternately forming conductor circuits and build-up layers on the core substrate, and the outermost layer is a solder resist layer for protecting the conductor circuits Form. However, due to the difference in material properties, after applying a thermal history such as solder reflow, if a thermal shock test was performed, there was a problem that a crack occurred in the solder resist layer, and that the crack caused damage to the build-up layer. . In order to solve such a problem, for example, in the patent document (Japanese Patent Laid-Open No. 2007-197706), by using a cyanate ester having a low linear thermal expansion coefficient and excellent in heat resistance, thermal shock resistance, and moisture resistance reliability, In the literature (Japanese Patent Laid-Open No. 2007-201453), a method for solving the problem by suppressing the difference in linear expansion coefficient between the insulating layer and the solder resist layer is disclosed. The high reliability required was not satisfactory.

Therefore, by making the resin composition that constitutes the solder resist layer and the resin composition that constitutes the build-up layer substantially the same configuration, it becomes possible to provide a multilayer printed wiring board in which no cracks occur in the solder resist layer. It was. Details will be described below.

<Solder resist layer>
The resin composition constituting the solder resist layer can be used without any particular limitation. Among these, (a) a resin composition containing an epoxy resin is preferable, and (a) an epoxy resin, (b) a curing agent, and (c) a resin composition containing a thermoplastic resin are more preferable. And a resin composition can be used as an adhesive film.

(a) As an epoxy resin, for example, bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, alicyclic Epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin having butadiene structure, diglycidyl etherified product of bisphenol, diglycidyl ether of naphthalenediol , Glycidyl etherified products of phenols, diglycidyl etherified products of alcohols, and alkyl-substituted products, halides and hydrogenated products of these epoxy resins, etc. And the like. These can use 1 type (s) or 2 or more types.

Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, epoxy having a butadiene structure from the viewpoint of improving heat resistance, insulation reliability, and adhesion to metal foil Resins are preferred. Specifically, for example, liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Mitsubishi Chemical Corporation), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by DIC Corporation), naphthalene type 4 Functional epoxy resins (“HP4700” and “HP4710” manufactured by DIC Corporation), naphthol type epoxy resins (“ESN-475V” manufactured by Nippon Steel Chemical Co., Ltd.), and epoxy resins having a butadiene structure (Daicel Chemical Industries, Ltd.) ) "PB-3600"), epoxy resins having a biphenyl structure ("NC3000H", "NC3000L", manufactured by Nippon Kayaku Co., Ltd., "YX4000" manufactured by Mitsubishi Chemical Corporation)), and the like.

(a) From the viewpoint of improving mechanical properties, the upper limit of the content of the epoxy resin is preferably 40% by mass or less, more preferably 30% by mass or less, when the nonvolatile content in the resin composition is 100% by mass. 20 mass% or less is still more preferable. On the other hand, the lower limit of the content of the epoxy resin is preferably 1% by mass or more when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of improving heat resistance and improving adhesion to the metal foil. More preferably, it is more preferably 5% by mass or more.

(b) As the curing agent, for example, an amine curing agent, a guanidine curing agent, an imidazole curing agent, a phenol curing agent, a naphthol curing agent, an acid anhydride curing agent, or an epoxy adduct or microencapsulation thereof. And active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and the like. These can use 1 type (s) or 2 or more types.

Among these, from the viewpoint of improving heat resistance and improving adhesion to the base copper, a phenolic curing agent and a naphtholic curing agent are preferable, and a triazine skeleton-containing phenolic curing agent and a naphtholic curing agent are more preferable.

Specific examples of the phenol-based curing agent and naphthol-based curing agent include, for example, MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH (manufactured by Nippon Kayaku Co., Ltd.) ), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), TD2090 (manufactured by DIC Corporation), and the like. Specific examples of the triazine skeleton-containing phenolic curing agent include LA3018, LA7052, LA7054, LA1356 (manufactured by DIC Corporation) and the like.

Active ester-based curing agents generally include compounds having two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. Is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like. The active ester compound can use 1 type (s) or 2 or more types. As an active ester compound, the active ester compound currently disclosed by Unexamined-Japanese-Patent No. 2004-277460 may be used, and a commercially available thing can also be used. Examples of commercially available active ester compounds include those containing a dicyclopentadienyl diphenol structure, EXB-9451, EXB-9460 (manufactured by DIC Corporation), DC808, phenol novolac as an acetylated product of phenol novolac. YLH1026 (Mitsubishi Chemical Co., Ltd.), etc. are mentioned as a benzoylation product.

Specific examples of the benzoxazine-based curing agent include Fa, Pd (manufactured by Shikoku Kasei Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.

In the case of (a) epoxy resin and (b) curing agent, the number of phenolic hydroxyl groups of the curing agent is 0.3 when the number of epoxy groups of the epoxy resin is 1 in the case of a phenolic curing agent or a naphthol curing agent. A ratio in the range of -2.0 is preferable, and a ratio in the range of 0.4-1.0 is more preferable. If the ratio of the reactive groups is outside this range, the mechanical strength and heat resistance of the cured product tend to decrease.

(c) The thermoplastic resin is blended for the purpose of imparting appropriate flexibility to the cured composition, for example, phenoxy resin, polyvinyl acetal resin, polyimide, polyamideimide, polyethersulfone. And polysulfone. These can use 1 type (s) or 2 or more types.

(c) From the viewpoint of improving heat resistance, the content of the thermoplastic resin is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass when the nonvolatile content in the resin composition is 100% by mass. % Or less is more preferable. Further, from the viewpoint of increasing the viscosity of the resin composition to obtain film thickness uniformity, when the nonvolatile content in the resin composition is 100% by mass, 0.5% by mass or more is preferable, and 1% by mass or more is preferable. More preferred is 3% by mass.

Specific examples of the phenoxy resin include, for example, FX280 and FX293 manufactured by Nippon Steel Chemical Co., Ltd., YX8100, YL6954, YL6974, YL7213, YL6794, YL7553, and YL7482 manufactured by Mitsubishi Chemical Corporation.

The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and specific examples of the polyvinyl acetal resin include those manufactured by Denki Kagaku Kogyo Co., Ltd., Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. ) Made S-Rec BH series, BX series, KS series, BL series, BM series and the like.

Specific examples of the polyimide include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Also, a linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A 2006-37083), a polysiloxane skeleton-containing polyimide (JP 2002-2002). And modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386.

Specific examples of the polyamide imide include polyamide imides “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. In addition, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. may be mentioned.

Specific examples of polyethersulfone include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

Specific examples of polysulfone include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers, Inc.

The resin composition may further contain (d) a curing accelerator from the viewpoint of efficiently curing the epoxy resin and the curing agent. Examples of such curing accelerators include imidazole compounds, pyridine compounds, and organic phosphine compounds. Specific examples include 2-methylimidazole, 4-dimethylaminopyridine, triphenylphosphine, and the like. be able to. These can use 1 type (s) or 2 or more types. (d) When using a hardening accelerator, it is preferable to use in 0.1-3.0 mass% with respect to an epoxy resin.

The resin composition may further contain (e) an inorganic filler from the viewpoint of reducing the thermal expansion coefficient of the insulating layer. Examples of the inorganic filler include silica, alumina, mica, mica, silicate, barium sulfate, magnesium hydroxide, titanium oxide and the like, and silica and alumina are preferable, and amorphous silica, fused silica, crystalline silica, Silica such as synthetic silica and hollow silica is preferred. The silica is preferably spherical. These can use 1 type (s) or 2 or more types.

The upper limit of the average particle size of the inorganic filler is preferably 5 μm or less, more preferably 4 μm or less, further preferably 3 μm or less, even more preferably 2 μm or less, and even more preferably 1.5 μm or less, from the viewpoint of improving the insulation reliability. Is more preferable, and 1 μm or less is particularly preferable. On the other hand, the lower limit of the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, and still more preferably 0.1 μm or more from the viewpoint of improving dispersibility. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba Ltd. can be used.

The upper limit of the content of the inorganic filler in the resin composition is 85% by mass or less when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of preventing a decrease in mechanical strength of the cured product. Preferably, 80 mass% or less is more preferable, 75 mass% or less is further more preferable, and 70 mass% or less is still more preferable. On the other hand, the lower limit of the content of the inorganic filler in the resin composition is from the viewpoint of lowering the coefficient of thermal expansion, from the viewpoint of improving the elastic modulus, and from the viewpoint of imparting rigidity to the prepreg. When the nonvolatile content is 100% by mass, it is preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more.

In order to improve moisture resistance, dispersibility, etc., the inorganic filler may be subjected to a surface treatment with a surface treatment agent or the like. For example, as a silane coupling agent, aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-2 (aminoethyl) aminopropyl trimethoxysilane, etc. Aminosilane coupling agents, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. Epoxysilane coupling agents, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane and other mercaptosilane coupling agents, methyltrimethoxysilane, Silane coupling agents such as Tadecyltrimethoxysilane, Phenyltrimethoxysilane, Methacryloxypropyltrimethoxysilane, Imidazolesilane, Triazinesilane, Hexamethyldisilazane, Hexaphenyldisilazane, Dimethylaminotrimethylsilane, Trisilazane, Cyclotri And organosilazane compounds such as silazane and 1,1,3,3,5,5-hexametacyclotrisilazane. Further, as titanate coupling agents, butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecyl) Phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phospha To titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tridodecylbenzenesulfonyl titanate, Examples thereof include isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-amidoethyl / aminoethyl) titanate, and the like. These can use 1 type (s) or 2 or more types.

The resin composition includes a bismaleimide-triazine resin, an acrylic resin, a maleimide compound, a bisallylnadiimide compound, a vinyl benzyl resin, a vinyl benzyl ether resin, a block as long as the effects of the present invention are exhibited as necessary. Thermosetting resins other than epoxy resins such as isocyanate compounds can also be blended. These can use 1 type (s) or 2 or more types. As maleimide resins, BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (manufactured by KEI Kasei Co., Ltd.), ANILIX-MI (Mitsui Chemical Fine) BANI-M, BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.) as a vinyl benzyl resin, V5000 (manufactured by Showa Polymer Co., Ltd.), vinyl benzyl ether resin V1000X, V1100X (manufactured by Showa Polymer Co., Ltd.).

The resin composition can contain a flame retardant as long as the effect of the present invention is exhibited as necessary. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Fine Techno. Reefos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ manufactured by Hokuko Chemical Co., Ltd., Clariant Phosphoric acid ester compounds such as OP930 made by Daihachi Chemical Co., Ltd., PX200 made by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 made by Nippon Steel Chemical Co., Ltd., FX310 etc., phosphorus such as ERF001 made by Toto Kasei Co., Ltd. Examples thereof include phenoxy resin. Examples of the organic nitrogen-containing phosphorus compound include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd. As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308, B manufactured by Sakai Kogyo Co., Ltd. And aluminum hydroxide such as -303 and UFH-20. These can use 1 type (s) or 2 or more types.

The resin composition may contain solid rubber particles for the purpose of increasing the mechanical strength of the cured product and for the purpose of stress relaxation as long as the effects of the present invention are exhibited. Solid rubber particles do not dissolve in the organic solvent when preparing the resin composition, are not compatible with the components in the resin composition such as epoxy resin, and exist in a dispersed state in the varnish of the resin composition Those that do are preferred. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles. Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer. Examples include a three-layer structure in which the shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, (Ganz Kasei Co., Ltd. trade name), and Metabrene KW-4426 (Mitsubishi Rayon Co., Ltd. trade name). Specific examples of acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of styrene butadiene rubber (SBR) particles include XSK-500 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Methbrene W300A (average particle size 0.1 μm), W450A (average particle size 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

Other components can be blended in the resin composition as necessary. Other components include, for example, fillers such as silicone powder, nylon powder, and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based, polymer-based antifoaming agent or leveling agent, imidazole-based, Examples thereof include adhesion imparting agents such as thiazole, triazole, and silane coupling agents, and colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which a compounding component is added with a solvent or the like as necessary and mixed using a stirring and heating dissolution apparatus or the like. The stirring and heating dissolution apparatus is not particularly limited, but a stirring and heating dissolution apparatus equipped with a high-speed rotary blade such as a homogenizer or a disperser blade is preferable in order to perform uniform dissolution faster. Specific examples of the stirring and heating dissolution apparatus include T.W. K homomixer, T.W. K. Homo disperse, T.W. K. Combimix, T. K. Hibis Disper Mix (above, product name manufactured by Primix Co., Ltd.), CLEARMIX (product name manufactured by M Technique Co., Ltd.), vacuum emulsification stirrer (product name manufactured by Mizuho Industry Co., Ltd.), vacuum mixing device “Nerimaze” DX "(trade name, manufactured by Mizuho Industry Co., Ltd.), BDM twin screw mixer, CDM concentric twin screw mixer, PD mixer (above, trade name manufactured by Inoue Seisakusho Co., Ltd.).

The adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.

Examples of the organic solvent include ketones such as acetone, MEK, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and carbitols such as cellosolve and butyl carbitol. , Aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.

Although the drying conditions are not particularly limited, the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, and more preferably 5% by mass or less. As drying conditions, suitable drying conditions can be appropriately set by simple experiments. Although depending on the amount of the organic solvent in the varnish, it is preferable to dry the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for 3 to 10 minutes.

The thickness of the resin composition layer formed in the adhesive film is preferably 10 to 100 μm, more preferably 15 to 90 μm, still more preferably 20 to 80 μm, still more preferably 25 to 70 μm, still more preferably 30 to 65 μm, 35-60 micrometers is especially preferable and 40-55 micrometers is especially preferable.

Examples of the support used for the adhesive film of the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and the like. The plastic film is mentioned. As the plastic film, PET is particularly preferable. A metal foil such as a copper foil or an aluminum foil can be used as a support, and an adhesive film with a metal foil can be obtained. Further, the support may be subjected to a release treatment in addition to the mat treatment and the corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. Although the thickness of a support body is not specifically limited, 10-150 micrometers is preferable and 25-50 micrometers is more preferable.

The support in the present invention is peeled off after being laminated on an inner layer circuit board or the like, or after forming an insulating layer by heat curing. If the support is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing step can be prevented, and the surface smoothness of the insulating layer after curing can be improved. In the case of peeling after curing, the support is preferably subjected to a release treatment in advance. The resin composition layer formed on the support is preferably formed so that the area of the resin composition layer is smaller than the area of the support.

A plastic film similar to the support can be further laminated as a protective film on the surface of the resin composition layer on which the support is not in close contact. The protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment. The release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent. Although the thickness of a protective film is not specifically limited, 1-40 micrometers is preferable. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be wound and stored in a roll.

In addition, the prepreg which impregnated the above-mentioned resin composition in the sheet-like reinforcement base material may be sufficient as a resin composition layer. As the sheet-like reinforcing substrate, for example, a glass cloth, an aramid fiber, or the like that is commonly used as a prepreg fiber can be used. The prepreg can be formed by impregnating a resin composition with a sheet-like reinforcing base material by a hot melt method or a solvent method and semi-curing by heating. In addition, the hot melt method, without dissolving the resin composition in an organic solvent, once coated the resin composition on the resin composition and good peelable coated paper, and laminate it on a sheet-like reinforcing substrate, Or it is the method of manufacturing a prepreg by coating directly with a die coater. The solvent method is a method in which a sheet-like reinforcing base material is immersed in a varnish obtained by dissolving a resin composition in an organic solvent, the varnish is impregnated into the sheet-like reinforcing base material, and then dried.

<Build-up layer>
The resin composition constituting the build-up layer can be used without any particular limitation, but it reduces the difference in thermal expansion coefficient between the build-up layer and the solder resist layer, thereby reducing stress distortion and preventing cracks. Therefore, it is preferable that 97% by mass or more of the nonvolatile component in the resin composition of the solder resist layer and the nonvolatile component in the resin composition of the build-up layer are the same component.

<Multilayer printed wiring board>
A method for producing a multilayer printed wiring board using the buildup layer and the solder resist layer produced as described above will be described. The “inner circuit board” is a circuit board having a conductor layer formed on one or both sides of a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. In addition, an intermediate product in which an insulating layer and a conductor layer are to be formed.

The build-up layer can be formed by laminating an adhesive film on the inner circuit board and thermosetting the resin composition layer of the adhesive film to form an insulating layer. For example, an adhesive film is stacked on one side or both sides of a circuit board, and a vacuum press is performed by heating and pressing under reduced pressure using a metal plate such as a SUS mirror plate. The pressure during pressing is preferably 5 to 40 kgf / cm 2 (49 × 104 to 392 × 104 N / m 2), the temperature during pressing is preferably 120 to 180 ° C., and the pressing time is preferably 20 to 200 minutes. Heating and pressurization can be performed by pressing a heated metal plate such as a SUS mirror plate from the plastic film side, but the adhesive film is sufficient for the circuit irregularities of the circuit board, not directly pressing the metal plate. It is preferable to press through an elastic material such as heat-resistant rubber so as to follow.

It can also be produced using a vacuum laminator. In this case, the adhesive film is heated and pressurized under reduced pressure, and the adhesive film is laminated on the circuit board. The laminate preferably has a temperature of 70 to 140 ° C., a pressure of 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and a time of 10 to 300 seconds. . The air pressure is preferably reduced under a reduced pressure of 20 mmHg (26.7 hPa) or less. After the laminating step, the laminated adhesive film is preferably smoothed by hot pressing with a metal plate. The smoothing step is performed by heating and pressurizing the adhesive film with a metal plate such as a heated SUS mirror plate under normal pressure (atmospheric pressure). As heating and pressurizing conditions, the same conditions as in the laminating step can be used. The laminating step and the smoothing step can be continuously performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like. After the laminating process or the smoothing process, a thermosetting process is performed. In the thermosetting step, the resin composition is thermoset to form an insulating layer. Although the thermosetting conditions vary depending on the type of the resin composition, the curing temperature is preferably 150 to 190 ° C., and the curing time is preferably 15 to 100 minutes.

When a vacuum laminator is used, the support may be peeled after lamination, or the support may be peeled after the insulating layer is formed. Moreover, you may peel a support body after via-hole formation. Peeling may be carried out manually or mechanically by an automatic peeling device.

Next, a laser beam is irradiated onto the surface of the insulating layer to form a via hole for establishing conduction between the layers. The size of the opening of the via hole is selected depending on the fineness of the component to be mounted, but the top diameter is preferably in the range of 30 to 500 μm. Examples of the laser light source include a carbon dioxide laser, a YAG laser, and an excimer laser, and a carbon dioxide laser is particularly preferable from the viewpoint of processing speed and cost. In the case of using a carbon dioxide laser device, laser light having a wavelength of 9.3 to 10.6 μm is generally used. Further, the number of shots is selected from 1 to 10 shots, although it varies depending on the depth and hole diameter of the via hole to be formed. From the viewpoint of increasing the via processing speed and improving the productivity of the circuit board, 1 to 5 shots are preferable, and 1 to 3 shots are more preferable. The energy of the laser beam when using the carbon dioxide laser device depends on the number of shots, the depth of the blind via, and the thickness of the support, but is preferably set to 0.5 mJ or more, more preferably 1 mJ or more, and further Preferably, it is set to 2 mJ or more. The upper limit is preferably 20 mJ or less, more preferably 15 mJ or less, still more preferably 10 mJ or less, and even more preferably 5 mJ or less. If the energy of the laser beam is too high, the underlying conductor layer of the via hole is likely to be damaged. Therefore, it is desirable to select an optimum energy value within the above range according to the number of shots. In addition, when processing with multiple shots, burst mode, which is a continuous shot, tends to accumulate processing heat in the hole and tends to cause differences in via processability, so multiple shots with time intervals The cycle mode is preferred. The pulse width of the laser beam used for irradiation is not particularly limited, and can be selected in a wide range from a middle range of 28 μs to a short pulse of about 4 μs. Is said to be excellent in the via processing shape. Examples of commercially available carbon dioxide laser devices include Mitsubishi Electric Corporation “ML605GTWII”, Hitachi Via Mechanics Corporation “LC-G Series”, Matsushita Welding System Co., Ltd. “YB-HCS301”, and the like. Can be mentioned.

In manufacturing a circuit board, generally, after forming a via hole, a desmear process is performed for the purpose of removing a via bottom smear and roughening a resin surface. The desmear treatment in the present invention can be carried out by various known methods, preferably a dry method using plasma and a wet method using an oxidant solution, which are particularly versatile and throughput. Since it is high, a wet method using an oxidant solution is preferably used.

When performing desmear treatment with an oxidant solution, it is preferable to perform a swelling treatment with a swelling solution, an oxidation treatment with an oxidant solution, and a neutralization treatment with a neutralization solution in this order. Examples of the swelling liquid include Swelling Dip Securiganth P (Swelling Dip Securiganth SBU) and Swelling Dip Securiganth SBU (manufactured by Atotech Japan Co., Ltd.). The swelling treatment is preferably performed by attaching the insulating layer to the swelling liquid heated to 60 to 80 ° C. for 5 to 10 minutes. The oxidant solution is preferably an aqueous alkaline permanganate solution, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with the alkaline permanganate aqueous solution is preferably performed by attaching at 60 to 80 ° C. for 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include “Concentrate Compact CP” manufactured by Atotech Japan Co., Ltd., “Dosing Solution Securigans P”, and the like. Neutralization treatment with a neutralizing solution is performed by immersing in a neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.

As the plasma desmear apparatus, commercially available apparatuses such as “Omi” manufactured by Sugawara Eugleite Co., Ltd. and atmospheric pressure plasma treatment apparatus manufactured by Sekisui Chemical Co., Ltd. can be used.

After the desmear process, circuit formation and via conduction are performed by a semi-additive process. In the semi-additive process, first, a seed layer is formed by performing electroless copper treatment using a palladium catalyst or the like on the via bottom, via wall surface, and entire resin surface after desmear treatment. The thickness of the seed layer is preferably 0.1 μm to 2 μm. If the seed layer is too thin, the connection reliability at the time of subsequent electroplating tends to decrease.If the seed layer is too thick, the etching amount when the seed layer between the wirings is later flash-etched must be increased. There is a tendency that the damage given to the wiring becomes large. The electroless copper treatment is performed by depositing metallic copper on the resin surface by the reaction between copper ions and a reducing agent. Examples of the electroless copper plating include “MSK-DK” manufactured by Atotech Japan Co., Ltd., “Sulcup PEA ver. 4” manufactured by Uemura Kogyo Co., Ltd., and the like.

After the electroless copper plating, a dry film resist for plating formation is thermocompression-bonded on the electroless copper plating by a hot roll laminator. The thickness of the dry film resist must be in a range higher than the wiring height after electrolytic copper plating, and a thickness of 5 to 30 μm is preferably used. If it is 5 μm or less, the dry film resist tends to be wrinkled, and if it is 30 μm or more, the photosensitivity and developability tend to decrease. As dry film resist, "Sunfort" series made by Asahi Kasei Co., Ltd., "ALPHO" series made by Nichigo-Morton Co., Ltd., etc. are preferable because of excellent photosensitivity, developability, adhesion to electroless copper, and tenting properties. Used. After the dry film resist is formed, the dry film resist is exposed through a mask on which a wiring pattern is drawn. The exposure is performed using an actinic ray of 50 to 250 mj / cm 2, although depending on the photosensitivity and thickness of the dry film resist. After the exposure, the support film is peeled off, development is performed using an alkaline aqueous solution, and the unexposed portion of the dry film resist is dissolved or dispersed and removed. Thereafter, if necessary, an operation of removing the development residue of the dry film resist may be performed using plasma or the like. After development, electrolytic copper plating is performed to form wiring and via filling. After electrolytic copper plating, the dry film resist is stripped using an alkaline aqueous solution or an amine stripping agent. Thereafter, the dry film residue on the copper may be removed using means such as plasma treatment as necessary.

After removing the dry film resist, flash etching is performed for the purpose of removing the seed layer between the wirings. The flash etch is performed using an acidic or oxidizing solution such as sulfuric acid and hydrogen peroxide. Specific examples include “SAC” manufactured by Sugawara Eugleite Co., Ltd. and “CPE-800” manufactured by Mitsubishi Gas Chemical Co., Ltd.

After the flash etching, palladium or the like attached to the portion between the wirings is removed as necessary. Palladium removal is preferably performed using an acidic solution such as nitric acid or hydrochloric acid. Specifically, Sugawara Eugelite “PJ” solution may be mentioned.

After the dry film resist is peeled off or after the flash etch process, a post bake process is performed. The post-baking step completely cures the unreacted thermosetting component, thereby further improving the insulation reliability, curing characteristics, and plating adhesion. Although the thermosetting conditions vary depending on the type of the resin composition, the curing temperature is preferably 150 to 240 ° C. and the curing time is preferably 15 to 100 minutes.

Thereafter, an etching process of the copper surface is performed for the purpose of improving the adhesion between the copper wiring and the buildup layer or solder resist layer immediately above the copper wiring. Fine irregularities are formed on the copper surface by the etching process, and the adhesion between the copper wiring and the build-up layer or the solder resist layer is improved by the anchor effect due to the irregularities. Examples of the roughening treatment include “CZ-8100” manufactured by MEC Corporation. The above is the description of the method for forming the buildup layer. If the formation of the insulating layer and the wiring is repeated by the same method, the buildup layer is formed in multiple stages.

After the buildup layer is formed, a solder resist layer is formed as the outermost layer. The solder resist layer may be formed by laminating an adhesive film, or may be formed using a technique such as coating a liquid resin composition.

In the present invention, the adhesive film is laminated on the circuit board, the adhesive film is thermally cured to form the insulating layer, and the operation of forming the opening by the laser can be performed according to the conventional method for forming the buildup layer. it can. Details are as described above.

After the formation of the solder resist layer and its opening, desmearing is preferably performed by the same method as the desmearing of the opening of the buildup layer. Thereafter, the surface of the conductor layer exposed at the bottom of the via hole may be subjected to various known surface treatments for the purpose of improving reliability and mounting accuracy and preventing oxidation of a conductor such as copper. Examples of the surface treatment include heat-resistant preflux treatment, solder leveler treatment, lead-free solder leveler treatment, electroless nickel-gold plating treatment, and electrolytic nickel-gold plating treatment.

In the multilayer printed wiring board thus obtained, 97% by mass or more of the nonvolatile component in the resin composition of the solder resist layer and the nonvolatile component in the resin composition of the build-up layer are the same component. As a result, the difference in linear thermal expansion coefficient is in a certain range, which is excellent in preventing cracks. Specifically, the linear thermal expansion coefficient a (ppm) of 25 to 150 ° C. of the solder resist layer and the linear thermal expansion coefficient b (ppm) of 25 to 150 ° C. of the buildup layer are 12 ≦ a ≦ (b +5) It is preferable that ≦ 30. In particular, the linear thermal expansion coefficient a (ppm) is preferably 25 or less.

From the viewpoint of preventing cracks, the elastic modulus (GPa) of the solder resist layer at 23 ° C. is preferably 7 GPa or more, more preferably 8 GPa or more, and further preferably 9 GPa or more. Further, from the viewpoint of practicality, it is preferably 100 GPa or less, more preferably 50 GPa or less, and further preferably 30 GPa or less.

From the viewpoint of improving the adhesion reliability of the underlying conductor layer, the adhesion strength after the high-temperature and high-humidity test between the solder resist layer and the copper foil is preferably 0.4 kgf / cm or more, and 0.45 kgf / cm or more. Is more preferably 0.5 kgf / cm or more. From the viewpoint of practicality, it is preferably 10 kgf / cm or less, more preferably 5 kgf / cm or less.

<Semiconductor device>
Furthermore, the semiconductor device of the present invention can be manufactured by using the multilayer printed wiring board of the present invention. A semiconductor device is manufactured by bonding a semiconductor element to the connection electrode portion on the multilayer printed wiring board. The mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like.

EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not restrict | limited to these Examples. In the following description, “part” means “part by mass”.

<Measurement method / Evaluation method>
First, various measurement methods and evaluation methods will be described.

<Measurement of surface roughness (Ra value)>
Spray both sides of glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18μm, substrate thickness 0.8mm, Matsushita Electric Works R-1766) with MEC CZ-8100 A roughening treatment (etching amount = 1 μm) was performed on the copper surface, and further CL-8300 was sprayed to carry out a rust prevention treatment on the copper surface. On the other hand, the adhesive films obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were subjected to a temperature laminator MVLP-500 (hereinafter referred to as a vacuum laminator) manufactured by Meiki Seisakusho Co., Ltd. at a temperature of 100 ° C. and a pressure of 7 kgf / cm 2. The both surfaces were simultaneously laminated under a pressure of 5 mmHg or less. Furthermore, smoothing with a SUS end plate was performed continuously under conditions of a temperature of 100 ° C. and a pressure of 5 kgf / cm 2. Thereafter, the resin composition was cured at 180 ° C. for 30 minutes after the PET film was peeled off. Then, it is immersed for 5 minutes at 60 ° C in swelling dip securigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. as a swelling liquid, and then as a roughening liquid, Concentrate Compact P of Atotech Japan Co., Ltd. (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally neutralized with Atotech Japan Co., Ltd. Reduction Sholyshin Securigant P at 40 ° C. for 5 minutes. Soaked. After drying this substrate, using a non-contact type surface roughness meter (WYKO NT3300 manufactured by Becoins Instruments Co., Ltd.) and using a PSI High Mag, a measurement range of 121 μm × 92 μm was randomly measured with a 50 × lens. The surface roughness (Ra value) was determined. In addition, Ra value was made into the average value of 10 points | pieces of all the measurements.

<Measurement of color (L * a * b color system)>
The adhesive films obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were cured at 180 ° C. for 90 minutes, and the cured product was peeled off from the release PET, which was placed on a ceramic standard white plate, and a color difference meter The color (L * a * b color system) was measured with “Color Reader CR-200” manufactured by Konica Minolta Sensing Co., Ltd.

<Measurement of color (Munsell color system)>
The adhesive films obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were cured at 180 ° C. for 90 minutes, and the cured product was peeled off from the release PET, which was placed on a ceramic standard white plate, and a color difference meter The color (Munsell color system) was measured with “Color Reader CR-200” manufactured by Konica Minolta Sensing Co., Ltd.

<Visual evaluation>
The adhesive films obtained in Examples 1 to 7 and Comparative Examples 1 to 5 were cured at 180 ° C. for 90 minutes, the cured product was peeled off from the release PET, and the color was visually confirmed.

<Evaluation of thermal shock resistance>

[Create core substrate]
As a core material, a double-sided copper-clad laminate (“Glass Epoxy Multi R-1766” manufactured by Panasonic Electric Works Co., Ltd., thickness 0.8 mm) was used. First, a total of 100 through-holes having a diameter of 180 μm in 10 rows and 10 columns at a pitch of 400 μm were formed by drilling in a 120 mm × 80 mm core material. A part having 100 through holes was defined as one zone, and a through hole area of 6 zones was provided in 3 rows and 2 columns at a pitch of 25 mm (FIG. 1). After washing with high pressure water, copper plating of the through hole (thickness 20 μm) was performed, and the hole diameter of the through hole after plating was 140 μm. The hole filling ink ("PHP900-IR-10F" manufactured by Yamaei Chemical Co., Ltd.) was printed on this, heat filled to fill the hole, polished on both sides, and after removing unnecessary hole filling ink, lid plating was performed. At this time, polishing and plating were adjusted so that the copper thickness after lid plating (the distance between the top of the lid plating and the core material) was 35 μm. Thereafter, a dry film resist was laminated on both sides of the copper after the lid plating with a hot roll laminator, followed by exposure, peeling of the support, and development with an alkaline aqueous solution. After this was etched with a ferric chloride aqueous solution, the dry film was peeled off with an alkaline aqueous solution. Then, a pad having a diameter of 200 μm and concentric with the through hole was formed on each through hole by the subtractive method (FIG. 2).

[Build-up layer stacking]
The build-up films obtained in Examples 8 to 10 and Comparative Examples 6 to 7 were laminated on the core substrate at the same time using a vacuum laminator at a temperature of 100 ° C., a pressure of 7 kgf / cm 2, and an atmospheric pressure of 5 mmHg or less. Further, hot pressing with a SUS end plate was performed continuously under conditions of a temperature of 100 ° C. and a pressure of 5 kgf / cm 2. Thereafter, the build-up layer was cured at 180 ° C. for 30 minutes after the PET film was peeled off. Next, the surface of the cured buildup layer was roughened with an alkaline oxidant of permanganate, electroless copper and electrolytic copper plating were performed, and post-baking was performed at 180 ° C. for 60 minutes. A pad was formed from this plated copper layer according to a subtractive method. The pad had a diameter of 105 μm and a copper thickness of 10 μm, and 729 pieces of 27 rows and 27 columns were formed at a pitch of 150 μm. It was created in the area where the core substrate had a through hole. (Figs. 3 and 4)

[Lamination of solder resist layer]
The 15 μm or 20 μm solder resist films obtained in Examples 8 to 10 and Comparative Examples 6 to 7 were simultaneously applied to both sides of the buildup layer using a vacuum laminator at a temperature of 100 ° C., a pressure of 7 kgf / cm 2 and an atmospheric pressure of 5 mmHg or less. Laminated. And after peeling of PET film, the soldering resist layer was hardened on 180 degreeC and the conditions for 90 minutes, and the board | substrate for evaluation was created. (Fig. 5)

Using an evaluation substrate (“TSB-51” manufactured by Espec Co., Ltd.), the substrate for evaluation was tested for 1000 cycles at a low temperature bath of −65 ° C., a high temperature bath of 150 ° C., and an exposure time of 5 minutes each. It was. Surface observation was performed on 12 zones of the printed wiring board after the thermal shock, and the total number of cracks was counted. The thermal shock resistance was evaluated as “◯” when no crack occurred and “×” when even one crack occurred.

<Measurement of linear thermal expansion coefficient>
The adhesive films obtained in Examples 8 to 10 and Comparative Examples 6 to 7 were cured at 180 ° C. for 90 minutes, and the cured product was peeled off from the release PET, and this was formed into a test piece having a width of about 5 mm and a length of about 15 mm. The sample was cut and subjected to thermomechanical analysis in a tensile mode using a thermomechanical analyzer Thermo plus TMA 8310 manufactured by Rigaku Corporation. The measurement was performed twice at a load of 1 g and a heating rate of 5 ° C./min. The average linear expansion coefficient from 25 ° C. to 150 ° C. in the second measurement was defined as the thermal expansion coefficient.

<Measurement of elastic modulus>
The adhesive films obtained in Examples 8 to 10 and Comparative Examples 6 to 7 were cured at 180 ° C. for 90 minutes, the cured product was peeled off from the release PET, and the tensile strength of the cured product was measured according to JIS K7127. The elastic modulus at 23 ° C. was determined.

<Measurement of copper foil adhesion after high temperature and high humidity test>
The glossy surface of 3EC-III (electrolytic copper foil, 35 μm) manufactured by Mitsui Mining Co., Ltd. is sprayed with Mec Etch Bond CZ-8100 manufactured by Mec Co., Ltd. to roughen the copper surface (etching amount = 1 μm). Further, CL-8300 was sprayed to carry out a rust prevention treatment on the copper surface. The soldering resist layer (40 μm) used in Examples 8 to 10 and Comparative Examples 6 to 7 was laminated on the roughened surface by a vacuum laminator under the conditions of a temperature of 100 ° C., a pressure of 7 kgf / cm 2, and an atmospheric pressure of 5 mmHg or less. And cured. Further, this test piece was exposed to high temperature and high humidity for 100 hours under the conditions of a temperature of 130 ° C. and a humidity of 85%. Thereafter, an adhesive was applied to the solder resist layer side of the test piece, and was brought into close contact with a 1 mm or more contact plate. A notch was cut into a 10 mm wide and 150 mm long portion from above the copper foil of the test piece on the coating plate, and one end of the copper foil was peeled off at the interface between the solder resist and the copper foil. Grasp one end of the peeled copper foil with a gripper and measure the load when peeling 35mm vertically at a speed of 50mm / min at room temperature (25 ° C) using an Instron universal testing machine. The average value was defined as the adhesion strength.

<Example 1>
21 parts liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation) and 25.5 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) 5 parts of naphthalene-type tetrafunctional epoxy resin (epoxy equivalent 162, “HP-4700” manufactured by DIC Corporation), phenoxy resin (weight average molecular weight 38000, “YL7553BH30” manufactured by Mitsubishi Chemical Corporation) having a nonvolatile content of 30% by mass and MEK 25 parts of a 1: 1 solution of cyclohexanone was dissolved in 8 parts of MEK and 6 parts of cyclohexanone with stirring while heating. Thereto, a phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile content of 60% by mass, phenolic hydroxyl group equivalent 124) 22 parts, naphthol resin having an aralkyl structure (Nippon Steel Chemical Co., Ltd.) ) "SN395" MEK solution having a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts, spherical silica (average particle size 0.5 µm, "SOC2" with aminosilane treatment manufactured by Admatechs) 70 parts, polyvinyl butyral resin 20 parts of a solution (glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd., a 1: 1 solution of ethanol and toluene with a nonvolatile content of 15% by mass), 0.03 part of dimethylaminopyridine, copper phthalocyanine (Pigment Blue 15; 3, Toyo Ink Mfg. Co., Ltd. “FG7351”) 0.5 part is mixed and dispersed uniformly with a high-speed rotary mixer. Fat varnish was prepared. The obtained resin varnish was applied to a release surface of a polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) film whose surface was release-treated with a die coater so as to have a thickness of 40 μm. Drying was carried out at 0 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount, about 2% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 × 336 mm.

<Example 2>
A naphthol resin having an aralkyl structure by changing 22 parts of the phenol novolak-based curing agent of Example 1 (“LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile content of 60% by mass, phenolic hydroxyl group equivalent 124) to 16 parts. (Nippon Chemical Co., Ltd. "SN395" MEK solution with a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts naphthol resin having an aralkyl structure (Nippon Chemical Co., Ltd. "SN485" nonvolatile content) An adhesive film was obtained in the same manner as in Example 1 except that 60 parts by mass of MEK solution and naphtholic hydroxyl group equivalent 215) were changed to 22 parts.

<Example 3>
Adhesive film in the same manner as in Example 1, except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Manufacturing Co., Ltd. “FG7351”) in Example 1 was changed to 1.5 parts. Got.

<Example 4>
Adhesive film in the same manner as in Example 1 except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Manufacturing Co., Ltd. "FG7351") in Example 1 was changed to 0.25 part. Got.

<Example 5>
Adhesive film in the same manner as in Example 1, except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Manufacturing Co., Ltd. “FG7351”) in Example 1 was changed to 0.1 part. Got.

<Example 6>
Except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Manufacturing Co., Ltd. “FG7351”) 0.5 part in Example 1 was changed to 4 parts of Ultramarine Blue (Wako Pure Chemical Industries, Ltd.) In the same manner as in Example 1, an adhesive film was obtained.

<Example 7>
A naphthol resin having an aralkyl structure by changing 22 parts of the phenol novolac curing agent of Example 1 (“LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile content of 60 mass%, phenolic hydroxyl group equivalent 124) to 2 parts. (Nippon Chemical Co., Ltd. "SN395" MEK solution with a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts naphthol resin having an aralkyl structure (Nippon Chemical Co., Ltd. "SN485" nonvolatile content) An adhesive film was obtained in the same manner as in Example 1 except that 60 parts by mass of MEK solution and naphtholic hydroxyl group equivalent 215) were changed to 66 parts.

<Comparative Example 1>
A naphthol resin having an aralkyl structure by changing 22 parts of the phenol novolac-based curing agent of Example 1 (“LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile content of 60 mass%, phenolic hydroxyl group equivalent 124) to 31 parts. (Nippon Steel Chemical Co., Ltd. "SN395" MEK solution with a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts were obtained in the same manner as in Example 1 except that 6 parts were not added.

<Comparative example 2>
A naphthol resin having an aralkyl structure of Example 1 (“SN395” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent of 107) was added to 6 parts of a phenol novolac curing agent (DIC Corporation). “TD-2090” manufactured by MEK solution having a nonvolatile content of 60% by mass, phenolic hydroxyl group equivalent 105) 6 parts were obtained in the same manner as in Example 1 except that the adhesive film was obtained.

<Comparative Example 3>
A naphthol resin having an aralkyl structure of Example 1 (“SN395” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent of 107) is mixed with 6 parts of a biphenyl type phenolic curing agent (Nippon Kayaku). “GPH-103” manufactured by Co., Ltd. An adhesive film was obtained in the same manner as in Example 1 except that it was changed to 10 parts of a cyclohexanone solution having a nonvolatile content of 50% by mass, phenolic hydroxyl group equivalent 231).

<Comparative example 4>
An adhesive film was obtained in the same manner as in Example 1 except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Mfg. Co., Ltd. "FG7351") was not added.

<Comparative Example 5>
An adhesive film was obtained in the same manner as in Example 2 except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Manufacturing Co., Ltd. "FG7351") was not added.

The results are shown in Table 1.

In Examples 1 to 7, the b * value was in the range of −25 to 40, green, and the roughness was 550 nm or less. On the other hand, the b * value did not fall within the range of −25 to 40 in the comparative examples, and none of them could exhibit a green color.

<Example 8>
[Create adhesive film for build-up layer]
21 parts liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation) and 25.5 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) 5 parts of naphthalene type tetrafunctional epoxy resin (epoxy equivalent 162, “HP-4700” manufactured by DIC Corporation), phenoxy resin (weight average molecular weight 38000, “YL7553BH30” manufactured by Japan Epoxy Resins Co., Ltd.) MEK having a nonvolatile content of 30% by mass And 25 parts of cyclohexanone (1: 1 solution) were dissolved in 8 parts of MEK and 6 parts of cyclohexanone with stirring. Thereto, a phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a nonvolatile content of 60% by mass, phenolic hydroxyl group equivalent 124) 22 parts, naphthol resin having an aralkyl structure (Nippon Steel Chemical Co., Ltd.) ) Manufactured "SN395" MEK solution with a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts, spherical silica (average particle size 0.5 μm, "SOC2 with aminosilane treatment" manufactured by Admatechs) 135 parts, polyvinyl butyral resin 20 parts of a solution (Glass transition temperature 105 ° C., “KS-1” manufactured by Sekisui Chemical Co., Ltd., a non-volatile content of 15% by mass of a 1: 1 solution of ethanol and toluene) and 20 parts of dimethylaminopyridine were mixed, and high speed A resin varnish was prepared by uniformly dispersing with a rotary mixer. The obtained resin varnish was applied to a release surface of a polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) film whose surface was release-treated with a die coater so as to have a thickness of 50 μm. Drying was carried out at 0 ° C. (average 100 ° C.) for 6 minutes (residual solvent amount, about 2% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm to obtain a sheet-like adhesive film having a size of 507 × 336 mm.

[Create adhesive film for solder resist layer]
Except for adding 0.5 parts of phthalocyanine copper (Pigment Blue 15; 3, “FG7351” manufactured by Toyo Ink Manufacturing Co., Ltd.) to the build-up layer adhesive film, Similarly, 20 μm and 15 μm adhesive films were obtained.

<Example 9>
[Create adhesive film for build-up layer]
The spherical silica of Example 8 (average particle size 0.5 μm, “SOC2 with aminosilane treatment” manufactured by Admatechs) 135 parts was changed to 150 parts, and naphthol resin having an aralkyl structure (manufactured by Nippon Steel Chemical Co., Ltd.) SN395 ”MEK solution with a nonvolatile content of 60% by mass, naphtholic hydroxyl group equivalent 107) 6 parts active ester resin (“ EXB9460S-65T ”non-volatile content 65% by mass toluene solution with active group equivalent of about 223) 6 The adhesive film was obtained like Example 8 except having changed into the part.

[Create adhesive film for solder resist layer]
Except for adding 0.5 parts of phthalocyanine copper (Pigment Blue 15; 3, Toyo Ink Mfg. Co., Ltd. "FG7351") to the above buildup layer adhesive film, the same as the buildup layer adhesive film Thus, adhesive films for 20 um and 15 um solder resist layers were obtained.

<Example 10>
[Create adhesive film for build-up layer]
Except that 135 parts of spherical silica of Example 8 (average particle size 0.5 μm, “SOC2 with aminosilane treatment” manufactured by Admatechs) was changed to 70 parts, the same procedure as in Example 8 was performed for the build-up layer. An adhesive film was obtained.

[Create adhesive film for solder resist layer]
Solder resist is the same as in Example 5 except that 0.5 part of phthalocyanine copper (Pigment Blue 15; 3, “FG7351” manufactured by Toyo Ink Co., Ltd.) is added to the adhesive film for the build-up layer. An adhesive film for the layer was obtained.

<Comparative Example 6>
[Create adhesive film for build-up layer]
The same adhesive film for buildup layers as in Example 10 was used.

[Create adhesive film for solder resist layer]
411 parts of ethyl carbitol acetate, 430 parts of an o-cresol novolac type epoxy resin (epoxy equivalent 215, having 6 phenol nuclei on average in one molecule), and 144 parts of acrylic acid are placed in a flask and stirred for 120 The reaction was carried out at 0 ° C. for 10 hours. Once the reaction product was cooled to room temperature, 288.8 parts of tetrahydrophthalic anhydride was added, heated to 80 ° C. and stirred for 4 hours. The reaction product was cooled again to room temperature, 105 parts of glycidyl methacrylate and 161 parts of propylene glycol methyl ether acetate were added, and the mixture was reacted at 110 ° C. for 6 hours with stirring. The reaction product was cooled to room temperature to obtain a resin solution (A) (nonvolatile content: about 62.9%, acid value: about 70 [KOHmg / g]).

Resin solution (A) 100 parts, biphenyl type epoxy resin (epoxy equivalent 291; “NC-3000H” manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene type epoxy resin (epoxy equivalent 277, manufactured by DIC Corporation) EPICLON HP-7200H ") 13 parts, photopolymerization initiator (Ciba Specialty Chemicals" 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone ") 7 parts, 1 part of photosensitizer (“2,4-diethylthioxanthone” manufactured by Nippon Kayaku Co., Ltd.), 16 parts of acrylic monomer (“M-310” manufactured by Toagosei Co., Ltd.), curing accelerator (Japan Epoxy Resin ( "Epicure DICY-7") 0.5 parts, fine silica ("Aerosil # 200" manufactured by Nippon Aerosil Co., Ltd.) 1 part, spherical silica (average particle size 0) 5 μm, 50 parts of “SOC2” with aminosilane treatment (manufactured by Admatechs) and 0.5 part of phthalocyanine copper (Pigment Blue 15; 3) are mixed and dispersed uniformly with a high-speed rotary mixer to obtain a photocurable resin composition varnish Was made. The adhesive film was obtained by the same method as Example 8 using the obtained varnish. Thereafter, a core layer was prepared in the same manner as in Example 8, and a buildup layer was laminated and cured. Then, the adhesive film for the solder resist layer is laminated on both sides simultaneously under the conditions of a temperature of 100 ° C., a pressure of 7 kgf / cm 2 and an atmospheric pressure of 5 mmHg or less, and is subjected to exposure at 1000 mj / cm 2 and heat curing at 160 ° C. for 90 minutes to form a solder resist layer. A substrate was created. Various evaluations were performed.

<Comparative Example 7>
[Create adhesive film for build-up layer]
The same adhesive film for buildup layers as in Example 10 was used.

[Create adhesive film for solder resist layer]
25 parts of novolak type cyanate ester resin (Lonza Japan, “PT-30” cyanate ester equivalent 124), biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), phenoxy resin (weight) Average molecular weight 38000, "YX8100" manufactured by Japan Epoxy Resins Co., Ltd. 10 parts of a non-volatile content of 30% by mass of MEK and cyclohexanone (1: 1 solution), 10 parts of a curing accelerator ("2-phenyl-4,5- Dihydroxymethylimidazole ”) 0.4 parts, spherical silica (average particle size 0.5 μm,“ SOC2 with aminosilane treatment ”manufactured by Admatechs) 50 parts, and phthalocyanine copper (Pigment Blue 15; 3) 1 part are mixed together. A resin varnish was prepared by uniformly dispersing with a rotary mixer. Using the obtained varnish, a sheet-like adhesive film was obtained in the same manner as in Example 8.

The results are shown in Tables 2 and 3.

Examples 8 to 10 all showed a good thermal shock resistance because the coefficients of linear thermal expansion were close. In Comparative Example 6, cracks occurred even when the solder resist layer was 20 μm. In Comparative Example 7, the copper foil adhesion after the high temperature and high humidity test is weak.

The resin composition containing the naphthol resin and the blue colorant of the present invention provides a halogen-free resin composition for a solder resist that has a low surface roughness of a cured product of the resin composition and exhibits a green color regardless of only the pigment. Now available. Furthermore, an adhesive film, a prepreg, and a multilayer printed wiring board using the same can be provided. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided. Also, by making the resin composition constituting the solder resist layer and the resin composition constituting the build-up layer substantially the same structure, it becomes possible to provide a multilayer printed wiring board in which no cracks occur in the solder resist layer. It was. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

Claims (12)

(A) Naphthol resin represented by formula (1)


(In formula, m is 1-2. N is 1-15.) And (B) The resin composition for soldering resists containing a blue coloring agent. 2. The resin composition according to claim 1, wherein the content of the (A) naphthol resin is 0.001 to 30 mass% when the nonvolatile content in the resin composition is 100 mass%. The resin composition according to claim 1 or 2 , wherein the content of the (B) blue colorant is 0.001 to 10% by mass when the nonvolatile content in the resin composition is 100% by mass. object. The resin composition according to any one of claims 1 to 3 , wherein the blending amount of (B) blue colorant is 0.01 to 1000000 mass% with respect to 100 mass% of (A) naphthol resin. . (A) Naphthol resin is represented by Formula (2)


(In formula, m is 1-2. N is 1-15.) The resin composition of any one of Claims 1-4 characterized by the above-mentioned. Furthermore, (C) an epoxy resin is contained, The resin composition of any one of Claims 1-5 characterized by the above-mentioned. The resin composition according to claim 6 , wherein the content of the epoxy resin (C) is 5 to 50% by mass when the nonvolatile content in the resin composition is 100% by mass. Furthermore (D), characterized in that it contains an inorganic filler, a resin composition according to any one of claims 1-7. Furthermore (E), characterized in that it contains a curing agent ((A) except naphthol resin.) The resin composition according to any one of claims 1-8. Adhesive film resin composition according is a layer formed on a support in any one of claims 1-9. Multilayer printed wiring board having an insulating layer formed by the cured product of the resin composition according to any one of claims 1-9. A semiconductor device in which a semiconductor element is bonded to a connection electrode portion on the multilayer printed wiring board according to claim 11 .