JP2015145498A - resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable for forming an insulating layer of a circuit board, which allows formation of a conductive layer that has high peeling strength even if an insulating layer obtained by curing the resin composition has low surface roughness degree.SOLUTION: The resin composition comprises: (A) a polyfunctional epoxy resin (excluding a phenoxy resin); (B) a phenolic curing agent and/or an active ester curing agent; (C) a thermoplastic resin selected from a phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamide-imide resin, polyether sulfone resin, and polysulfone resin; (D) an inorganic filler; and (E) at least one quaternary phosphonium curing accelerator selected from a tetrabutylphosphonium decane acid salt, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

Description

  The present invention provides a resin composition suitable for forming an insulating layer of a circuit board such as a multilayer printed wiring board, an insulating film obtained from the resin composition, an insulating resin sheet such as a prepreg, and a cured product of the resin composition. The present invention relates to a circuit board on which an insulating layer is formed.

With recent downsizing and higher performance of electronic devices, further fine wiring of circuit boards is required. When the conductor layer is formed by plating after roughening the surface of the insulating layer, increasing the roughness increases the peel strength, but is disadvantageous for making fine wiring. Therefore, it is desired to simultaneously satisfy the conflicting performance of increasing the peel strength of the conductor layer with the lowest possible roughness.
For example, when an epoxy resin composition containing an epoxy resin, a specific phenolic curing agent, and polyvinyl acetal is used for an insulating layer of a multilayer printed wiring board, the resulting roughened surface has a relatively low roughness. Also disclosed is that it can be adhered to the plated conductor with high adhesion (Patent Document 1).

JP 2007-254710 A

  According to the present invention, in a resin composition suitable for forming an insulating layer of a circuit board, a conductor layer having high peel strength can be formed even if the roughness of the surface of the insulating layer obtained by curing the resin composition is low. It aims at providing a resin composition.

  In view of the above problems, the present inventors paid attention to the influence of the curing accelerator in the resin composition. Then, the present inventors use a combination of a specific curing agent and a specific phosphorus curing agent in a resin composition containing a polyfunctional epoxy resin, a thermoplastic resin, and an inorganic filler. In an insulating layer formed by curing an object, the present invention has been completed by finding that the formed conductor layer has a high peel strength even when the surface of the insulating layer has low roughness. That is, the present invention includes the following contents.

[1] (A) polyfunctional epoxy resin, (B) phenolic curing agent and / or active ester curing agent, (C) thermoplastic resin, (D) inorganic filler, (E) tetrabutylphosphonium decanoate , (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and a resin composition containing one or more quaternary phosphonium-based curing accelerators selected from butyltriphenylphosphonium thiocyanate.
[2] Including the component (E) in a range where the ratio of the mass of the component (E) to the total mass of the non-volatile components of the component (A) and the component (B) is 100: 0.05 to 100: 2. 1] The resin composition according to the above.
[3] The component (B) is contained in a range where the ratio of the epoxy group present in the resin composition and the reactive group of the curing agent of the component (B) is 1: 0.3 to 1: 1 in a molar ratio. The resin composition according to [1] or [2].
[4] The resin composition according to any one of [1] to [3], wherein the content of the component (C) is 1 to 20% by mass when the nonvolatile content of the resin composition is 100% by mass. .
[5] The resin composition according to any one of [1] to [4], wherein the content of the component (D) is 10 to 70% by mass when the nonvolatile content of the resin composition is 100% by mass.
[6]
The resin composition according to any one of [1] to [5] above, wherein the peel strength is 0.4 kgf / cm to 2 kgf / cm, and the surface roughness is 30 nm to 400 nm.
[7] An adhesive film in which the resin composition according to any one of [1] to [6] is layered on a support.
[8] A prepreg in which the resin composition according to any one of [1] to [6] is impregnated in a sheet-like fiber base material.
[9] A circuit board on which an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [6].

  The resin composition of the present invention is suitable for forming an insulating layer on a circuit board, and the insulating layer obtained by curing the resin composition is a conductor layer having a high peel strength even if the surface roughness is low. It can be formed, which is advantageous for the fine wiring of the circuit board.

  The present invention includes (A) a polyfunctional epoxy resin, (B) a phenolic curing agent and / or an active ester curing agent, (C) a thermoplastic resin, (D) an inorganic filler, and (E) a specific curing accelerator. It is a resin composition characterized by containing.

[(A) Multifunctional epoxy resin]
The component (A) polyfunctional epoxy resin in the present invention is not particularly limited as long as the effects of the present invention are achieved. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl -Catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring contained An epoxy resin, a cyclohexane dimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, etc. are mentioned.

  Two or more epoxy resins may be used in combination, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component in the resin composition is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Furthermore, an epoxy resin that is an aromatic epoxy resin that has two or more epoxy groups in one molecule and is liquid at a temperature of 20 ° C, and a solid that has three or more epoxy groups in one molecule and has a temperature of 20 ° C. The aspect which contains a shape-like aromatic epoxy resin is preferable. In addition, the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule | numerator.

  Moreover, when using together a liquid epoxy resin and a solid epoxy resin as an epoxy resin, the mixture ratio (liquid: solid) has the preferable range of 1: 0.1-1: 2 by mass ratio. If the proportion of the liquid epoxy resin is too large beyond this range, the tackiness of the resin composition increases, and when used in the form of an adhesive film, the deaeration during vacuum lamination is reduced and voids are likely to occur. There is a tendency. Moreover, there exists a tendency for the peelability of a protective film and a support film to fall at the time of vacuum lamination, and the heat resistance after hardening to fall. Moreover, it exists in the tendency for sufficient breaking strength to be hard to be obtained in the hardened | cured material of a resin composition. On the other hand, if the proportion of the solid epoxy resin is too large beyond this range, sufficient flexibility cannot be obtained when using it in the form of an adhesive film, and the handleability is lowered. There is a tendency that it is difficult to obtain.

  In the resin composition of the present invention, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is preferably 10 to 50% by mass, more preferably 20 to 45% by mass. Particularly preferred is 25 to 42% by mass. When the content of the epoxy resin (A) is out of this range, the curability of the resin composition tends to decrease.

[(B) Phenolic curing agent and / or active ester curing agent]
The phenol-based curing agent and / or active ester-based curing agent of component (B) in the present invention is not particularly limited as long as the effects of the present invention are exhibited, but each may be used alone or in combination. . In particular, from the viewpoint of mechanical properties of the cured product, a phenolic curing agent is preferable.

  The phenolic curing agent is a compound containing a phenol skeleton or a naphthol skeleton, and has a curing action for an epoxy resin. As the phenolic curing agent, a phenolic curing agent having a novolak structure or a naphthol curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Examples of commercially available products include MEH-7700, MEH-7810, MEH-7785 (Maywa Kasei Co., Ltd.), NHN, CBN, GPH (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Tohto Kasei Co., Ltd.), LA7052, LA7054 (manufactured by Dainippon Ink & Chemicals, Inc.), and the like. The active ester curing agent has an ester group with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, and has a curing action of epoxy resin. Say. Examples of the active ester curing agent include EXB-9460 (manufactured by Dainippon Ink & Chemicals, Inc.), DC808, and YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.).

  In the present invention, the content of the phenolic curing agent and / or active ester curing agent in the resin composition is the total number of epoxy groups of the epoxy resin and the total number of reactive groups of the curing agent present in the resin composition. It is preferable that the ratio is 1: 0.3 to 1: 2, more preferably 1: 0.4 to 1: 1.5. The total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent. The total number of (active hydroxyl group, active ester group) is a value obtained by totaling the values obtained by dividing the solid content mass of each curing agent by the reactive group equivalent for all curing agents. When the content of the curing agent is out of the preferable range, there is a tendency that the heat resistance of the cured product obtained by curing the resin composition becomes insufficient.

[(C) Thermoplastic resin]
The component (C) thermoplastic resin in the present invention is not particularly limited as long as the effects of the present invention are achieved. For example, phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polysulfone resin, etc. Phenoxy resin and polyvinyl acetal resin are preferable, and phenoxy resin is particularly preferable. Two or more thermoplastic resins may be mixed and used. The content of the thermoplastic resin is preferably in the range of 1 to 20% by mass and more preferably in the range of 5 to 15% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. If the content is too small, the flexibility of the cured product tends to decrease. If the content is too large, the viscosity of the resin composition becomes too high and the laminating property decreases, leading to a wiring pattern on the circuit. Tend to be difficult to embed. It is preferable that the weight average molecular weight of a thermoplastic resin is the range of 8000-70000, More preferably, it is 10000-60000, More preferably, it is 20000-60000. If the molecular weight is too small, the peel strength of the conductor layer tends to decrease. If the molecular weight is too large, the roughness tends to increase and the thermal expansion coefficient tends to increase. The weight average molecular weight is measured by 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, novolac 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 Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin, YX6954 (containing bisphenolacetophenone skeleton) manufactured by Japan Epoxy Resin. Phenoxy resin), FX280, FX293 manufactured by Toto Kasei Co., Ltd., YL7553, 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, 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 (as described in JP 2006-37083 A), 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. These various thermoplastic resins may be used in combination of two or more.

[Inorganic filler of (D)]
The component (D) inorganic filler in the present invention is not particularly limited as long as the effects of the present invention are achieved. For example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, carbonate Calcium, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc. Of these, silica such as amorphous silica, fused silica, crystalline silica, and synthetic silica is particularly suitable. The silica is preferably spherical. Two or more inorganic fillers may be used in combination.

  The average particle size of the inorganic filler is preferably 1 μm or less, more preferably 0.8 μm or less, and particularly preferably 0.7 μm or less. When the average particle diameter exceeds 1 μm, the peel strength of the conductor layer formed by plating tends to decrease. If the average particle size of the inorganic filler is too small, when the resin composition is a resin varnish, the viscosity of the varnish tends to increase and the handleability tends to decrease, so the average particle size is 0.05 μm. The above is preferable. 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.

  Inorganic fillers include aminopropylmethoxysilane, aminopropyltriethoxysilane, ureidopropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and N-2 (aminoethyl) amino to improve moisture resistance, dispersibility, and the like. Aminosilane coupling agents such as provirtrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxy (Cyclohexyl) Epoxysilane coupling agents such as ethyltrimethoxysilane, mercaptosilane coupling agents such as mercatopropyltrimethoxysilane, mercatopropyltriethoxysilane, methyltrimethoxysilane, Silane coupling agents such as tadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilane, trisilazane, cyclotri Organosilazane compounds such as silazane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, butyl titanate dimer, titanium octylene glycolate, diisopropoxytitanium bis (triethanolaminate), dihydroxytitanium bislactate, Dihydroxybis (ammonium lactate) titanium, bis (dioctylpyrophosphate) ethylene titanate, bis (dioctylpyrophosphate) oxyacetate Totitanate, tri-n-butoxy titanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, isopropyl trioctanoyl titanate, isopropyl tricumyl phenyl titanate, isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl dimethacrylisostearoyl Titanate, isopropyltri (dioctylphosphate) titanate, isopropyltridodecylbenzenesulfonylthio It may be treated with one or more surface treating agents such as titanate, isopropyltris (dioctylpyrophosphate) titanate, titanate coupling agent of isopropyltri (N-amidoethyl / aminoethyl) titanate.

  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 content of the inorganic filler is preferably in the range of 10 to 70% by mass and more preferably in the range of 15 to 65% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. More preferably, it is -60 mass%. If the content of the inorganic filler is too small, the coefficient of thermal expansion tends to increase. If the content is too large, the flexibility of the insulating resin sheet tends to decrease.

[Quaternary phosphonium curing accelerator]
The component (E) quaternary phosphonium-based curing accelerator in the present invention is not particularly limited as long as the effects of the present invention are exhibited. Here, the quaternary is a functional group selected from an alkyl group, an aralkyl group, and an aryl group. Indicates. Specific examples include quaternary phosphonium thiocyanate and quaternary phosphonium long chain fatty acid salts. In particular, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate are preferable. The lower limit of the content (% by mass) of the component (E) with respect to the total mass of the non-volatile components of the component (A) and the component (B) is preferably 0.05, more preferably 0.07, and further 0.09 Preferably, 0.11 is even more preferred, 0.13 is even more preferred, and 0.15 is particularly preferred. The upper limit of the content (% by mass) of the component (E) relative to the total mass of the non-volatile components of the component (A) and the component (B) is preferably 2, more preferably 1, still more preferably 0.8, and 7 is still more preferred, 0.6 is particularly preferred, and 0.5 is particularly preferred. If the ratio of the component (E) is less than 0.05, the desired low roughness effect tends not to be obtained, and if it exceeds 2, the peel strength tends to decrease.

  The resin composition of the present invention comprises (A) component, (B) component, (C) component, (D) component, and (E) component, and the surface roughness of the insulating layer obtained by curing the resin composition. Even if it is low, the resin composition which can form the conductor layer which has high peel strength can be provided.

  The peel strength of the cured product of the resin composition containing the (A) component, (B) component, (C) component, (D) component, and (E) component of the present invention will be described later. Strength (peel strength) measurement and evaluation> can be grasped by the measurement method described in>.

  The upper limit of the peel strength (kgf / cm) of the cured product of the resin composition of the present invention is preferably 0.8, more preferably 0.9, still more preferably 1.0, and even more preferably 1.1. 1.2 is particularly preferred and 2 is particularly preferred. The lower limit of the peel strength (kgf / cm) of the cured product of the resin composition of the present invention is preferably 0.4, more preferably 0.5, and still more preferably 0.6.

  The surface roughness of the cured product of the resin composition containing the component (A), the component (B), the component (C), the component (D), and the component (E) of the present invention is described below. Roughness (Ra value) measurement and evaluation> It can be grasped by the measurement method described in>.

  The upper limit of the surface roughness (nm) of the cured product of the resin composition of the present invention is preferably 700, more preferably 500, still more preferably 400, still more preferably 300, even more preferably 200, and particularly preferably 170. . The lower limit of the surface roughness (nm) of the cured product of the resin composition of the present invention is preferably 150, more preferably 120, still more preferably 90, still more preferably 70, even more preferably 50, and particularly preferably 30. .

[Rubber particles]
The resin composition of the present invention can contain solid rubber particles for the purpose of increasing the mechanical strength of the cured product and for reducing the stress. The rubber particles are not dissolved in the organic solvent when preparing the resin composition, are not compatible with components in the resin composition such as an epoxy resin, and exist in a dispersed state in the varnish of the resin composition. preferable. 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 glass layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made 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 the acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation). Specific examples of the 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.).

  The average particle size of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber particles is created on a mass basis using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.). The average particle size can be measured.

  When the rubber particles are blended, the content is preferably in the range of 1 to 10% by mass and more preferably in the range of 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. .

[Other thermosetting resins]
The resin composition of the present invention is blended with other thermosetting resins such as a maleimide compound, a bisallyl nadiimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin within a range in which the effects of the present invention are exhibited as necessary. You can also Such thermosetting resins may be used in combination of two or more. 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.).

[Flame retardants]
The resin composition of the present invention may contain a flame retardant as long as the effects of the present invention are exhibited. Two or more flame retardants may be mixed and used. 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 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. Examples of the organic nitrogen-containing phosphorus compound include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., 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 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.

[Resin additive]
The resin composition of the present invention may optionally contain various resin additives other than those described above as long as the effects of the present invention are exhibited. Examples of the resin additive include 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 or leveling agents, and silane coupling. Examples thereof include adhesion-imparting agents such as an agent, a triazole compound, a thiazole compound, a triazine compound, and a porphyrin compound, and a colorant such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow, and carbon black. Also, imidazole compounds such as Curezol 2MZ, 2E4MZ, C11Z, C11Z-CN, C11Z-CNS, C11Z-A, 2MZ-OK, 2MA-OK, 2PHZ (trade names of Shikoku Kasei Kogyo Co., Ltd.); Amine adduct compounds such as Fujicure (Fuji Kasei Kogyo Co., Ltd.); 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU) tetraphenylborate salt And tertiary amine compounds such as amine-based curing accelerators.

  The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like, if necessary, by adding a solvent or the like.

  The use of the resin composition of the present invention is not particularly limited, but includes insulating resin sheets such as adhesive films and prepregs, circuit boards, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embeddings. It can be used in a wide range of applications that require a resin composition such as a resin. Especially, it is preferable to apply | coat on a support body and to form a resin composition layer to make an adhesive film, or to impregnate this resin composition in the sheet-like fiber base material which consists of fibers to make a prepreg. The resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but industrially, in general, the insulating layer is formed in the form of a sheet-like laminated material such as an adhesive film or a prepreg. It is preferably used.

[Adhesive film]
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, applying the resin varnish on a support, and further heating or blowing hot air. It can manufacture by drying an organic solvent by etc. and forming a resin composition layer.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone 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. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. One organic solvent may be used, or two or more organic solvents may be used in combination.

  The drying conditions are not particularly limited, but the organic solvent content 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 it depends on the amount of organic solvent in the varnish, for example, a varnish containing 30 to 60% by mass of an organic solvent can be dried at 50 to 150 ° C. for about 3 to 10 minutes.

  The thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. The resin composition layer may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  Examples of the support in the present invention include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, plastic films such as polycarbonate and polyimide. Can be 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. The protective film is preferably a similar plastic film. Further, the support and the protective film may be subjected to release treatment in addition to mat treatment and 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, The range of 10-150 micrometers is preferable and it is more preferable to use in the range of 25-50 micrometers. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 to 40 μm, and more preferably in the range of 10 to 30 μm.

  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. In addition, it is preferable to form the resin composition layer formed on a support body so that the area of a layer may become smaller than the area of a support body. The adhesive film can be wound up in a roll shape and stored and stored.

[Method for producing multilayer printed wiring board using adhesive film]
Next, a method for producing a circuit board such as the multilayer printed wiring board of the present invention using the adhesive film of the present invention will be described. When the resin composition layer is protected with a protective film, the resin composition layer is peeled off and then laminated on one or both sides of the inner circuit board so that the resin composition layer is in direct contact with the inner circuit board. In the adhesive film of the present invention, a method of laminating the inner layer circuit board under reduced pressure by a vacuum laminating method is preferably used. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the inner layer circuit board may be heated (preheated) as necessary before lamination.

  The inner layer circuit board in the present invention is mainly a conductor layer (circuit) patterned on one or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. The one formed by. In addition, when manufacturing a multilayer printed wiring board in which conductor layers and insulating layers are alternately formed, and one or both surfaces are patterned conductor layers (circuits), an insulating layer and a conductor layer are further formed. The intermediate product to be included is also included in the inner layer circuit board in the present invention. In the inner layer circuit board, the surface of the conductor circuit layer is preferably roughened by a blackening process or the like from the viewpoint of adhesion of the insulating layer to the inner layer circuit board.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  The vacuum lamination can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.

  Moreover, the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine. For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.

  As pressing conditions, the degree of reduced pressure is preferably 1 × 10 −2 MPa or less, and more preferably 1 × 10 −3 MPa or less. Although heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin. For example, the first stage press has a temperature of 70 to 150 ° C. and the pressure is in the range of 1 to 15 kgf / cm 2, and the second stage press has the temperature of 150 to 200 ° C. and the pressure is in the range of 1 to 40 kgf / cm 2 It is preferred to do so. The time for each stage is preferably 30 to 120 minutes. Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.

  After laminating the adhesive film on the inner layer circuit board in this way, the support can be peeled off and the resin composition can be thermally cured to form an insulating layer on the inner layer circuit board. The conditions of heat curing are selected in the range of 20 to 180 minutes at 150 to 220 ° C, more preferably 30 to 120 minutes at 160 to 200 ° C.

  If the support is not peeled off after the insulating layer is formed, it is peeled off here. Next, holes are formed in the insulating layer formed on the inner circuit board to form via holes and through holes. Drilling can be performed by a known method such as drilling, laser, or plasma, or a combination of these methods if necessary. However, drilling by a laser such as a carbon dioxide laser or YAG laser is the most common method. .

  Next, a roughening process is performed on the surface of the insulating layer. The roughening treatment in the present invention is preferably performed by a wet roughening method using an oxidizing agent. Examples of the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. Preferably, an alkaline permanganate solution (eg, potassium permanganate, sodium hydroxide solution of sodium permanganate), which is an oxidizer widely used for roughening an insulating layer in the production of multilayer printed wiring boards by a built-up method. It is preferable to perform roughening using.

  The roughness of the roughened surface obtained by roughening the surface of the insulating layer is preferably 0.05 to 0.5 μm in Ra value when forming fine wiring. The Ra value is a kind of numerical value representing the surface roughness, and is called arithmetic average roughness. Specifically, the absolute value of the height changing in the measurement region is determined from the surface that is the average line. Measured and arithmetically averaged. For example, by using WYKO NT3300 manufactured by Becoin Instruments Co., Ltd., it can be obtained from a numerical value obtained by setting the measurement range to 121 μm × 92 μm with a VSI contact mode and a 50 × lens.

  Next, a conductor layer is formed on the surface of the resin composition layer on which uneven anchors are formed by the roughening treatment by a method combining electroless plating and electrolytic plating. Alternatively, a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating. After forming the conductor layer, the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes. The peel strength of the conductor layer is preferably 0.6 kgf / cm or more.

  Moreover, as a method of patterning the conductor layer to form a circuit, for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.

[Prepreg]
The prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like fiber substrate made of fibers by a hot melt method or a solvent method and semi-curing by heating. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like fiber base material which consists of fibers.

  As the sheet-like fiber base material composed of fibers, for example, glass cloth and aramid fibers, which are commonly used as prepreg fibers, can be used.

  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.

[Method for producing multilayer printed wiring board using prepreg]
Next, a method for producing a circuit board such as the multilayer printed wiring board of the present invention using the prepreg of the present invention will be described. One or several prepregs of the present invention are stacked on the inner layer circuit board, and a metal plate is sandwiched through a release film, and press laminated under pressure and heating conditions. The pressure is preferably 5 to 40 kgf / cm ² (49 × 10 ^{4 to} 392 × 10 ⁴ N / m ² ), and the temperature is preferably 120 to 200 ° C. for 20 to 100 minutes. In addition, as with the adhesive film, it can be produced by laminating on an inner layer circuit board by a vacuum laminating method and then heat-curing. Thereafter, in the same manner as described above, the surface of the prepreg cured with an oxidizing agent is roughened, and then the conductor layer is formed by plating, whereby a circuit board such as a multilayer printed wiring board can be manufactured.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example and a comparative example, these do not restrict | limit this invention in any meaning. In the following description, “part” means “part by mass”.

Example 1
35 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 35 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.), phenoxy MEK 10 parts, cyclohexanone 40 parts of resin (weight average molecular weight 38000, "YX6954" manufactured by Japan Epoxy Resins Co., Ltd., 30 parts by mass of methyl ethyl ketone (hereinafter abbreviated as "MEK") and cyclohexanone 1: 1) The mixture was dissolved in 3 parts 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) 45 parts, a quaternary phosphonium-based curing accelerator (4-methyl Phenyl) triphenylphosphonium thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPTP-SCN” dimethylformamide (hereinafter abbreviated as “DMF”) solution having a nonvolatile content of 10% by mass), spherical silica (average particle size 0) The resin varnish was prepared by uniformly dispersing 70 parts with 5 μm, “SOC2” (manufactured by Admatechs Co., Ltd.) and a high-speed rotary mixer. Next, the resin varnish was applied onto polyethylene terephthalate (thickness 38 μm, hereinafter abbreviated as “PET”) with a die coater so that the resin thickness after drying was 40 μm, and 80 to 120 ° 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, and a sheet-like adhesive film having a size of 507 × 336 mm was obtained therefrom.

(Example 2)
2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPTP-SCN” in a DMF solution having a nonvolatile content of 10% by mass), which is a quaternary phosphonium-based curing accelerator of Example 1, Adhering in exactly the same way except changing to 4 parts tetraphenylphosphonium thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPP-SCN” DMF solution with a nonvolatile content of 5% by mass), which is also a quaternary phosphonium-based curing accelerator. A film was obtained. Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

(Example 3)
18 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 20 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), naphthalene 6 parts of type 4 functional epoxy resin (epoxy equivalent 162, “HP-4700” manufactured by DIC Corporation), phenoxy resin (weight average molecular weight 38000, “YL7553” manufactured by Japan Epoxy Resins Co., Ltd.) MEK having a nonvolatile content of 30% by mass and 12 parts of a cyclohexanone (1: 1 solution) was dissolved in 8 parts of MEK and 8 parts of cyclohexanone with heating while stirring. There, 13 parts of 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), an active ester curing agent (“EXB manufactured by DIC Corporation”) -9460 "Toluene solution with a nonvolatile content of 65 mass%, active ester equivalent 223) 20 parts, Tetrabutylphosphonium decanoate which is a quaternary phosphonium-based curing accelerator (" TBP-DA "manufactured by Hokuko Chemical Co., Ltd.) 0.2 parts, 75 parts of spherical silica (average particle size 0.5 μm, “SOC2” with aminosilane treatment, manufactured by Admatechs), polyvinyl butyral resin solution (glass transition temperature 105 ° C., “KS-” manufactured by Sekisui Chemical Co., Ltd.) 1 ”18 parts of ethanol / toluene with a non-volatile content of 15% by mass) (18 parts) are mixed and dispersed uniformly with a high-speed rotary mixer. To prepare a varnish. Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

Example 4
25 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resin Co., Ltd.), 25 parts biphenyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.), naphthalene 6 parts of type 4 functional epoxy resin (epoxy equivalent 162, “HP-4700” manufactured by DIC Corporation), phenoxy resin (weight average molecular weight 38000, “YL7553” manufactured by Japan Epoxy Resins Co., Ltd.) MEK having a nonvolatile content of 30% by mass and 12 parts of a 1: 1 solution of cyclohexanone) was dissolved in 5 parts of MEK and 5 parts of cyclohexanone with heating while stirring. Thereto, 36 parts of 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), butyltriphenylphosphonium which is a quaternary phosphonium-based curing accelerator. 2 parts of thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPPB-SCN” DMF solution having a nonvolatile content of 10% by mass), 190 parts of spherical silica (average particle size 0.5 μm, “SOC2” with aminosilane treatment, manufactured by Admatechs) , 12 parts of a polyvinyl butyral resin 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) are mixed uniformly with a high-speed rotating mixer To obtain a resin varnish. Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

(Comparative Example 1)
An adhesive film was obtained in exactly the same manner except that the quaternary phosphonium-based curing accelerator of Example 1 was not added. Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

(Comparative Example 2)
2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPTP-SCN” in a DMF solution having a nonvolatile content of 10% by mass), which is a quaternary phosphonium-based curing accelerator of Example 1, Adhering in exactly the same manner except that it is changed to 2 parts of DBU-based tetraphenylborate salt ("U-CAT 5002", MEK solution with a nonvolatile content of 10% by mass), which is also a quaternary phosphonium-based curing accelerator. A film was obtained. Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

(Comparative Example 3)
0.2 part of tetrabutylphosphonium decanoate (made by Hokuko Chemical Co., Ltd., “TBP-DA”), which is a quaternary phosphonium curing accelerator of Example 3, is also a quaternary phosphonium curing accelerator. An adhesive film was obtained in exactly the same manner except that the content was changed to 2 parts of triphenylphosphine triphenylborane (manufactured by Hokuko Chemical Co., Ltd., “TPP-S” DMF solution having a nonvolatile content of 10 mass%). Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

(Comparative Example 4)
2 parts of (4-methylphenyl) triphenylphosphonium thiocyanate (manufactured by Hokuko Chemical Co., Ltd., “TPTP-SCN” in a DMF solution having a nonvolatile content of 10% by mass), which is a quaternary phosphonium-based curing accelerator of Example 1, An adhesive film was obtained in exactly the same manner except that it was changed to 0.2 parts of tetraphenylphosphonium tetraphenylborate (“TPP-K” manufactured by Hokuko Chemical Co., Ltd.), which is also a quaternary phosphonium-based curing accelerator. . Next, using this resin varnish, an adhesive film was obtained in the same manner as in Example 1.

<Preparation of peel strength and Ra value measurement sample>
(1) Ground treatment of inner layer circuit board Both sides of a glass cloth base epoxy resin double-sided copper clad laminate [copper foil thickness 18 μm, substrate thickness 0.3 mm, Matsushita Electric Works R5715ES] on which an inner layer circuit is formed The copper surface was roughened by dipping in CZ8100 manufactured by MEC Co., Ltd.

(2) Lamination of adhesive film The adhesive film created in the examples and comparative examples was laminated on both sides of the inner layer circuit board using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by Meiki Co., Ltd.). . Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

(3) Curing of resin composition The PET film was peeled from the laminated adhesive film, and the resin composition was cured under a curing condition of 180 ° C for 30 minutes to form an insulating layer.

(4) Roughening treatment The inner layer circuit board on which the insulating layer is formed is immersed in a swelling dip seculigand P containing diethylene glycol monobutyl ether of Atotech Japan Co., Ltd. for 5 minutes at 60 ° C., and then roughened. As a chemical solution, it is immersed in an Atotech Japan Co., Ltd. Concentrate Compact P (KMnO4: 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally as a neutralizing solution, Atotech Japan Co., Ltd. Were dipped in 40 g of reduction Shoryushin securigant P for 5 minutes. Using this substrate, the surface roughness (Ra value) of the surface of the insulating layer after the roughening treatment was measured.

(5) Plating by semi-additive method In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in an electroless plating solution containing PdCl ₂ and then immersed in an electroless copper plating solution. After annealing at 150 ° C. for 30 minutes, an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 30 ± 5 μm. Next, annealing was performed at 180 ° C. for 60 minutes. The peel strength of the plated conductor layer was measured for this circuit board.

<Measurement and Evaluation of Peeling Strength (Peel Strength) of Plating Conductor Layer>
Use a cutter to cut the conductor layer of the circuit board with a width of 10 mm and a length of 100 mm. Remove one end and use a gripping tool (TSE, Inc., Autocom type testing machine AC-50C-SL). The load was measured when 35 mm was grabbed and peeled in the vertical direction at a speed of 50 mm / min at room temperature. When the load is 0.75 kgf / cm or more, “◎”, when the load is less than 0.75 kgf / cm, 0.62 kgf / cm or more, “◯”, and when less than 0.62 kgf / cm, 0.40 kgf / cm or more Was evaluated as “x”, and the case of less than 0.40 kgf / cm was evaluated as “x”.

<Measurement and evaluation of surface roughness (Ra value) after roughening>
Using a non-contact type surface roughness meter (BYCO Instruments WYKO NT3300), a numerical value obtained with a measurement range of 121 μm × 92 μm was measured with a VSI contact mode and a 50 × lens. The Ra value was determined by obtaining the average surface roughness of 10 points. The case where the Ra value is 500 nm or more is “XX”, the case where it is less than 500 nm and 420 nm or more is “X”, the case where it is less than 420 nm and 380 nm or more is “Δ”, and the case where it is less than 380 nm and 300 nm or more is “◯”, The case of less than 300 nm and 200 nm or more was evaluated as “◎”, and the case of less than 200 nm was evaluated as “◎”.

  The results of peel strength and roughened surface roughness (Ra value) of the plated conductor layers of the evaluation samples using the varnishes obtained in Examples and Comparative Examples are shown in Table 1 below. As is clear from Table 1, in the resin compositions of the examples, a conductor layer having a high peel strength is formed even though the surface roughness of the insulating layer is low. Thus, in this invention, since low surface roughness is achieved, it turns out that it is advantageous to miniaturization. In Comparative Example 1 in which no quaternary phosphonium-based curing accelerator is added, the roughness for obtaining the same peel strength is increased. In Comparative Example 2, an amine curing agent was used, but the result was that the roughness increased. In Comparative Examples 3 and 4, the same triphenylphosphine-based curing accelerator was used as the curing accelerator, but both low roughness and high peel were not achieved as compared with the Examples.

  To provide a resin composition, an adhesive film, a prepreg, and a multilayer printed wiring board capable of forming a conductor layer having high peel strength even when the surface roughness of the insulating layer obtained by curing the resin composition is low. became. 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 (17)

(A) Polyfunctional epoxy resin (excluding phenoxy resin), (B) phenolic curing agent and / or active ester curing agent, (C) phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, poly A thermoplastic resin selected from ether sulfone resins and polysulfone resins, (D) inorganic fillers, and (E) tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and A resin composition containing one or more quaternary phosphonium curing accelerators selected from butyltriphenylphosphonium thiocyanate. The component (E) is contained in the range in which the ratio of the mass of the component (E) to the total mass of the non-volatile components of the component (A) and the component (B) is 100: 0.05 to 100: 2. Resin composition. The component (B) is contained in the range in which the ratio of the epoxy group present in the resin composition and the reactive group of the curing agent of the component (B) is 1: 0.3 to 1: 2 in molar ratio. 2. The resin composition according to 2. The resin composition of any one of Claims 1-3 whose content of a component (C) is 1-20 mass% when the non volatile matter in a resin composition is 100 mass%. The resin composition according to any one of claims 1 to 4, wherein the content of the component (D) is 10 to 70 mass% when the nonvolatile content in the resin composition is 100 mass%. The resin composition according to any one of claims 1 to 5, wherein the content of the component (A) is 10 to 50 mass% when the nonvolatile component in the resin composition is 100 mass%. The resin composition according to any one of claims 1 to 6, wherein the component (A) is selected from a bisphenol A type epoxy resin, a naphthalene type epoxy resin, and a biphenyl type epoxy resin. Component (A) is a liquid epoxy resin and a solid epoxy resin, The resin composition of any one of Claims 1-7. The weight average molecular weight of a component (C) is the range of 8000-70000, The resin composition of any one of Claims 1-8. The resin composition according to claim 1, wherein the component (D) has an average particle size of 0.05 to 1 μm. The resin composition according to any one of claims 1 to 10, wherein the component (D) is silica. The resin composition according to any one of claims 1 to 11, wherein the component (D) is treated with a surface treatment agent. The peel strength between the cured product of the resin composition and the conductor layer formed on the surface thereof is 3.9 N / cm to 19.6 N / cm, and the surface roughness of the cured product of the resin composition is 30 nm to 400 nm. It is these. The resin composition of any one of Claims 1-12. The resin composition according to claim 1, which is for forming an insulating layer on a circuit board. The adhesive film by which the resin composition of any one of Claims 1-14 is layer-formed on the support body. A prepreg in which the resin composition according to any one of claims 1 to 14 is impregnated in a sheet-like fiber base material. The circuit board by which the insulating layer is formed with the hardened | cured material of the resin composition of any one of Claims 1-14.