JP2007231246A - Resin composition, prepreg, and metal-clad laminate board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having low thermal expansion properties by the use of which not only an abrasion loss of a drill is reduced during a drill processing of a multilayer printed circuit board, but also the connection reliability of a multilayer printed circuit board can be secured, and a prepreg as well as metal-clad laminate board using the same. <P>SOLUTION: This resin composition is a resin composition containing: (A) a thermosetting resin; 10 to 35% by mass of (B) a silica having an average particle diameter of 0.4 to 4.5 μm; and 10 to 20% by mass of (C) a metal dialkylphosphinate salt having an average particle diameter of 2.0 to 4.0 μm, based on the total mass of the resin composition, wherein the total amount of the (B) and (C) components is 20 to 50% by mass, based on the total mass of the resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin composition, a prepreg, and a metal-clad laminate.

  As electronic devices become smaller, lighter, and have higher performance, printed wiring boards used in such devices are becoming increasingly multilayered and dense. Therefore, many drills are used to form through holes in multilayer printed wiring boards. Further, a method is known in which a large amount of filler is added in order to ensure connection reliability of a multilayer printed wiring board (see, for example, JP-A-2003-64198). However, when a high-hardness filler represented by silica is added, there is a problem that the drill life is shortened and the drill consumption is increased because the drill wear amount is large.

JP 2003-64198 A

  The present invention has been made in view of the above-described problems, and has low thermal expansion characteristics that can reduce the amount of drill wear when drilling a multilayer printed wiring board and can ensure the connection reliability of the multilayer printed wiring board. It aims at providing the resin composition which has this. Another object of the present invention is to provide a prepreg and a metal-clad laminate using the resin composition of the present invention.

As a result of continuing intensive studies, the present inventors have found that the above object can be achieved by blending specific silica and dialkylphosphinic acid metal salts with specific individual contents and total contents.
The present invention has been completed based on such findings.
That is, the present invention relates to the following.
(1) In the resin composition containing (A) thermosetting resin, (B) silica, and (C) metal salt of dialkylphosphinic acid, (B) silica has an average particle diameter of 0.4 to 4.5 μm. 10 to 35% by mass in the total resin composition, 10 to 20% by mass in the total resin composition of (C) dialkylphosphinic acid metal salt having an average particle size of 2.0 to 4.0 μm, and ( B) and a resin composition characterized by containing 20 to 50% by mass in the total resin composition as a total amount of components (C),
2. (A) The thermosetting resin is at least one selected from an epoxy resin system, a polyimide resin system, a triazine resin system, a phenol resin system, a melamine resin system, an unsaturated polyester resin system, and a modified thermosetting resin thereof. The resin composition according to 1 above,
3. (C) The resin composition according to the above 1 or 2, wherein the metal salt of dialkylphosphinic acid is aluminum dialkylphosphinate,
4). A prepreg obtained by impregnating a substrate with the resin composition according to any one of the above 1 to 3, drying, and B-stage,
5). The prepreg as described in 4 above, wherein the substrate is a glass woven fabric,
6). 6. A metal-clad laminate in which metal layers are formed on both sides or one side of the prepreg or laminate thereof according to 4 or 5 above

  Resin composition having low thermal expansion characteristics that can reduce the amount of drill wear when drilling a multilayer printed wiring board and can secure connection reliability of the multilayer printed wiring board, and a prepreg and a metal-clad laminate using the resin composition It became possible to provide a board.

  The (A) thermosetting resin used in the present invention is not particularly limited, and examples thereof include an epoxy resin system, a polyimide resin system, a triazine resin system, a phenol resin system, a melamine resin system, an unsaturated polyester resin system, and a modified system thereof. A thermosetting resin or the like is used. These resins may be used in combination of two or more, and various curing agents, curing accelerators, silane coupling agents, coloring agents, antioxidants, reducing agents, ultraviolet absorbers, etc. as necessary. You may mix | blend these as a solvent solution using an additive.

  Examples of epoxy resin-based thermosetting resins and modified thermosetting resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, alicyclic epoxy resins, and phenol novolacs. Type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ether compound of polyfunctional phenols, and hydrogenated products thereof .

  In the case of using an epoxy resin-based thermosetting resin and a modified thermosetting resin, conventionally known dicyandiamide, diaminophenylmethane, diaminophenylsulfone, phthalic anhydride, pyromellitic anhydride, phenol novolac, and cresol are used as curing agents. Polyfunctional phenols such as novolak can be used. Several kinds of these curing agents can be used in combination. In addition, the type and blending amount of the curing accelerator are not particularly limited. For example, imidazole compounds, organophosphorus compounds, tertiary amines, quaternary ammonium salts and the like are used, and two or more kinds are used in combination. You may do it.

  Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-hepta. Decylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4- Examples include methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline. These imidazole compounds may be masked with a masking agent. Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate. Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra Examples include phenylphosphonium tetraphenylborate. Secondary amines include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiomorpholine, etc. Is mentioned. Tertiary amines include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and the like. The quaternary ammonium salts include tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, benzalkonium chloride, benzyldi (2-hydroxyethyl) methylammonium chloride, decyldi (2- And hydroxyethyl) methylammonium bromide.

Examples of the polyimide resin-based thermosetting resin include those obtained by condensation polymerization of aromatic tetracarboxylic dianhydride and diamine. Examples of the tetracarboxylic dianhydride include 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,4,5,6 -Naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 3,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrene Tetracarboxylic acid Anhydride, 4,4 '- (hexafluoro isopropylidene) phthalic dianhydride, and the like.
Examples of diamines include aromatic diamines and siloxane diamines. Examples of the aromatic diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP), bis [4- (3-aminophenoxy) phenyl] sulfone, and bis [4- (4- Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] methane, 4,4′-bis (4- Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 2,2′-dimethylbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) B) Biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4 '-Diamine, 3,3'-dihydroxybiphenyl-4,4'-diamine, (4,4'-diamino) diphenyl ether, (4,4'-diamino) diphenyl sulfone, (4,4'-diamino) benzophenone, (3,3′-diamino) benzophenone, (4,4′-diamino) diphenylmethane, (4,4′-diamino) diphenyl ether, (3,3′-diamino) diphenyl ether and the like. Examples of the siloxane diamine include diamine compounds having a polysiloxane chain. Siloxane diamines are “X-22-161AS” (amine equivalent 450), “X-22-161A” (amine equivalent 840), “X-22-161B” (amine equivalent 1500) (manufactured by Shin-Etsu Chemical Co., Ltd.). , Trade name), “BY16-853” (amine equivalent 650), “BY16-853B” (amine equivalent 2200) (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like are commercially available.

  The triazine resin-based thermosetting resin and the modified thermosetting resin are cured products having a triazine ring generated by heating a cyanate compound as a repeating unit. Examples of the cyanate compound include 2,2-bis (4-cyanatephenyl) propane, bis (4-cyanatephenyl) ethane, 2,2-bis (3,5-dimethyl-4-cyanatephenyl) methane, Of 2-bis (4-cyanatephenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatephenyl) -m-diisopropylbenzene, phenol novolac and alkylphenol novolac Examples include cyanate esterified products. The cyanate compound may be partially oligomerized in advance to a trimer or a pentamer. Furthermore, bismaleimide triazine resin (BT) obtained by reacting bismaleimide with diisocyanate may be used.

  Examples of the curing catalyst for the cyanate compound include organic acid metal catalysts such as zinc naphthenate, manganese naphthenate, and titanium naphthenate. Examples of the curing accelerator for the cyanate compound include compounds having a phenolic hydroxyl group such as monophenol compounds such as phenol, nonylphenol, phenoxyphenol and p-cumylphenol, and polyphenol compounds such as bisphenol A and phenol novolac resins. Is mentioned.

  As a phenol resin thermosetting resin, a novolak type or a resol type may be used alone, or both may be used in combination. The novolac type phenol resin can be synthesized by reacting phenols with formaldehyde in the presence of an acid catalyst such as oxalic acid. Although it does not specifically limit about novolak type phenol resin, For example, random novolak resin and high ortho novolak resin are mentioned. Although it does not specifically limit about a resole type phenol resin, A methylol type and a dimethylene ether type are mentioned. The methylol type resol resin can be synthesized by reacting phenols with formaldehyde in the presence of a normal basic catalyst. As the basic catalyst, ammonia and hexamethylenetetramine are preferable. The dimethylene ether type resole resin reacts phenol and formaldehyde in the presence of a group 2 element or transition element and an organic monocarboxylic acid such as formic acid or acetic acid or an inorganic acid such as boric acid, hydrochloric acid or nitric acid. Can be synthesized.

  Examples of the melamine resin-based thermosetting resin include methyl etherified melamine resin, n-butyl etherified melamine resin, and iso-butyl etherified melamine resin. The molecular weight, addition degree, and etherification degree of the melamine resin are not particularly limited.

  Examples of the unsaturated polyester resin-based thermosetting resin and modified thermosetting resin include copolymer resins of styrenes and maleic anhydride. In the copolymer resin of styrenes and maleic anhydride, examples of styrenes include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, vinylnaphthalene, and the like. Furthermore, in addition to the monomer unit, it may be copolymerized with various polymerizable components. Examples of these various polymerizable components include vinyl compounds such as ethylene, propylene, isobutylene and acrylonitrile; Diene compounds; compounds having a methacryloyl group or an acryloyl group such as methyl methacrylate and methyl acrylate. Moreover, a substituent can be introduce | transduced arbitrarily by Friedel-Crafts reaction and reaction using metal catalysts, such as lithium. Examples of the substituent to be introduced include an allyl group, a methacryloyl group, an acryloyl group, and a hydroxyl group. Further, a part of maleic anhydride can be reacted with various hydroxyl group-containing compounds, amino group-containing compounds, isocyanato group-containing compounds, epoxy group-containing compounds and the like, and substituents can be arbitrarily introduced. For example, it can be reacted with 2-hydroxyethyl acrylate, glycidyl methacrylate, methacryloyloxyethyl isocyanate or allylamine to introduce a methacryloyl group, an acryloyl group or an allyl group. Further, a copolymer resin containing N-substituted phenylmaleimides in addition to styrenes and maleic anhydride is particularly preferable. Examples of N-substituted phenylmaleimides include N-phenylmaleimide and N-hydroxyphenylmaleimide having a phenolic hydroxyl group.

  As the silane coupling agent, a carbon functional silane is used, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (2,3-epoxycyclohexyl) ethyltrimethoxy. Epoxy group-containing silane such as silane; 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl (methyl) Amino group-containing silanes such as dimethoxysilane; cationic silanes such as 3- (trimethoxylyl) propyltetramethylammonium chloride; vinyl group-containing silanes such as vinyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane Such acrylic group-containing silanes; and Mercapto group-containing silanes such as 3-mercaptopropyl trimethoxysilane.

  Examples of the ultraviolet absorber include benzotriazole compounds, and examples of the antioxidant include hindered phenol compounds and styrenated phenol compounds.

  The silica of the component (B) used in the present invention is not limited in the production method, and commercially available products such as synthetic silica and crushed silica can be used. For example, silica is commercially available from companies such as Admatechs Co., Ltd., Electrochemical Industry Co., Ltd., Micron Co., Ltd. and Tonen Co., Ltd. Silica having an average particle diameter of 0.4 to 4.5 μm, preferably 0.5 to 3.5 μm is used. The addition amount of silica is 10 to 35% by mass, preferably 10 to 25% by mass, based on the total resin composition. By setting the silica content in the total resin composition to 10% by mass or more, low thermal expansion characteristics for ensuring connection reliability can be obtained, and by setting it to 35% by mass or less, the outer layer peel strength is reduced. And increase in drill wear is suppressed. Moreover, when the average particle diameter of silica is 0.4 μm or more, the increase in the varnish viscosity is small, and coating is easy, which is desirable. Moreover, since there is no large particle | grains as it is 4.5 micrometers or less, even if a drill blade hits a silica particle, there is no break of a drill and it is preferable.

The dialkylphosphinic acid metal salt of component (C) used in the present invention has the following formula (1)
It is a phosphinic acid salt represented by In the formula, R ₁ and R ₂ may be the same or different from each other, and are linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, Examples include isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group and the like. Among these, a methyl group or an ethyl group is preferable. In the formula, M is a metal of Group IA, Group IIA, Group IIIA, Group IVA, Group VA, Group IIB, Group IVB, Group VIIB or Group VIIIB, or cerium of the periodic table. . Among these, lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, tin, iron, etc. are mentioned. Aluminum is particularly desirable from the viewpoint of increasing the phosphorus content in the compound and the hygroscopicity.

  (C) As the dialkylphosphinic acid metal salt, one having an average particle diameter of 2.0 to 4.0 μm, preferably 2.5 to 3.5 μm is used. The addition amount of the metal salt of dialkylphosphinic acid is 10 to 20% by mass, preferably 10 to 15% by mass, based on the total resin composition. Since the content of the dialkylphosphinic acid metal salt is 10% by mass or more, it is not necessary to increase the amount of silica as the component (B) in order to obtain low thermal expansion characteristics for ensuring connection reliability. A tendency to decrease the amount of wear is observed. Moreover, by setting it as 20 mass% or less, the raise of an outer layer peel strength, an interlayer adhesive strength, and the raise of an alkali-proof characteristic are recognized. Furthermore, when the average particle size is 2.0 μm or more, it has an appropriate specific surface area and exhibits good alkali resistance, and when it is 4.0 μm or less, from the hole wall in which through-hole formation was performed by a drill. It is preferable because large particles of the metal salt of dialkylphosphinic acid do not fall and there is no possibility of deteriorating the through-hole shape.

  Further, the content of each of the silica as the component (B) and the dialkylphosphinic acid metal salt as the component (C) in the total resin composition is as described above, and at the same time, the components (B) and (C ) The total content of the components is 20 to 50% by mass, preferably 23 to 40% by mass. (B) component and (C) component by making the total content of the silica which is (B) component and the dialkylphosphinic acid metal salt which is (C) component in all resin compositions into 20 mass% or more. Since there is no uneven distribution, the location where the drill workability is remarkably deteriorated is not confirmed. Further, when the total content is 50% by mass or less, an increase in the amount of drill wear is not recognized.

  The resin composition of the present invention is preferably used after being diluted with a solvent to form a varnish. The type of the solvent used at this time is not particularly limited, and examples thereof include alcohol solvents such as methanol, ethanol, butanol and isopropanol, ether solvents such as tetrahydrofuran and ethylene glycol monomethyl ether, acetone, methyl ethyl ketone (hereinafter referred to as “MEK”). ), Ketone solvents such as methyl isobutyl ketone, amide solvents such as N-methylpyrrolidone, N, N′-dimethylformamide, aromatic hydrocarbon solvents such as benzene, toluene, xylene and trimethylbenzene, acetic acid There are ester solvents such as ethyl and methyl cellosolve acetate, and nitrile solvents such as butyronitrile. These may be used alone or in combination.

  The solid content concentration of the varnish is not particularly limited and can be appropriately changed depending on the resin composition, blending amount, and the like. However, when a prepreg is produced, it is preferably 50 to 80% by mass, more preferably 50 to 70% by mass. is there. By setting it to 50% by mass or more, there is a tendency that the varnish viscosity is high and the resin content of the prepreg tends to be high. Tend to be.

  The prepreg used in the present invention is obtained by impregnating a base material with the resin composition according to the present invention. Although it will not restrict | limit especially if it is used when manufacturing a metal foil clad laminated board and a multilayer printed wiring board as a base material, Usually, fiber base materials, such as a woven fabric and a nonwoven fabric, are used. Examples of the fiber base material include glass, alumina, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyether ether ketone, polyether imide, polyether sulfone. Further, there are organic fibers such as carbon and cellulose, and mixed papers thereof, and glass fiber woven fabrics are particularly preferably used. As the substrate used for the prepreg, a glass woven fabric of 20 to 200 μm is particularly preferably used. Examples of the metal foil include metals such as copper, aluminum, and nickel, alloys, composite foils, and the like, and copper foil is preferable.

  A varnish of these resin compositions is impregnated into a base material, and dried, for example, in the range of 80 to 200 ° C., preferably 120 to 180 ° C., and B-staged (semi-cured) to produce a prepreg. Examples of the method of impregnating the substrate with the resin composition include a method of impregnating the substrate with varnish, a method of applying the resin composition to the surface of the substrate, and the like.

  The production conditions of the prepreg are not particularly limited, but it is preferable that the solvent used for the varnish is volatilized by 80% by mass or more, preferably 95% by mass or more. For this reason, the production method and drying conditions are not limited, and the temperature during drying is 80 to 200 ° C., preferably 120 to 180 ° C., and the time is appropriately selected without any limitation in consideration of the gelation time of the varnish. . Moreover, it is preferable that the amount of impregnations of a varnish shall be 35-80 mass% with respect to a varnish solid content and the total amount of a base material.

  In the metal-clad laminate in the present invention, the prepreg is heated at a temperature of usually 130 to 250 ° C., preferably 150 to 200 ° C., and usually at a pressure of 0.5 to 20 MPa, preferably 1 to 8 MPa. Obtained by pressure molding. The constituent material is not particularly limited, and a laminate with copper foil, a metal foil (metal layer) such as copper foil, a laminate with aluminum foil, a release film (Asahi Glass: Aflex), and the like are used.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention.
Example 1
In a glass flask equipped with a stirrer, a condenser and a thermometer, (A) BPA novolac type epoxy resin (epoxy equivalent: 210, manufactured by Dainippon Ink & Chemicals, Inc., containing 30% by mass of MEK, N865-70) 100.0% Part, cresol skeleton-containing melamine-modified phenol resin [hydroxyl equivalent: 184, nitrogen content: 24.0% by mass, Dainippon Ink & Chemicals, Inc., solvent (MEK, propylene glycol monomethyl ether) 50% by mass, phenolite EXB9831] 122.7 parts by mass, (B) 17.1 parts by mass of silica (Tokuyama GU manufactured by Tokuyama Corporation, average particle size: 3.0 μm), (C) dialkylphosphinic acid aluminum salt (OP930 manufactured by Clariant) as dialkylphosphinic acid metal salt 22.4 parts by mass of an average particle size of 3.1 μm) It melt | dissolved and diluted with MEK, it stirred at room temperature for 1 hour, and it adjusted with MEK so that it might become a resin composition varnish with a solid content of 60 mass%.

  This varnish was impregnated into a glass cloth (style 2116, E glass) having a thickness of about 100 μm and dried at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 50% by mass. Four prepregs and 12 μm copper foils were stacked on both sides of the prepreg, and a copper clad laminate having a thickness of about 0.4 mm was produced under the pressing conditions of 170 ° C., 90 minutes, 4.0 MPa. At this time, the component (B) is 10.0% by mass in the total resin composition, the component (C) is 13.1% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 23.1 mass% in a thing.

(Example 2)
A copper-clad laminate having a thickness of about 0.4 mm was made in the same manner as in Example 1 except that the amount of component (B) was changed to 53.2 parts by mass and the amount of component (C) was changed to 30.8 parts by mass. A plate was made. At this time, the component (B) is 24.7% by mass in the total resin composition, the component (C) is 14.3% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 39.0 mass% in a thing.

(Example 3)
As component (A), bis (3,5-dimethyl-4-cyanatephenyl) methane prepolymer (cyanate equivalent 219, conversion rate 30%, manufactured by Asahi Kasei Epoxy Corporation, trade name M-30) 100 parts by mass, dicyclo 127 parts by mass of a pentadiene type epoxy (epoxy equivalent: 278, manufactured by Dainippon Ink & Chemicals, Inc., HP7200H), as a curing accelerator, 0.02 parts by mass of zinc naphthenate, 0.3 parts by mass of 2-methylimidazole, (B ) 60.0 parts by mass of silica (Tokuyama GU manufactured by Tokuyama Corporation, average particle size 3.0 μm), (C) aluminum salt of dialkylphosphinic acid (OP930 manufactured by Clariant, average particle size 3.1 μm) as metal salt of dialkylphosphinic acid A thickness of about 0.4 mm was obtained in the same manner as in Example 1 except that 40.0 parts by mass was dissolved in toluene. To prepare a copper-clad laminate. At this time, the component (B) is 18.4% by mass in the total resin composition, the component (C) is 12.2% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 30.6 mass% in a thing.

Example 4
As component (A), 100 parts by mass of a dicyclopentadiene type epoxy (epoxy equivalent: 278, manufactured by Dainippon Ink and Chemicals, HP 7200H), a copolymer resin of styrene and maleic anhydride (manufactured by Sartomer, trade name EF-) 40) 185 parts by mass, as a curing accelerator, 0.02 parts by mass of zinc naphthenate, 0.3 parts by mass of 2-methylimidazole, (B) silica (Tokuyama GU manufactured by Tokuyama Corporation, average particle size 3.0 μm) 50 0.0 part by mass, as in Example 1, except that 50.0 parts by mass of (C) aluminum dialkylphosphinate (OP930 manufactured by Clariant, average particle size 3.1 μm) as a dialkylphosphinic acid metal salt was dissolved in toluene. Thus, a copper clad laminate having a thickness of about 0.4 mm was produced. At this time, the component (B) is 13.0% by mass in the total resin composition, the component (C) is 13.0% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 26.0 mass% in a thing.

(Example 5)
As component (A), bis (3,5-dimethyl-4-cyanatephenyl) methane prepolymer (cyanate equivalent 219, conversion rate 30%, manufactured by Asahi Kasei Epoxy Corporation, trade name M-30) 100 parts by mass, dicyclo 51 parts by mass of a pentadiene type epoxy (epoxy equivalent: 278, manufactured by Dainippon Ink & Chemicals, Inc., HP7200H), 51 parts by mass of a copolymer resin of styrene and maleic anhydride (trade name EF-40, manufactured by Sartomer), curing acceleration As agents, 0.02 parts by mass of zinc naphthenate, 0.3 parts by mass of 2-methylimidazole, (B) 30.0 parts by mass of silica (Tokuyama GU manufactured by Tokuyama Corporation, average particle size 3.0 μm), dialkylphosphinic acid (C) Aluminum salt of dialkylphosphinic acid (OP930 manufactured by Clariant, average particle size 3.1 μm) ), Except that 40.0 parts by mass was dissolved in toluene in the same manner as in Example 1 to prepare a copper-clad laminate having a thickness of about 0.4 mm. At this time, the component (B) is 11.0% by mass in the total resin composition, the component (C) is 14.7% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 25.7 mass% in a thing.

(Comparative Example 1)
A prepreg having a thickness of about 0.4 mm was used in the same manner as in Example 1 except that an inorganic filler or other inorganic material (manufactured by Hitachi Chemical Co., Ltd., GEA-67N (trade name) was used) was used. A copper clad laminate was prepared. At this time, the component (B) is 0% by mass in the total resin composition, the component (C) is 0% by mass in the total resin composition, and the total content of (B) and (C) is 0% by mass in the total resin composition. %.

(Comparative Example 2)
A copper clad laminate having a thickness of about 0.4 mm in the same manner as in Example 1 except that the amount of component (B) was changed to 112.0 parts by mass and the amount of component (C) was changed to 28.0 parts by mass. Was made. At this time, the component (B) is 41.3% by mass in the total resin composition, the component (C) is 10.3% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 51.6 mass% in a thing.

(Comparative Example 3)
A copper clad laminate having a thickness of about 0.4 mm in the same manner as in Example 1 except that the amount of component (B) was changed to 28.0 parts by mass and the amount of component (C) was changed to 42.0 parts by mass. Was made. At this time, the component (B) is 13.9% by mass in the total resin composition, the component (C) is 20.9% by mass in the total resin composition, and the total content of (B) and (C) is the total resin composition. It is 34.8 mass% in a thing.

Using the copper clad laminate produced as described above, drill wear amount, drill life, through-hole connection reliability test, thermal expansion coefficient, and alkali resistance were evaluated. The results are shown in Table 1 below.

(1) Amount of drill wear and drill life Drill diameter 0.1mm, number of revolutions 160,000rpm, feed rate 1.6m / min, number of stacked copper-clad laminates, entry board 150μm aluminum plate drilling conditions The drill wear amount and drill life were evaluated. As for the amount of wear of the drill, the amount of wear in the width direction and length direction of the drill blade at 1000 hours was measured. The evaluation of the drill life was evaluated as follows: ◯: No break at 1500 hits, Δ: Break at 1000 to 1499 hits, ×: Break at less than 1000 hits.

(2) Through-hole connection reliability A test pattern with a drill diameter of φ0.4 mm, a plating thickness of 20 μm, and a land diameter of φ0.6 mm was prepared. One cycle was 260 ° C. (oil) 10 seconds and 20 ° C. (water) The number of cycles until the through-hole connection resistance value decreased by 10% was counted. The test was conducted with 10 cycles as one set.

(3) Alkali resistance Substrate when the copper foil on both sides of the copper-clad laminate is etched and cut into 50 mm x 50 mm x substrate thickness is immersed in a 10% strength by weight sodium hydroxide solution at a liquid temperature of 40 ° C. Mass change was observed. Evaluation was as follows: ○: Mass reduction rate of less than 0.1%, Δ: Mass reduction rate of less than 0.1-0.2%, and X: Mass reduction rate of 0.2% or more.

  The copper clad laminates in Examples 1 to 5 were found to have a small amount of drill wear, excellent drill life, excellent through-hole connection reliability, and no problem with alkali resistance. Comparative Example 1 was found to be inferior in through-hole connection reliability although the amount of drill wear was small. Comparative Example 2 was found to be excellent in through-hole connection reliability due to its high silica filling rate, but it was found that the amount of drill wear was large, the drill life was short, and the alkali resistance was slightly inferior. In Comparative Example 3, it was found that the drill wear amount, the drill life, and the through-hole connection reliability show average characteristics, but the alkali resistance is inferior.

  The present invention provides a resin composition having excellent low thermal expansion characteristics capable of ensuring connection reliability of a multilayer printed wiring board, and a prepreg and a metal-clad laminate using the resin composition. The prepreg using the resin composition of the present invention is excellent in appearance in addition to being excellent in low thermal expansion characteristics. Moreover, since the metal-clad laminate using the resin composition of the present invention has low thermal expansion characteristics, a multilayer printed wiring board having excellent connection reliability can be produced.

Claims (6)

  In the resin composition containing (A) thermosetting resin, (B) silica and (C) metal salt of dialkylphosphinic acid, (B) all having an average particle diameter of 0.4 to 4.5 μm as silica 10 to 35% by mass in the resin composition, 10 to 20% by mass in the total resin composition of (C) dialkylphosphinic acid metal salt having an average particle size of 2.0 to 4.0 μm, and (B) and (C) 20-50 mass% of total resin composition is contained as a total amount of a component, The resin composition characterized by the above-mentioned.   (A) The thermosetting resin is at least one selected from an epoxy resin system, a polyimide resin system, a triazine resin system, a phenol resin system, a melamine resin system, an unsaturated polyester resin system, and a modified thermosetting resin thereof. The resin composition according to claim 1.   (C) The resin composition according to claim 1 or 2, wherein the metal salt of dialkylphosphinic acid is aluminum dialkylphosphinate.   A prepreg obtained by impregnating a substrate with the resin composition according to any one of claims 1 to 3 and drying to form a B-stage.   The prepreg according to claim 4, wherein the substrate is a glass woven fabric.   A metal-clad laminate comprising metal layers formed on both sides or one side of the prepreg or laminate thereof according to claim 4 or 5.