WO2012070202A1 - High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board - Google Patents

High-heat-resistant epoxy resin composition, prepreg, metal-clad laminate, and printed wiring board Download PDF

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Publication number
WO2012070202A1
WO2012070202A1 PCT/JP2011/006387 JP2011006387W WO2012070202A1 WO 2012070202 A1 WO2012070202 A1 WO 2012070202A1 JP 2011006387 W JP2011006387 W JP 2011006387W WO 2012070202 A1 WO2012070202 A1 WO 2012070202A1
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Prior art keywords
epoxy resin
resin composition
phosphorus
compound
formula
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PCT/JP2011/006387
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French (fr)
Japanese (ja)
Inventor
博晴 井上
岸野　光寿
孝寿 阿部
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パナソニック株式会社
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Priority to CN201180056296.3A priority Critical patent/CN103228697B/en
Publication of WO2012070202A1 publication Critical patent/WO2012070202A1/en

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates

Definitions

  • the present invention relates to a substantially halogen-free epoxy resin composition, and more particularly to an epoxy resin composition suitably used as an insulating material for a printed wiring board or the like. Furthermore, the present invention relates to a prepreg, a metal-clad laminate and a printed wiring board using such an epoxy resin composition.
  • Epoxy resin compositions are widely used as printed wiring board materials because of their excellent adhesion, electrical insulation, and chemical resistance.
  • epoxy resin compositions used for printed wiring boards generally include halogen-based flame retardants such as bromine-based flame retardants and tetrabromobisphenol A-type epoxy
  • halogen-based flame retardant having a high effect of imparting flame retardancy
  • cured products of such halogen-containing epoxy resin compositions have the disadvantage that they may produce harmful substances such as hydrogen halide during combustion, which adversely affects the human body and the natural environment. .
  • Patent Document 1 an epoxy resin compounded with a phosphorus compound instead of a halogen-based flame retardant
  • blended with a resin composition as a flame-retardant method of such halogen free material has an addition type and a reaction type.
  • a resin composition using phenoxyphosphazene as an addition type phosphorus compound has been reported (for example, Patent Document 2)
  • a resin composition using a reaction type phosphazene compound as a reaction type phosphorus compound has also been reported (for example, Patent Document 3).
  • the resin composition using the additive phosphorus compound has a problem that the glass transition temperature (Tg) is lowered and the hygroscopic heat resistance is poor, and the resin composition using the reactive phosphorus compound is It has become a problem that the flame retardancy deteriorates.
  • the present invention is an epoxy resin composition capable of obtaining a highly reliable base material which is halogen-free, has high Tg, and exhibits excellent moisture absorption heat resistance, a prepreg obtained from this composition, and this composition It is an object of the present invention to provide a metal-clad laminate and a printed wiring board in which a resin insulation layer is formed from a metal.
  • the present invention is an epoxy resin composition
  • an epoxy resin composition comprising a phosphorus-modified phenol curing agent and an epoxy compound, wherein the phosphorus-modified phenol curing agent is a phosphorus compound and the following formula (I): (Wherein, R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more) And an epoxy resin composition characterized in that the compound represented by the formula (I) is contained, and the phosphorus compound is bonded to the aliphatic carbon of the compound represented by the formula (I).
  • the present invention it is possible to maintain flame retardancy without containing a halogen-based flame retardant, and to obtain a highly reliable base material having high Tg and exhibiting excellent moisture absorption heat resistance.
  • the composition can be provided.
  • the metal-clad laminate and the printed wiring board in which the prepreg obtained from the said composition and the resin insulating layer were formed by the said composition can be provided.
  • the epoxy resin composition of the present invention contains a phosphorus-modified phenol curing agent and an epoxy compound as a basic constitution.
  • the phosphorus-modified phenol curing agent used in the present invention comprises a phosphorus compound and the following formula (I): (Wherein R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more) And the phosphorus compound is bonded to the aliphatic carbon of the compound represented by the formula (I).
  • the phosphorus compound used in the phosphorus-modified phenol curing agent according to the present invention is particularly limited as long as it has a phosphorus-containing skeleton and can be bonded to the aliphatic carbon of the compound represented by the formula (I). It is not done. Specific examples thereof include phosphaphenanthrenes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter also referred to as HCA) or derivatives thereof, and the like, among which II): HCA represented by is preferably used as a phosphorus compound.
  • HCA 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • the epoxy resin of the present invention can be provided with flame retardancy, high Tg, and excellent moisture absorption heat resistance, and can be suitably used as a material of various substrates. .
  • the bonding site is preferably aliphatic carbon at the molecular terminal.
  • the proportion is preferably 3% by mass or less.
  • the ratio of the phosphorus compound not bonded to the aliphatic carbon of the compound represented by the formula (I) is 1% by mass or less with respect to the organic component in the epoxy resin composition according to the present invention preferable.
  • the hydroxyl equivalent of the phosphorus-modified phenol curing agent used in the present invention is preferably about 150 to 300, and more preferably 150 to 250.
  • the phosphorus-modified phenol curing agent as described above can also be obtained as a commercial product, and for example, EXB 9000, EXB 9005 and the like manufactured by DIC Corporation can be obtained.
  • the content of the phosphorus-modified phenol curing agent in the epoxy resin composition of the present invention is usually 0.1 to 90% by mass, and further 0.1 to 80% by mass, based on the total amount of the epoxy resin composition. It is more preferable that
  • any epoxy resin can be used without particular limitation as long as the effects of the present invention are not impaired.
  • two or more epoxy groups in one molecule Epoxy compounds and the like can be suitably used.
  • cresol novolac epoxy resin bisphenol F epoxy resin, phenol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, naphthalene epoxy, bisphenol A epoxy resin,
  • An epoxy resin such as a phenol aralkyl type epoxy resin can be mentioned. These may be used alone or in combination of two or more. Further, among these, novolac epoxy resins such as cresol novolac epoxy resins are particularly preferably used.
  • the epoxy equivalent of the epoxy compound contained in the epoxy resin of the present invention is preferably about 150 to 300 on average.
  • the content of the component (B) in the epoxy resin composition of the present invention is preferably 0.1 to 90% by mass, and more preferably 20 to 90% by mass in the total amount of the epoxy resin composition.
  • the epoxy resin composition of the present invention may further contain a curing accelerator to accelerate the curing reaction.
  • a curing accelerator any curing accelerator can be used without particular limitation as long as it can accelerate the curing reaction between the above-mentioned epoxy resin component and the phosphorus-modified phenol curing agent.
  • imidazoles such as 2-methylimidazole and cyanoethylimidazole
  • metal soaps such as zinc octanoate, copper naphthenate, cobalt naphthenate
  • organophosphorus compounds such as triphenylphosphine
  • amine compounds such as triethylamine
  • bases such as 1,8-diazabicyclo [5.4.0] undecene-7.
  • a curing accelerator in the present invention it is preferably about 0.01 to 2% by mass in the total amount of the epoxy resin composition.
  • the epoxy resin composition of the present invention can also contain a filler in order to improve the rigidity.
  • a filler inorganic fillers such as powders of metal powders such as silica powder, aluminum hydroxide and magnesium hydroxide, and powders of clay minerals such as talc and clay can be used. In addition to single use alone, it is also possible to use a combination of multiple species.
  • Such a filler is preferably blended in an amount of 0.1 to 250% by mass based on the total amount of the epoxy resin composition.
  • the epoxy resin composition of the present invention may further contain other additives, for example, a flame retardant, a flame retardant auxiliary, a leveling agent, a coloring agent, etc., as needed, as long as the effects of the present invention are not impaired. Good.
  • the epoxy resin composition of the present invention is usually prepared in the form of varnish and used.
  • a varnish is prepared, for example, as follows.
  • an organic solvent is blended with each component of the propoxy resin composition described above, and an inorganic filler and the like are further added as necessary, and uniformly dispersed and mixed using a ball mill, bead mill, mixer, blender, etc. It can be prepared in the form of a varnish.
  • the organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), ketones such as acetone and methyl ethyl ketone, methanol, ethanol and the like Alcohols, cellosolves, etc. can be mentioned. These may be used alone or in combination of two or more.
  • the prepreg of the present invention is obtained by impregnating the above-described varnish-like epoxy resin composition into a fibrous base material.
  • the fibrous base material is impregnated with the varnish-like resin by, for example, immersing the fibrous base material in the varnish-like resin. Impregnation is carried out by dipping (dipping), coating and the like. The impregnation can be repeated several times as needed. At this time, it is also possible to repeat the impregnation using a plurality of solutions having different compositions and concentrations, and finally adjust to the desired composition and resin amount.
  • the fibrous substrate is not particularly limited, but preferably a sheet-like fibrous substrate is used.
  • woven (cross) or non-woven fabric of inorganic fibers such as glass, aramid cloth, polyester cloth And paper can be used.
  • the thickness of the substrate may generally be 0.02 to 0.2 mm.
  • the substrate impregnated with the varnish-like epoxy resin composition is then heat dried under desired heating conditions (for example, at 100 to 180 ° C. for 3 to 10 minutes) to remove the solvent and semi-cure the resin component (B Staged to obtain a prepreg.
  • desired heating conditions for example, at 100 to 180 ° C. for 3 to 10 minutes
  • the amount of resin in the prepreg is preferably 30 to 80% by mass with respect to the total amount of the prepreg.
  • Metal-clad laminate As a method of producing a metal-clad laminate using the prepreg obtained as described above, one or more sheets of the prepreg are laminated, and metal foil such as copper foil is laminated on both upper and lower sides or one side There is a method of producing a double-sided metal-foiled or single-sided metal-foiled laminate by heat-pressing and laminating and integrating this.
  • the heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be produced, the type of resin composition of the prepreg, etc. For example, the temperature is 150 to 250 ° C., the pressure is 1 to 5 Pa, and the time is 30 to 240 It can be a minute.
  • Multilayer printed wiring board By forming a circuit by etching the metal foil on the surface of the laminate produced as described above, a printed wiring board provided with a conductor pattern as a circuit on the surface of the laminate can be obtained.
  • the printed wiring board obtained in this manner is excellent in heat resistance corresponding to lead-free solder, and further has sufficient flame retardancy even without containing a halogen-based flame retardant.
  • Hardening agent Phosphorus-modified phenol curing agent 1 DIC Corporation, “EXB 9000” (hydroxy group equivalent 207) -Phosphorus-modified phenol curing agent 2: DIC Corporation, "EXB 9005" (hydroxyl equivalent: 167) -Phenol curing agent: DIC Corporation "TD-2090" (hydroxy group equivalent 105) ⁇ Phosphorus compound> -Phenoxy phosphazene (addition type phosphorus compound): Otsuka Chemical Co., Ltd. product, "SPB-100” Phosphaphenanthrene (HCA): Sanko Co., Ltd.
  • Examples 1 to 4 and Comparative Examples 1 to 5 In addition to the compounding composition (parts by mass) shown in Table 1, methyl ethyl ketone is further added as a solvent to prepare the epoxy resin varnish according to Examples 1 to 4 and Comparative Examples 1 to 5 having a solid content of 50 to 70% by mass. did.
  • a glass cloth (2116 manufactured by Asahi Kasei E-materials) is immersed in each of the resin varnishes described above to impregnate the resin varnish with the glass cloth and then heat dried at 150 to 170 ° C. for 3 to 5 minutes.
  • the prepreg was produced by removing the solvent and semi-curing the resin component (B-staging). At this time, the amount of resin in the prepreg was 45 to 55% by mass with respect to the total amount of the prepreg.
  • a copper foil of 12 ⁇ m thickness JTCLPZ manufactured by Nippon Mining & Metals Co., Ltd.
  • a pressure target at a temperature of 220 ° C and a pressure of 30 kg / cm 2
  • a heat and pressure was applied for 240 minutes to obtain a copper-clad laminate with a thickness of 0.8 mm in which copper foils were adhered on both sides.
  • the glass transition temperature (Tg), the PCT solder heat resistance, and the flame retardancy were evaluated by the methods described below using the prepreg and the copper-clad laminate obtained as described above as samples for evaluation. The results are shown in Table 1.
  • Tg Glass transition temperature
  • DMA dynamic viscoelasticity measurement
  • PCT solder heat resistance After removing the copper foil on the surface of the copper-clad laminate, a test piece having a length of 50 mm and a width of 50 mm was cut out. The test piece was placed in a pressure cooker test (PCT) machine at 121 ° C., 2 atm, 100% humidity for 4 hours and 6 hours. Dip the test piece into the solder bath at 260 ° C for 20 seconds, and if there are no 3 meslings or swelling out of 3 samples, ⁇ , 2 out of 3 samples no meringing or swelling The remaining samples were evaluated as ⁇ ⁇ ⁇ if there was measling or blistering, or as x if there were more than two of the three being measling or blistering.
  • PCT pressure cooker test
  • Example 4 is obtained by further adding phosphaphenanthrene (HCA) to Example 1, but 1% by mass or more of a non-bonded phosphorus compound is contained with respect to the organic component of the resin composition As a result, the PCT solder heat resistance was slightly inferior to that of Examples 1 to 3.
  • HCA phosphaphenanthrene
  • the epoxy resin composition according to one embodiment of the present invention is an epoxy resin composition containing a phosphorus-modified phenol curing agent and an epoxy compound, and the phosphorus-modified phenol curing agent is a phosphorus compound ,
  • the phosphorus compound has the following formula (II): It is preferable that it is a phosphorus compound shown by these.
  • the base material formed of the epoxy resin having such a constitution has a high Tg, and is excellent in hygroscopic heat resistance and flame retardancy.
  • bonded with the compound represented by Formula (I) in a phosphorus modified phenol curing agent is 3 mass% or less.
  • bonded with the compound represented by Formula (I) is 1 mass% or less with respect to the organic component in an epoxy resin composition. With such a configuration, high flame retardancy and hygroscopic heat resistance can be obtained more reliably.
  • a prepreg according to another embodiment of the present invention is characterized in that it is obtained by impregnating and drying the above-mentioned epoxy resin composition in a fibrous base material.
  • the metal-clad laminate according to another embodiment of the present invention is characterized in that it is obtained by laminating a metal foil on the above-mentioned prepreg and subjecting it to heat and pressure forming.
  • the printed wiring board according to a further embodiment of the present invention is characterized in that it is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate.

Abstract

The purpose is to provide the following: an epoxy resin composition capable of maintaining flame retardancy without containing a halogenated flame retardant in the epoxy resin composition, being heat-resistant for lead-free soldering, and with which it is possible to obtain a substrate that maintains excellent plating adhesion; a prepreg obtained from the composition; and a metal-clad laminate and a printed wiring board on which a resin insulating layer is formed from the composition. An epoxy resin composition containing a phosphorus-modified phenolic curing agent and an epoxy compound, the epoxy resin composition being characterized in that the phosphorus-modified phenolic curing agent contains a phosphorus compound and a compound represented by formula (I) (In the formula, R represents a hydroxyl group or a O-methyl group, and n represents an integer of 2 or greater), and by the phosphorus compound being bonded to the aliphatic carbon in the compound represented by formula (I).

Description

高耐熱性エポキシ樹脂組成物、プリプレグ、金属張積層板およびプリント配線板High heat resistant epoxy resin composition, prepreg, metal-clad laminate and printed wiring board
　本発明は、実質的にハロゲンを含有しないエポキシ樹脂組成物に関し、特に、プリント配線板等の絶縁材として好適に用いられるエポキシ樹脂組成物に関する。さらに本発明は、このようなエポキシ樹脂組成物を用いたプリプレグ、金属張積層板およびプリント配線板に関する。 The present invention relates to a substantially halogen-free epoxy resin composition, and more particularly to an epoxy resin composition suitably used as an insulating material for a printed wiring board or the like. Furthermore, the present invention relates to a prepreg, a metal-clad laminate and a printed wiring board using such an epoxy resin composition.
　エポキシ樹脂組成物は、その優れた接着性、電気絶縁性、および耐薬品性等から、プリント配線板材料として広く用いられている。 Epoxy resin compositions are widely used as printed wiring board materials because of their excellent adhesion, electrical insulation, and chemical resistance.
　ところが、エポキシ樹脂は比較的難燃性に乏しいために、プリント配線板に用いられるエポキシ樹脂組成物には、一般的に、臭素系難燃剤等のハロゲン系難燃剤や、テトラブロモビスフェノールＡ型エポキシ樹脂等のハロゲン含有エポキシ樹脂等の難燃性を付与する効果の高いハロゲン系難燃剤が配合されている。しかしながら、このようなハロゲンを含有するエポキシ樹脂組成物の硬化物は、燃焼時にハロゲン化水素等の有害物質を生成するおそれがあり、人体や自然環境に対し悪影響を及ぼすという欠点を有している。 However, since epoxy resins have relatively poor flame retardancy, epoxy resin compositions used for printed wiring boards generally include halogen-based flame retardants such as bromine-based flame retardants and tetrabromobisphenol A-type epoxy A halogen-based flame retardant having a high effect of imparting flame retardancy such as a halogen-containing epoxy resin such as a resin is blended. However, cured products of such halogen-containing epoxy resin compositions have the disadvantage that they may produce harmful substances such as hydrogen halide during combustion, which adversely affects the human body and the natural environment. .
　この欠点を解消するために、例えば、ハロゲン系難燃剤の代わりに、リン化合物を配合したエポキシ樹脂を用いることが知られている（例えば、特許文献１）。 In order to eliminate this drawback, for example, it is known to use an epoxy resin compounded with a phosphorus compound instead of a halogen-based flame retardant (for example, Patent Document 1).
　また、このようなハロゲンフリー材料の難燃化手法として樹脂組成物に配合され得るリン化合物には、添加型と反応型があることがこれまでにも知られている。例えば、添加型リン化合物としてフェノキシホスファゼンを用いる樹脂組成物が報告されており（例えば、特許文献２）、さらに反応型リン化合物として反応型ホスファゼン化合物を用いる樹脂組成物も報告されている（例えば、特許文献３）。 Moreover, it is known that the phosphorus compound which can be mix | blended with a resin composition as a flame-retardant method of such halogen free material has an addition type and a reaction type. For example, a resin composition using phenoxyphosphazene as an addition type phosphorus compound has been reported (for example, Patent Document 2), and a resin composition using a reaction type phosphazene compound as a reaction type phosphorus compound has also been reported (for example, Patent Document 3).
特開２００７－３２６９２９号公報Unexamined-Japanese-Patent No. 2007-326929 特開２００８－５６８２０号公報JP, 2008-56820, A 特開２００６－３６７３６号公報JP, 2006-36736, A
　しかしながら、添加型リン化合物を用いた樹脂組成物は、ガラス転移温度（Ｔｇ）の低下と吸湿耐熱性が悪いことが問題となっており、さらに、反応型リン化合物を用いた樹脂組成物は、難燃性が悪くなることが問題となってきている。 However, the resin composition using the additive phosphorus compound has a problem that the glass transition temperature (Tg) is lowered and the hygroscopic heat resistance is poor, and the resin composition using the reactive phosphorus compound is It has become a problem that the flame retardancy deteriorates.
　近年、材料樹脂に対する高品質化の要求は高まっており、より信頼性の高い、高Ｔｇ、高吸湿耐熱性のハロゲンフリー材料が求められている。 In recent years, demands for higher quality of material resins are increasing, and halogen-free materials having higher reliability, high Tg, and high moisture absorption heat resistance are required.
　よって、本発明は、ハロゲンフリーで、高Ｔｇを有し、さらに優れた吸湿耐熱性を示す信頼性の高い基材を得ることができるエポキシ樹脂組成物、この組成物から得られるプリプレグ、この組成物から樹脂絶縁層が形成された金属張積層板およびプリント配線板を提供することを目的とする。 Therefore, the present invention is an epoxy resin composition capable of obtaining a highly reliable base material which is halogen-free, has high Tg, and exhibits excellent moisture absorption heat resistance, a prepreg obtained from this composition, and this composition It is an object of the present invention to provide a metal-clad laminate and a printed wiring board in which a resin insulation layer is formed from a metal.
　本発明者は、前記課題を解決すべく鋭意検討した結果、以下の手段により前記課題を解決できることを見出した。 MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject could be solved by the following means, as a result of earnestly examining in order to solve the said subject.
　すなわち、本発明は、リン変性フェノール硬化剤とエポキシ化合物を含むエポキシ樹脂組成物であって、前記リン変性フェノール硬化剤がリン化合物と下記式（Ｉ）：
Figure JPOXMLDOC01-appb-I000001
（式中、Ｒは水酸基又はＯ－メチル基であり、ｎは２以上の整数を示す）
で表される化合物を含むこと、及び前記リン化合物が前記式（Ｉ）で表される化合物の脂肪族炭素に結合していることを特徴とする、エポキシ樹脂組成物を包含する。 That is, the present invention is an epoxy resin composition comprising a phosphorus-modified phenol curing agent and an epoxy compound, wherein the phosphorus-modified phenol curing agent is a phosphorus compound and the following formula (I):
Figure JPOXMLDOC01-appb-I000001
(Wherein, R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more)
And an epoxy resin composition characterized in that the compound represented by the formula (I) is contained, and the phosphorus compound is bonded to the aliphatic carbon of the compound represented by the formula (I).
　本発明によれば、ハロゲン系難燃剤を含有させなくとも難燃性を維持でき、かつ高Ｔｇを有し、さらに優れた吸湿耐熱性を示す信頼性の高い基材を得ることができるエポキシ樹脂組成物を提供できる。また、前記組成物から得られるプリプレグ、ならびに前記組成物によって樹脂絶縁層が形成された金属張積層板およびプリント配線板を提供することができる。 According to the present invention, it is possible to maintain flame retardancy without containing a halogen-based flame retardant, and to obtain a highly reliable base material having high Tg and exhibiting excellent moisture absorption heat resistance. The composition can be provided. Moreover, the metal-clad laminate and the printed wiring board in which the prepreg obtained from the said composition and the resin insulating layer were formed by the said composition can be provided.
　（エポキシ樹脂組成物）
　まず、本発明のエポキシ樹脂組成物は、基本構成としてリン変性フェノール硬化剤とエポキシ化合物を含む。 (Epoxy resin composition)
First, the epoxy resin composition of the present invention contains a phosphorus-modified phenol curing agent and an epoxy compound as a basic constitution.
　本発明において用いるリン変性フェノール硬化剤は、リン化合物と下記式（Ｉ）：
Figure JPOXMLDOC01-appb-I000002
（式中、Ｒは水酸基、又はＯ－メチル基であり、ｎは２以上の整数を示す）
で表される化合物とを有しており、かつ前記リン化合物は前記式（Ｉ）で表される化合物の脂肪族炭素に結合している。 The phosphorus-modified phenol curing agent used in the present invention comprises a phosphorus compound and the following formula (I):
Figure JPOXMLDOC01-appb-I000002
(Wherein R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more)
And the phosphorus compound is bonded to the aliphatic carbon of the compound represented by the formula (I).
　本発明に係るリン変性フェノール硬化剤に用いられるリン化合物としては、リン含有骨格を有し、前記式（Ｉ）で表される化合物の脂肪族炭素に結合することができるものであれば特に限定はされない。具体的には、９，１０－ジヒドロ－９－オキサ－１０－ホスファフェナントレン－１０－オキシド（以下、ＨＣＡとも称す）またはその誘導体などのホスファフェナントレン類などが挙げられ、なかでも下記式（ＩＩ）：
Figure JPOXMLDOC01-appb-I000003
で表されるＨＣＡがリン化合物として好ましく用いられる。 The phosphorus compound used in the phosphorus-modified phenol curing agent according to the present invention is particularly limited as long as it has a phosphorus-containing skeleton and can be bonded to the aliphatic carbon of the compound represented by the formula (I). It is not done. Specific examples thereof include phosphaphenanthrenes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter also referred to as HCA) or derivatives thereof, and the like, among which II):
Figure JPOXMLDOC01-appb-I000003
HCA represented by is preferably used as a phosphorus compound.
　このようなリン変性フェノール硬化剤を用いることにより、本発明のエポキシ樹脂は、難燃性、高Ｔｇ、及び優れた吸湿耐熱性を備えることができ、各種基材の材料として好適に用いられ得る。 By using such a phosphorus-modified phenol curing agent, the epoxy resin of the present invention can be provided with flame retardancy, high Tg, and excellent moisture absorption heat resistance, and can be suitably used as a material of various substrates. .
　さらに、本発明のリン変性フェノール硬化剤では、前記式（Ｉ）で表される化合物の脂肪族炭素に結合しているが、その結合箇所は分子末端の脂肪族炭素であることが好ましい。このようにリンが化合物の骨格の末端に存在することによって、一般的な反応型リン化合物が引きおこす難燃性低下の問題が生じることもなく、高い難燃性を確実に維持することができる。 Furthermore, in the phosphorus-modified phenol curing agent of the present invention, although it is bonded to the aliphatic carbon of the compound represented by the formula (I), the bonding site is preferably aliphatic carbon at the molecular terminal. Thus, by the presence of phosphorus at the end of the skeleton of the compound, high flame retardancy can be reliably maintained without the problem of decrease in flame retardancy caused by general reactive phosphorus compounds.
　また、リン変性フェノール硬化剤に含まれるリン化合物はすべて前記式（Ｉ）で表される化合物の脂肪族炭素に結合していることが理想的であるが、少なくとも、結合していないリン化合物が、リン変性フェノール硬化剤中において３質量％以下の割合であることが好ましい。あるいは、本発明に係るエポキシ樹脂組成物中の有機成分に対して、前記式（Ｉ）で表される化合物の脂肪族炭素に結合していないリン化合物が１質量％以下の割合であることが好ましい。 In addition, although it is ideal that all phosphorus compounds contained in the phosphorus-modified phenol curing agent are bonded to the aliphatic carbon of the compound represented by the formula (I), at least the phosphorus compounds which are not bonded are In the phosphorus-modified phenol curing agent, the proportion is preferably 3% by mass or less. Alternatively, the ratio of the phosphorus compound not bonded to the aliphatic carbon of the compound represented by the formula (I) is 1% by mass or less with respect to the organic component in the epoxy resin composition according to the present invention preferable.
　また、本発明に用いるリン変性フェノール硬化剤の水酸基当量は１５０～３００程度であることが好ましく、さらに１５０～２５０の範囲であればより好ましい。 The hydroxyl equivalent of the phosphorus-modified phenol curing agent used in the present invention is preferably about 150 to 300, and more preferably 150 to 250.
　上述したようなリン変性フェノール硬化剤は、市販品として入手することも可能であり、例えば、ＤＩＣ株式会社製のＥＸＢ９０００、ＥＸＢ９００５等が入手し得る。 The phosphorus-modified phenol curing agent as described above can also be obtained as a commercial product, and for example, EXB 9000, EXB 9005 and the like manufactured by DIC Corporation can be obtained.
　また、本発明のエポキシ樹脂組成物中の前記リン変性フェノール硬化剤の含有割合としては、エポキシ樹脂組成物全量中に通常０．１～９０質量％であり、さらには０．１～８０質量％であることがより好ましい。 The content of the phosphorus-modified phenol curing agent in the epoxy resin composition of the present invention is usually 0.1 to 90% by mass, and further 0.1 to 80% by mass, based on the total amount of the epoxy resin composition. It is more preferable that
　次に、本発明のエポキシ樹脂に含まれるエポキシ化合物としては、本発明の効果を妨げない範囲で特に限定なくあらゆるエポキシ樹脂を使用することができ、例えば、１分子中に２個以上のエポキシ基を有するエポキシ化合物等が好適に使用できる。 Next, as the epoxy compound contained in the epoxy resin of the present invention, any epoxy resin can be used without particular limitation as long as the effects of the present invention are not impaired. For example, two or more epoxy groups in one molecule Epoxy compounds and the like can be suitably used.
　より具体的な例示としては、例えば、クレゾールノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン型エポキシ、ビスフェノールＡ型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂等のエポキシ樹脂が挙げられる。これらは、単独で用いても、２種以上を組み合わせて用いてもよい。また、これらの中では、特に、クレゾールノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂が好ましく用いられる。 More specific examples include, for example, cresol novolac epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, naphthalene epoxy, bisphenol A epoxy resin, An epoxy resin such as a phenol aralkyl type epoxy resin can be mentioned. These may be used alone or in combination of two or more. Further, among these, novolac epoxy resins such as cresol novolac epoxy resins are particularly preferably used.
　なお、本発明のエポキシ樹脂に含まれるエポキシ化合物のエポキシ当量としては、平均で１５０～３００程度であることが好ましい。 The epoxy equivalent of the epoxy compound contained in the epoxy resin of the present invention is preferably about 150 to 300 on average.
　また、本発明のエポキシ樹脂組成物中の前記（Ｂ）成分の含有割合としては、エポキシ樹脂組成物全量中に０．１～９０質量％、さらには２０～９０質量％であることが好ましい。 The content of the component (B) in the epoxy resin composition of the present invention is preferably 0.1 to 90% by mass, and more preferably 20 to 90% by mass in the total amount of the epoxy resin composition.
　さらに、本発明のエポキシ樹脂組成物には、前述の必須成分以外に硬化反応を促進するために硬化促進剤を含有させてもよい。硬化促進剤としては上述したエポキシ樹脂成分とリン変性フェノール硬化剤との硬化反応を促進することができるものであれば、特に限定なく使用することができる。具体的には、例えば、２－メチルイミダゾールやシアノエチルイミダゾール等のイミダゾール類；オクタン酸亜鉛、ナフテン酸銅、ナフテン酸コバルト等の金属石鹸；トリフェニルホスフィンなどの有機リン化合物；トリエチルアミンなどのアミン化合物；１，８－ジアザビシクロ［５．４．０］ウンデセン－７などの塩基類等が挙げられる。これらは単独で用いても、２種以上を組み合わせて用いてもよい。 In addition to the above-mentioned essential components, the epoxy resin composition of the present invention may further contain a curing accelerator to accelerate the curing reaction. As the curing accelerator, any curing accelerator can be used without particular limitation as long as it can accelerate the curing reaction between the above-mentioned epoxy resin component and the phosphorus-modified phenol curing agent. Specifically, for example, imidazoles such as 2-methylimidazole and cyanoethylimidazole; metal soaps such as zinc octanoate, copper naphthenate, cobalt naphthenate; organophosphorus compounds such as triphenylphosphine; amine compounds such as triethylamine; And bases such as 1,8-diazabicyclo [5.4.0] undecene-7. These may be used alone or in combination of two or more.
　本発明において硬化促進剤を含有する場合には、エポキシ樹脂組成物全量中に、０．０１～２質量％程度であることが好ましい。 In the case of containing a curing accelerator in the present invention, it is preferably about 0.01 to 2% by mass in the total amount of the epoxy resin composition.
　また、本発明のエポキシ樹脂組成物には剛性を向上させるために、フィラーを含有させることもできる。フィラーの具体例としては、シリカ粉末、水酸化アルミニウム、水酸化マグネシウム等の金属水和物の粉末、タルク、クレー等の粘土鉱物の粉末といった、無機フィラーを用いることができ、これらのフィラーは一種のみを単独で用いるほか、複数種を併用することもできる。このようなフィラーは、エポキシ樹脂組成物全量に対して０．１～２５０質量％配合することが好ましい。 The epoxy resin composition of the present invention can also contain a filler in order to improve the rigidity. As specific examples of the filler, inorganic fillers such as powders of metal powders such as silica powder, aluminum hydroxide and magnesium hydroxide, and powders of clay minerals such as talc and clay can be used. In addition to single use alone, it is also possible to use a combination of multiple species. Such a filler is preferably blended in an amount of 0.1 to 250% by mass based on the total amount of the epoxy resin composition.
　本発明のエポキシ樹脂組成物は、さらに、本発明の効果を損なわない範囲でその他の添加剤、例えば、難燃剤、難燃助剤、レベリング剤、着色剤等を必要に応じて含有してもよい。 The epoxy resin composition of the present invention may further contain other additives, for example, a flame retardant, a flame retardant auxiliary, a leveling agent, a coloring agent, etc., as needed, as long as the effects of the present invention are not impaired. Good.
　本発明のエポキシ樹脂組成物は、通常、ワニス状に調製されて用いられる。このようなワニスは、例えば、以下のようにして調製される。 The epoxy resin composition of the present invention is usually prepared in the form of varnish and used. Such a varnish is prepared, for example, as follows.
　つまり、上述したポキシ樹脂組成物の各成分に有機溶剤を配合し、必要に応じてさらに無機充填剤などを添加して、ボールミル、ビーズミル、ミキサー、ブレンダー等を用いて均一に分散・混合し、ワニス状に調製することができる。 That is, an organic solvent is blended with each component of the propoxy resin composition described above, and an inorganic filler and the like are further added as necessary, and uniformly dispersed and mixed using a ball mill, bead mill, mixer, blender, etc. It can be prepared in the form of a varnish.
　前記有機溶剤としては、特に限定されず、例えば、ベンゼン、トルエン等の芳香族炭化水素類、Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）等のアミド類、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール等のアルコール類、セロソルブ類等を挙げることができる。これらは単独で用いても、２種以上を組み合わせて用いてもよい。 The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene and toluene, amides such as N, N-dimethylformamide (DMF), ketones such as acetone and methyl ethyl ketone, methanol, ethanol and the like Alcohols, cellosolves, etc. can be mentioned. These may be used alone or in combination of two or more.
　（プリプレグ）
　本発明のプリプレグは、上述のワニス状エポキシ樹脂組成物を繊維質基材に含浸して得られる。 (Prepreg)
The prepreg of the present invention is obtained by impregnating the above-described varnish-like epoxy resin composition into a fibrous base material.
　具体的には、例えば、まず、前記ワニス状樹脂中に繊維質基材を浸漬するなどして、ワニス状樹脂を繊維質基材に含浸させる。含浸は浸漬（ディッピング）、塗布等によって行われる。含浸は必要に応じて複数回繰り返すことも可能である。またこの際に組成や濃度の異なる複数の溶液を用いて含浸を繰り返し、最終的に希望とする組成および樹脂量に調整することも可能である。 Specifically, for example, the fibrous base material is impregnated with the varnish-like resin by, for example, immersing the fibrous base material in the varnish-like resin. Impregnation is carried out by dipping (dipping), coating and the like. The impregnation can be repeated several times as needed. At this time, it is also possible to repeat the impregnation using a plurality of solutions having different compositions and concentrations, and finally adjust to the desired composition and resin amount.
　前記繊維質基材としては、特に限定されるものではないが、好ましくはシート状繊維基材が用いられ、例えば、ガラス等の無機質繊維の織布（クロス）または不織布や、アラミドクロス、ポリエステルクロス、および紙等を用いることができる。また、基材の厚みとしては、０．０２～０．２ｍｍのものを一般的に使用できる。 The fibrous substrate is not particularly limited, but preferably a sheet-like fibrous substrate is used. For example, woven (cross) or non-woven fabric of inorganic fibers such as glass, aramid cloth, polyester cloth And paper can be used. The thickness of the substrate may generally be 0.02 to 0.2 mm.
　ワニス状エポキシ樹脂組成物が含浸された基材を、その後、所望の加熱条件（例えば、１００～１８０℃で３～１０分間）で加熱乾燥し、溶剤を除去するとともに樹脂成分を半硬化（Ｂステージ化）させて、プリプレグを得る。このときプリプレグ中の樹脂量は、プリプレグ全量に対して３０～８０質量％であることが好ましい。 The substrate impregnated with the varnish-like epoxy resin composition is then heat dried under desired heating conditions (for example, at 100 to 180 ° C. for 3 to 10 minutes) to remove the solvent and semi-cure the resin component (B Staged to obtain a prepreg. At this time, the amount of resin in the prepreg is preferably 30 to 80% by mass with respect to the total amount of the prepreg.
　（金属張積層板）
　上述のようにして得られたプリプレグを用いて金属張積層板を作成する方法としては、前記プリプレグを一枚または複数枚重ね、さらにその上下の両面または片面に銅箔等の金属箔を重ね、これを加熱加圧成形して積層一体化することによって、両面金属箔張りまたは片面金属箔張りの積層体を作製する方法が挙げられる。加熱加圧条件は、製造する積層板の厚みやプリプレグの樹脂組成物の種類等により適宜設定することができるが、例えば、温度を１５０～２５０℃、圧力を１～５Ｐａ、時間を３０～２４０分間とすることができる。 (Metal-clad laminate)
As a method of producing a metal-clad laminate using the prepreg obtained as described above, one or more sheets of the prepreg are laminated, and metal foil such as copper foil is laminated on both upper and lower sides or one side There is a method of producing a double-sided metal-foiled or single-sided metal-foiled laminate by heat-pressing and laminating and integrating this. The heating and pressing conditions can be appropriately set depending on the thickness of the laminate to be produced, the type of resin composition of the prepreg, etc. For example, the temperature is 150 to 250 ° C., the pressure is 1 to 5 Pa, and the time is 30 to 240 It can be a minute.
　（多層プリント配線板）
　上述のようにして作製された積層体の表面の金属箔をエッチング加工等して回路形成をすることによって、積層体の表面に回路として導体パターンを設けたプリント配線板を得ることができる。 (Multilayer printed wiring board)
By forming a circuit by etching the metal foil on the surface of the laminate produced as described above, a printed wiring board provided with a conductor pattern as a circuit on the surface of the laminate can be obtained.
　このようにして得られるプリント配線板は、鉛フリーはんだ対応の耐熱性に優れており、さらに、ハロゲン系難燃剤を含有しなくとも充分な難燃性を備えたものである。 The printed wiring board obtained in this manner is excellent in heat resistance corresponding to lead-free solder, and further has sufficient flame retardancy even without containing a halogen-based flame retardant.
　以下に、本発明について、実施例によりさらに具体的に説明する。なお、本発明は以下の実施例により何ら限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples. The present invention is not limited at all by the following examples.
　はじめに、本実施例で用いた原材料をまとめて示す。
〈硬化剤〉
・リン変性フェノール硬化剤１：ＤＩＣ（株）製、「ＥＸＢ９０００」（水酸基当量２０７）
・リン変性フェノール硬化剤２：ＤＩＣ（株）製、「ＥＸＢ９００５」（水酸基当量１６７）
・フェノール硬化剤：ＤＩＣ（株）製、「ＴＤ－２０９０」（水酸基当量１０５）
〈リン化合物〉
・フェノキシホスファゼン（添加型リン化合物）：大塚化学（株）製、「ＳＰＢ－１００」
・ホスファフェナントレン（ＨＣＡ）：三光（株）製、「ＨＣＡ」
・反応型ホスファゼン：大塚化学（株）製、「ＳＰＨ－１００」（水酸基当量２５０）
〈エポキシ化合物〉
・クレゾールノボラックエポキシ：ＤＩＣ（株）製、「Ｎ－６９０」（クレゾールノボラックエポキシ樹脂，エポキシ当量２１５）
・リン変性エポキシ樹脂：東都化成（株）製、「ＦＸ２８９」（エポキシ当量３１８）
〈フィラー〉
・水酸化アルミニウム：住友化学（株）製、「ＣＬ－３０３」
・溶融シリカ：（株）アドマテックス製、「ＳＣ－２５００－ＳＥＪ」
〈硬化促進剤〉
・イミダゾール：四国化成工業（株）製「２Ｅ４ＭＺ」。 First, raw materials used in this example are summarized.
Hardening agent
Phosphorus-modified phenol curing agent 1: DIC Corporation, “EXB 9000” (hydroxy group equivalent 207)
-Phosphorus-modified phenol curing agent 2: DIC Corporation, "EXB 9005" (hydroxyl equivalent: 167)
-Phenol curing agent: DIC Corporation "TD-2090" (hydroxy group equivalent 105)
<Phosphorus compound>
-Phenoxy phosphazene (addition type phosphorus compound): Otsuka Chemical Co., Ltd. product, "SPB-100"
Phosphaphenanthrene (HCA): Sanko Co., Ltd. product "HCA"
Reactive phosphazene: Otsuka Chemical Co., Ltd. "SPH-100" (hydroxy group equivalent 250)
<Epoxy compound>
・ Cresol novolac epoxy: manufactured by DIC Corporation, “N-690” (cresol novolac epoxy resin, epoxy equivalent 215)
Phosphorus-modified epoxy resin: manufactured by Tohto Kasei Co., Ltd., "FX 289" (epoxy equivalent weight 318)
<Filler>
-Aluminum hydroxide: manufactured by Sumitomo Chemical Co., Ltd., "CL-303"
· Fused silica: manufactured by Admatex, "SC-2500-SEJ"
<Hardening accelerator>
-Imidazole: "2E4MZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.
　（実施例１～４および比較例１～５）
　表１に示した、配合組成（質量部）に加え、さらにメチルエチルケトンを溶剤として加え、固形分が５０～７０質量％の、実施例１～４および比較例１～５に係るエポキシ樹脂ワニスを調整した。 (Examples 1 to 4 and Comparative Examples 1 to 5)
In addition to the compounding composition (parts by mass) shown in Table 1, methyl ethyl ketone is further added as a solvent to prepare the epoxy resin varnish according to Examples 1 to 4 and Comparative Examples 1 to 5 having a solid content of 50 to 70% by mass. did.
　次に、上記のそれぞれの樹脂ワニス中にガラスクロス（旭化成イーマテリアルズ製の２１１６）を浸漬して、樹脂ワニスをガラスクロスに含浸させた後、１５０～１７０℃で３～５分間加熱乾燥し、溶剤を除去するとともに樹脂成分を半硬化（Ｂステージ化）させることによってプリプレグを作製した。このときプリプレグ中の樹脂量は、プリプレグ全量に対して４５～５５質量％とした。 Next, a glass cloth (2116 manufactured by Asahi Kasei E-materials) is immersed in each of the resin varnishes described above to impregnate the resin varnish with the glass cloth and then heat dried at 150 to 170 ° C. for 3 to 5 minutes. The prepreg was produced by removing the solvent and semi-curing the resin component (B-staging). At this time, the amount of resin in the prepreg was 45 to 55% by mass with respect to the total amount of the prepreg.
　さらに、製造したプリプレグを８枚重ね合わせ、その両側に厚さ１２μｍの銅箔（日鉱金属株式会社製のＪＴＣＬＰＺ）を配置して被圧体とし、温度２２０℃、圧力３０ｋｇ／ｃｍ２の条件で２４０分加熱・加圧して両面に銅箔が接着された、厚み０．８ｍｍの銅張り積層板を得た。 Furthermore, eight sheets of the manufactured prepreg are stacked, and a copper foil of 12 μm thickness (JTCLPZ manufactured by Nippon Mining & Metals Co., Ltd.) is placed on both sides of the prepreg to form a pressure target at a temperature of 220 ° C and a pressure of 30 kg / cm 2 A heat and pressure was applied for 240 minutes to obtain a copper-clad laminate with a thickness of 0.8 mm in which copper foils were adhered on both sides.
　上記のようにして得られたプリプレグおよび銅張り積層板を評価用サンプルとして用いて、以下に示す方法により、ガラス転移温度（Ｔｇ）、ＰＣＴはんだ耐熱、および難燃性の評価を行った。これらの結果を表１に示す。 The glass transition temperature (Tg), the PCT solder heat resistance, and the flame retardancy were evaluated by the methods described below using the prepreg and the copper-clad laminate obtained as described above as samples for evaluation. The results are shown in Table 1.
　［ガラス転移温度（Ｔｇ）］
　セイコーインスツルメンツ株式会社製の粘弾性スペクトロメータ「ＤＭＳ１００」を用いて、積層板のＴｇを測定した。このとき、曲げモジュールで周波数を１０Ｈｚとして動的粘弾性測定（ＤＭＡ）を行い、昇温速度５℃／分の条件で室温から２８０℃まで昇温した際のｔａｎδが極大を示す温度をＴｇとした。 [Glass transition temperature (Tg)]
The Tg of the laminate was measured using a viscoelastic spectrometer "DMS 100" manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) is performed with a bending module at a frequency of 10 Hz, and a temperature at which tan δ shows a maximum at a temperature rising from room temperature to 280 ° C. under a condition of a temperature raising rate of 5 ° C./min did.
　［ＰＣＴはんだ耐熱］
　銅張り積層板の表面の銅箔を除去した後、長さ５０ｍｍ、幅５０ｍｍのテストピースを切り出した。このテストピースを１２１℃、２気圧、湿度１００％のプレッシャークッカーテスト（ＰＣＴ）機に４時間および６時間投入した。投入後のテストピースを２６０℃のはんだ槽中に２０秒間浸漬し、サンプル数３個のうち全てミーズリングやフクレがなければ○、サンプル数３個のうち２個がミーズリングやフクレがなく、残りのサンプルにミーズリングやフクレがあれば△、ミーズリングやフクレがサンプル数３個のうち２個以上にあれば×と評価した。 [PCT solder heat resistance]
After removing the copper foil on the surface of the copper-clad laminate, a test piece having a length of 50 mm and a width of 50 mm was cut out. The test piece was placed in a pressure cooker test (PCT) machine at 121 ° C., 2 atm, 100% humidity for 4 hours and 6 hours. Dip the test piece into the solder bath at 260 ° C for 20 seconds, and if there are no 3 meslings or swelling out of 3 samples, ○, 2 out of 3 samples no meringing or swelling The remaining samples were evaluated as あ れ ば if there was measling or blistering, or as x if there were more than two of the three being measling or blistering.
　［難燃性］
　銅張積層板の銅箔を除去した後、長さ１２７ｍｍ、幅１２.７ｍｍのテストピースを切り出した。そして、このテストピースについて、Ｕｎｄｅｒｗｒｉｔｅｒｓ　Ｌａｂｏｒａｔｏｒｉｅｓの“Ｔｅｓｔ　ｆｏｒ　Ｆｌａｍｍａｂｉｌｉｔｙ　ｏｆ　Ｐｌａｓｔｉｃ　Ｍａｔｅｒｉａｌｓ　ＵＬ　９４”の燃焼試験法に準じて燃焼試験を行い、判定した。 [Flame retardance]
After removing the copper foil of the copper clad laminate, a test piece 127 mm long and 12.7 mm wide was cut out. And about this test piece, the burning test was done and judged according to the burning test method of "Test for Flammability of Plastic Materials UL 94" of Underwriters Laboratories.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（結果）
　表１の結果より、本発明に係る実施例１～４の積層板は、いずれも高いＴｇを有しており、またハロゲン系難燃剤を用いなくとも優れた難燃性を示したことがわかる。さらに、いずれの実施例の多層プリント板においても、良好なＰＣＴはんだ耐熱性を示した。 (result)
From the results in Table 1, it can be seen that the laminates of Examples 1 to 4 according to the present invention all have high Tg and show excellent flame retardancy without using a halogen-based flame retardant. . Furthermore, the multilayer printed circuit board of any of the examples showed good PCT solder heat resistance.
　なお、実施例４は、実施例１にさらにホスファフェナントレン（ＨＣＡ）を加えたものであるが、結合していないリン化合物が樹脂組成物の有機成分に対して1質量％以上含まれることとなるため、ＰＣＴはんだ耐熱性が実施例１～３に比べるとやや劣っていた。 Example 4 is obtained by further adding phosphaphenanthrene (HCA) to Example 1, but 1% by mass or more of a non-bonded phosphorus compound is contained with respect to the organic component of the resin composition As a result, the PCT solder heat resistance was slightly inferior to that of Examples 1 to 3.
　一方、本発明に係るリン変性フェノール硬化剤の代わりに、フェノール硬化剤とフェノキシホスファゼン（添加型リン化合物）を２０質量部用いた比較例１の積層板、並びにフェノール硬化剤を含まずエポキシ樹脂としてリン変性エポキシ樹脂を用いた比較例２の積層板では、Ｔｇの低下が見られた。この点、フェノキシホスファゼンの添加量を比較例１の半分にした比較例４では、Ｔｇは上がったが、難燃性が下がった。 On the other hand, instead of the phosphorus-modified phenol curing agent according to the present invention, a laminate of Comparative Example 1 using 20 parts by mass of a phenol curing agent and phenoxyphosphazene (addition type phosphorus compound) and an epoxy resin containing no phenol curing agent In the laminated board of the comparative example 2 which used the phosphorus modified epoxy resin, the fall of Tg was seen. In this respect, in Comparative Example 4 in which the amount of phenoxyphosphazene added was half that of Comparative Example 1, the Tg increased but the flame retardancy decreased.
　また、本発明に係るリン変性フェノール硬化剤の代わりに、フェノール硬化剤とホスファフェナントレン（ＨＣＡ）を１５質量部用いた比較例３では、ＰＣＴはんだ耐熱性が悪かった。 In addition, in Comparative Example 3 in which 15 parts by mass of a phenol curing agent and phosphaphenanthrene (HCA) were used instead of the phosphorus-modified phenol curing agent according to the present invention, the PCT solder heat resistance was poor.
　さらに、本発明に係るリン変性フェノール硬化剤の代わりに、フェノール硬化剤と反応型ホスファゼン（反応型リン化合物）を用いた比較例５においては、燃焼試験においてテストピースが完全に燃焼してしまった。 Furthermore, in Comparative Example 5 in which a phenol curing agent and a reactive phosphazene (reactive phosphorus compound) were used instead of the phosphorus-modified phenol curing agent according to the present invention, the test piece was completely burned in the combustion test. .
　これらの結果により、本発明に係るエポキシ樹脂組成物を用いることにより、ハロゲンフリーで、高Ｔｇを有し、吸湿耐熱性および難燃性のいずれにおいても優れたプリプレグ、金属張積層板並びにプリント配線板を得ることができることが示された。 From these results, by using the epoxy resin composition according to the present invention, a prepreg, a metal-clad laminate, and a printed wiring which are halogen-free, have a high Tg, and are excellent in both hygroscopic heat resistance and flame resistance It was shown that a board could be obtained.
　以上、説明したように、本発明の一つの実施態様に係るエポキシ樹脂組成物は、リン変性フェノール硬化剤とエポキシ化合物を含むエポキシ樹脂組成物であって、前記リン変性フェノール硬化剤がリン化合物と、下記式（Ｉ）：
Figure JPOXMLDOC01-appb-I000004
（式中、Ｒは水酸基、又はＯ－メチル基であり、ｎは２以上の整数を示す）
で表される化合物とを有すること、及び前記リン化合物が前記式（Ｉ）で表される化合物の脂肪族炭素に結合していることを特徴とし、前記エポキシ樹脂組成物を使用することにより、これまでのハロゲンフリーの樹脂組成物に用いられていた添加型又は反応型のリン化合物の欠点を抑えることができ、ひいては、高いＴｇ、吸湿耐熱性および難燃性を有する信頼性の高い基材を得ることができる。 As described above, the epoxy resin composition according to one embodiment of the present invention is an epoxy resin composition containing a phosphorus-modified phenol curing agent and an epoxy compound, and the phosphorus-modified phenol curing agent is a phosphorus compound , The following formula (I):
Figure JPOXMLDOC01-appb-I000004
(Wherein R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more)
And a compound represented by the formula: and the phosphorus compound is bonded to the aliphatic carbon of the compound represented by the formula (I), and by using the epoxy resin composition, It is possible to suppress the defects of the addition type or reaction type phosphorus compound used in the halogen-free resin composition so far and, consequently, a highly reliable base material having high Tg, hygroscopic heat resistance and flame retardancy. You can get
　さらに、前記リン化合物が下記式（ＩＩ）：
Figure JPOXMLDOC01-appb-I000005
で示されるリン化合物であることが好ましい。このような構成のエポキシ樹脂によって成形された基材は、Ｔｇが高く、吸湿耐熱性および難燃性により優れている。 Furthermore, the phosphorus compound has the following formula (II):
Figure JPOXMLDOC01-appb-I000005
It is preferable that it is a phosphorus compound shown by these. The base material formed of the epoxy resin having such a constitution has a high Tg, and is excellent in hygroscopic heat resistance and flame retardancy.
　また、リン変性フェノール硬化剤中、式（Ｉ）で表される化合物と結合していないリン化合物が３質量％以下であることが好ましい。このような構成により、より確実に高い難燃性と吸湿耐熱性を得ることができる。 Moreover, it is preferable that the phosphorus compound which is not couple | bonded with the compound represented by Formula (I) in a phosphorus modified phenol curing agent is 3 mass% or less. With such a configuration, high flame retardancy and hygroscopic heat resistance can be obtained more reliably.
　さらに、エポキシ樹脂組成物中の有機成分に対して、式（Ｉ）で表される化合物と結合していないリン化合物が１質量％以下であることが好ましい。このような構成により、より確実に高い難燃性と吸湿耐熱性を得ることができる。 Furthermore, it is preferable that the phosphorus compound which is not couple | bonded with the compound represented by Formula (I) is 1 mass% or less with respect to the organic component in an epoxy resin composition. With such a configuration, high flame retardancy and hygroscopic heat resistance can be obtained more reliably.
　さらに、リン変性フェノール硬化剤中において、リン化合物が式（Ｉ）で表される化合物の分子末端の脂肪族炭素に結合している場合には、より高い難燃性を確保することができる。 Furthermore, when the phosphorus compound is bonded to the aliphatic carbon at the molecular terminal of the compound represented by formula (I) in the phosphorus-modified phenol curing agent, higher flame retardancy can be secured.
　また、本発明の別の実施態様に係るプリプレグは、前記エポキシ樹脂組成物を繊維質基材に含浸および乾燥させて得られることを特徴とするものである。このようなプリプレグを用いることにより、高Ｔｇと優れた吸湿耐熱性を有し、さらに、ハロゲン系難燃剤を含有しなくとも充分な難燃性を有する、信頼性の高い金属張積層板およびプリント配線板を得ることができる。 Further, a prepreg according to another embodiment of the present invention is characterized in that it is obtained by impregnating and drying the above-mentioned epoxy resin composition in a fibrous base material. By using such a prepreg, a highly reliable metal-clad laminate and print having high Tg and excellent moisture absorption heat resistance, and further having sufficient flame retardancy even without containing a halogen-based flame retardant A wiring board can be obtained.
　本発明の別の実施態様に係る金属張積層板は、前記プリプレグに金属箔を積層して、加熱加圧成形して得られることを特徴とする。 The metal-clad laminate according to another embodiment of the present invention is characterized in that it is obtained by laminating a metal foil on the above-mentioned prepreg and subjecting it to heat and pressure forming.
　また、本発明のさらなる実施態様に係るプリント配線板は、前記金属張積層板の表面の金属箔を部分的に除去することにより回路形成して得られたことを特徴とする。 The printed wiring board according to a further embodiment of the present invention is characterized in that it is obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate.

Claims (8)

  1. 　リン変性フェノール硬化剤とエポキシ化合物を含むエポキシ樹脂組成物であって、
    　前記リン変性フェノール硬化剤がリン化合物と、下記式（Ｉ）：
    Figure JPOXMLDOC01-appb-I000006
    （式中、Ｒは水酸基又はＯ－メチル基であり、ｎは２以上の整数を示す）
    で表される化合物とを含むこと、及び
    　前記リン化合物が前記式（Ｉ）で表される化合物の脂肪族炭素に結合していることを特徴とする、エポキシ樹脂組成物。     An epoxy resin composition comprising a phosphorus-modified phenol curing agent and an epoxy compound,
    The phosphorus-modified phenol curing agent is a phosphorus compound, and the following formula (I):
    Figure JPOXMLDOC01-appb-I000006
    (Wherein, R is a hydroxyl group or an O-methyl group, and n is an integer of 2 or more)
    An epoxy resin composition comprising: a compound represented by the formula: and the phosphorus compound bonded to an aliphatic carbon of the compound represented by the formula (I).
  2. 　リン化合物が下記式（ＩＩ）：
    Figure JPOXMLDOC01-appb-I000007
    で示されるリン化合物である、請求項１に記載のエポキシ樹脂組成物。     The phosphorus compound has the following formula (II):
    Figure JPOXMLDOC01-appb-I000007
    The epoxy resin composition of Claim 1 which is a phosphorus compound shown by these.
  3. 　リン変性フェノール硬化剤中、式（Ｉ）で表される化合物と結合していないリン化合物が３質量％以下である、請求項１又は２に記載のエポキシ樹脂組成物。 The epoxy resin composition of Claim 1 or 2 whose phosphorus compound which is not couple | bonded with the compound represented by Formula (I) in a phosphorus modified phenol curing agent is 3 mass% or less.
  4. 　エポキシ樹脂組成物中の有機成分に対して、式（Ｉ）で表される化合物と結合していないリン化合物が１質量％以下である、請求項１～３のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3, wherein the amount of the phosphorus compound not bound to the compound represented by the formula (I) is 1% by mass or less based on the organic component in the epoxy resin composition. object.
  5. 　リン変性フェノール硬化剤中において、リン化合物が式（Ｉ）で表される化合物の分子末端の脂肪族炭素に結合している、請求項１～４のいずれかに記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 4, wherein in the phosphorus-modified phenol curing agent, the phosphorus compound is bonded to the aliphatic carbon at the molecular terminal of the compound represented by formula (I).
  6. 　請求項１～５のいずれかに記載のエポキシ樹脂組成物を繊維質基材に含浸させて得られるプリプレグ。 A prepreg obtained by impregnating a fiber base material with the epoxy resin composition according to any one of claims 1 to 5.
  7. 　請求項６に記載のプリプレグに金属箔を積層して、加熱加圧成形して得られる金属張積層板。 The metal-clad laminated board obtained by laminating | stacking metal foil on the prepreg of Claim 6, and heat-pressing it.
  8. 　請求項７に記載された金属張積層板の表面の金属箔を部分的に除去することにより回路形成して得られるプリント配線板。 A printed wiring board obtained by forming a circuit by partially removing the metal foil on the surface of the metal-clad laminate described in claim 7.
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