JP2007045968A - Thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition enhanced in water absorption properties and more excellent in mechanical characteristics such as elasticity and the like in a resin composition containing a resin from cyanic acid esters and a maleimide compound. <P>SOLUTION: The resin composition contains the cyanic acid ester resin prepared by polycondensing a naphthol aralkyl resin with cyanic acid and the maleimide compound as essential components. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition containing a specific cyanate ester resin and a maleimide compound, which are used for printed wiring board materials for forming electric circuits.

      Cyanate ester resin has long been known as a thermosetting resin excellent in high heat resistance, dielectric properties, etc., and a method of using a bismaleimide compound in combination as this resin composition (see, for example, Patent Document 1) and BT resin. Based on this technology, in recent years, it has been widely used as a material for high-performance printed wiring boards for semiconductor plastic packages. The resin composition using this bisphenol A type cyanate ester resin has excellent properties such as high heat resistance and mechanical properties such as elastic modulus, but has a high water absorption rate and further in mechanical properties such as elastic modulus. Improvement is desired, and cyanate ester resins having other structures are being studied. As examples of cyanate ester resins having other structures, there are many examples of novolak-type cyanate ester resins (see, for example, Patent Document 2), but novolak-type cyanate ester resins are insufficiently cured under normal curing conditions. The resulting cured product has problems such as high water absorption and reduced moisture absorption heat resistance. As a method for improving the novolak-type cyanate ester resin, a prepolymer with a bisphenol A-type cyanate ester resin is disclosed (for example, see Patent Document 3), but the prepolymer has improved curability, In terms of improving the characteristics, it was still insufficient.

Japanese Patent Publication No.54-30440 Japanese Patent Laid-Open No. 11-124433 JP 2000-191776 A

  The present invention mainly aims to improve water absorption characteristics in a resin composition containing a cyanate ester resin and a maleimide compound, and also has thermosetting properties having further excellent mechanical properties such as elastic modulus. A resin composition is provided.

（式中、Ｒは水素原子またはメチル基を示し、ｎは１から５０までの整数を示す。また、ｎが異なる化合物の混合物であってもよい。） As a result of intensive studies to solve the above problems, the present inventors have used a maleimide compound in combination with a cyanate ester resin having a specific structure, thereby having a resin composition having excellent water absorption and elastic modulus. The present invention was completed. That is, the present invention is a resin composition containing the cyanate ester resin (A) represented by the general formula (1) and the maleimide compound (B) as essential components.

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50. In addition, a mixture of compounds in which n is different may be used.)

  Since the resin composition according to the present invention has good curability and has excellent properties such as heat resistance, water absorption, and elastic modulus, it has the disadvantages of the conventional cyanate ester resin-bismaleimide compound-based resin composition. The problem is solved, and industrial practicality is extremely high.

（式中、Ｒは水素原子またはメチル基を示し、ｎは１から５０までの整数を示す。また、ｎが異なる化合物の混合物であってもよい。）
また、シアン酸エステル樹脂(A)としては、特にＲが水素であるα−ナフトールアラルキル型のシアン酸エステル樹脂が好ましいが、複数のシアン酸エステル樹脂(A)を、１種もしくは２種以上を適宜混合して使用することも可能である。 The cyanate ester resin (A) used in the present invention is not particularly limited as long as it is a cyanate ester resin represented by the general formula (1) and a prepolymer thereof. The cyanate ester resin (A) represented by the general formula (1) includes naphthols such as α-naphthol and β-naphthol, p-xylene glycol, α, α'-dimethoxy-p-xylene, 1,4-di- It is obtained by condensation polymerization of naphthol aralkyl resin obtained by reaction with a condensing agent such as (2-hydroxy-2-propyl) benzene and cyanic acid, its production method is not particularly limited, and cyanate ester synthesis May be produced by any existing method. Specifically, it can be obtained by reacting a naphthol aralkyl resin represented by the general formula (2) with cyanogen halide in an inert organic solvent in the presence of a basic compound. Further, a similar method may be employed in which a salt of a naphthol aralkyl resin and a basic compound is formed in a solution containing water, and then a two-phase interface reaction with cyanogen halide is performed.

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50. In addition, a mixture of compounds in which n is different may be used.)
In addition, as the cyanate ester resin (A), an α-naphthol aralkyl cyanate ester resin in which R is hydrogen is particularly preferable, but a plurality of cyanate ester resins (A) are used alone or in combination of two or more. It is also possible to mix and use as appropriate.

  The blending amount of the cyanate ester resin (A) in the present invention is not particularly limited. However, if the blending amount is excessively small, the moisture absorption characteristics of the resulting laminated plate are deteriorated. The range of 25 to 95% by weight of the total amount of the acid ester resin (A) and the maleimide compound (B) is preferable, and the range of 30 to 90% by weight is particularly preferable.

  The maleimide compound (B) used in the present invention is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, prepolymers of these maleimide compounds, or maleimide compounds and amine compounds A prepolymer etc. are mentioned, It is also possible to use 1 type or 2 types or more mixed suitably. More preferred are bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) Methane is mentioned. The blending amount of the maleimide compound (B) in the present invention is not particularly limited, but if the blending amount is too small, the heat resistance of the resulting laminate will decrease, and if it is too large, the hygroscopic properties will decrease. The range of 5 to 75% by weight of the total amount of the resin (A) and the maleimide compound (B) is preferable, and the range of 10 to 70% by weight is particularly preferable.

  In the resin composition of the present invention, it is also possible to use a cyanate ester resin other than the cyanate ester resin (A) represented by the general formula (1) as long as the desired properties are not impaired. . As the cyanate ester resin other than the general formula (1), known resins can be used. For example, bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol P type cyanate ester resin, bisphenol E type cyanate ester resin, phenol novolac type cyanate ester resin, Examples include cresol novolac-type cyanate ester resin, dicyclopentadiene novolak-type cyanate ester resin, tetramethylbisphenol F-type cyanate ester resin, biphenol-type cyanate ester resin, and prepolymers thereof. It is also possible to use a mixture of more than one species as appropriate.

  In the present invention, the method for preparing the resin composition containing the cyanate ester resin (A) and the maleimide compound (B) is not particularly limited.For example, the cyanate ester resin (A) and the maleimide compound (B) It can be simply melt-mixed or dissolved and mixed in an organic solvent such as methyl ethyl ketone, N-methyl pyrodrine, dimethylformamide, dimethylacetamide, toluene, xylene and the like. In addition, it is possible to mix one or two kinds of cyanate ester resin (A) and maleimide compound (B) after oligomerization in advance, or to mix them in advance and then oligomerize them.

  An epoxy resin can be used in combination with the resin composition of the present invention. As an epoxy resin used together, a well-known thing is applicable, and if it is a compound which has a 2 or more epoxy group in 1 molecule, it will not specifically limit. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, 3 Functional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy Resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene epoxidized compound, hydroxyl group-containing silicon resin And compounds obtained by a reaction between epichlorohydrin and the like, can also be used by mixing one or two or more appropriately.

  The resin composition of the present invention is cured by heating as it is, but a known curing accelerator can be blended for the purpose of accelerating the curing. Examples of such compounds include organic peroxides exemplified by benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-diperphthalate, and the like; azobisnitrile Azo compounds of interest: 2-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl- Imidazoles exemplified by 2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylmidazole, 1-cyanoethyl-2-ethyl-methylimidazole, 1-guanaminoethyl-2-methylimidazole, etc. As well as carboxylic acids of these imidazoles or their acids Water adducts, etc .; N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine, pyridine, quinoline, N- Tertiary amines such as methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol; lead naphthenate, lead stearate, naphthene Organic metal salts such as zinc oxide, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, and acetylacetone iron; those obtained by dissolving these organic metal salts in hydroxyl-containing compounds such as phenol and bisphenol ; Tin chloride, zinc chloride, aluminum chloride, etc. Inorganic metal salts; dioctyltin oxide, other alkyltin, and an organic tin compound such as an alkyl tin oxide. The amount of these curing accelerators used is sufficient in a general range, for example, 10 wt% or less, usually about 0.01 to 2 wt%, based on the resin composition.

  The resin composition of the present invention includes other thermosetting resins, thermoplastic resins and oligomers thereof, various polymer compounds such as elastomers, and other flame retardants, as long as the desired properties are not impaired. A combination of a compound and an additive is also possible. These are not particularly limited as long as they are generally used. For example, phosphorus compounds such as phosphate esters and melamine phosphate, nitrogen-containing compounds such as melamine and benzoguanamine, oxazine ring-containing compounds, silicon compounds, polyimides, polyvinyl acetals, phenoxy resins, acrylic resins, hydroxyl groups or carboxyl groups Elastomers such as acrylic resin, alkyd resin, thermoplastic polyurethane resin, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, butadiene-styrene copolymer, polyisoprene, butyl rubber, fluororubber, natural rubber; styrene-isoprene rubber, Acrylic rubber, these core shell rubbers, epoxidized butadiene, maleated butadiene, polyethylene, polypropylene, polyethylene-propylene copolymer, poly-4-methylpentene-1, poly Vinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl toluene, polyvinyl phenol, AS resin, ABS resin, MBS resin, poly-4-fluoroethylene, fluorinated ethylene-propylene copolymer, 4-fluorinated ethylene-6-fluoride Polymers such as vinylidene fluoride, vinyl compound polymers such as vinylidene fluoride, thermoplastic resins such as polycarbonate, polyester carbonate, polyphenylene ether, polysulfone, polyester, polyethersulfone, polyamide, polyamideimide, polyesterimide, polyphenylene sulfite And their low molecular weight polymers; poly (meth) acrylates such as (meth) acrylate, epoxy (meth) acrylate, di (meth) acryloxy-bisphenol, styrene, vinyl pyrrolidone, diacrylic Polymeric double bonds, such as polyallyl compounds such as rate, divinylbenzene, diallylbenzene, diallyl ether bisphenol, trialkenyl isocyanurate and their prepolymers, dicyclopentadiene and their prepolymers, phenol resins, unsaturated polyesters, etc. Examples thereof include monomers and prepolymers thereof, and curable monomers or prepolymers such as polyisocyanates. Additives include UV absorbers, antioxidants, photopolymerization initiators, optical brighteners, photosensitizers, dyes, pigments, thickeners, lubricants, antifoaming agents, dispersants, leveling agents, brighteners In addition, a polymerization inhibitor or the like can be used in appropriate combination as desired.

  In the resin composition of the present invention, an inorganic or organic fibrous reinforcing material can be used. Examples of the inorganic or organic fiber reinforcing material include glass fibers such as E, NE, D, S, and T glass, quartz glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, asbestos, rock wool, slag wool, Inorganic fibers such as gypsum whiskers or their woven or non-woven fabrics or mixtures thereof; organics such as wholly aromatic polyamide fibers, polyimide fibers, liquid crystal polyester, polyester fibers, fluorine fibers, polybenzoxazole fibers, cotton, hemp, semi-carbon fibers Fiber or its fine or non-woven fabric or a mixture thereof; glass fiber and wholly aromatic polyamide fiber, glass fiber and carbon fiber, glass fiber and polyamide fiber, glass fiber and liquid crystalline aromatic polyester, etc .; glass paper, mica paper Inorganic such as alumina paper Paper: Kraft paper, cotton paper, paper-glass mixed paper, etc., and fibrous reinforcing base materials made by mixing and using two or more of these, etc. are exemplified, and these base materials have adhesion to resin. In order to improve this, it is preferable to perform a known surface treatment. For thin film applications, polyimide films, wholly aromatic polyamide films, polybenzoxazole films, liquid crystal polyester films, and the like can be used.

  An inorganic filler can be used in combination with the resin composition of the present invention. The inorganic filler is not particularly limited as long as it is generally used, and specific examples thereof include natural silica, fused silica, amorphous silica, silica such as hollow silica, aluminum hydroxide, Aluminum hydroxide heat-treated products (heat treated with aluminum hydroxide and reduced in part of crystal water), boehmite, metal hydrates such as magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, boron Examples thereof include zinc oxide, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), and hollow glass.

The curing conditions of the resin composition of the present invention vary depending on the composition ratio of the resin composition, the presence or absence of a curing accelerator, and the gelation or preliminary curing can be performed at a temperature of 100 ° C. or less by selecting a curing accelerator. Although it is possible to apply it, in the case of complete curing, a cured product is usually obtained by heating in a range of 100 to 300 ° C. for a predetermined time. The pressure level at this time is not particularly limited, but in general, it is preferable to apply pressure, and it is appropriately selected in the range of usually 0.01 to 50 MPa, preferably 0.5 to 15 MPa. The resin composition of the present invention is used for various applications by utilizing its excellent physical properties and workability. These are suitably used, for example, for printed wiring board materials such as prepregs and copper clad laminates, structural materials, and casting resins.
Synthesis examples, examples, and comparative examples are shown below to describe the present invention in detail.

（式中、ｎは1〜5の混合物）
式(3)で表されるα−ナフトールアラルキル樹脂(SN485、OH基当量：219g/eq.、新日鐵化学製) 0.47モル (OH基換算)をクロロホルム 500mlに溶解後、トリエチルアミン 0.7モルを添加混合し、これに 0.93モルの塩化シアンのクロロホルム溶液 300ｇを、-10℃で1.5時間かけて滴下し、30分撹拌した後、更に 0.1モルのトリエチルアミンとクロロホルム 30ｇの混合溶液を滴下し、30分撹拌して反応を完結させた。生成するトリエチルアミンの塩酸塩を濾別した後、得られた濾液を 0.1Ｎ塩酸 500mlで洗浄した後、水 500mlでの洗浄を4回繰り返した。これに硫酸ナトリウムによる乾燥後、75℃でエバポレートし、更に90℃で減圧脱気することにより、褐色固形の式(4)で表されるα−ナフトールアラルキル型のシアン酸エステル樹脂(赤外吸収スペクトルにおいて、2264cm-1付近にシアネート基の吸収を確認)を得た。

（式中、ｎは1〜5の混合物） Synthesis Example 1 Synthesis of α-naphthol aralkyl-type cyanate ester resin

(Where n is a mixture of 1 to 5)
Α-naphthol aralkyl resin represented by formula (3) (SN485, OH group equivalent: 219 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.) 0.47 mol (OH group equivalent) dissolved in 500 ml of chloroform, 0.7 mol of triethylamine was added. Then, 300 g of a 0.93 mol solution of cyanogen chloride in chloroform was added dropwise at −10 ° C. over 1.5 hours, stirred for 30 minutes, and then a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise for 30 minutes. Stir to complete the reaction. The resulting triethylamine hydrochloride was filtered off, and the obtained filtrate was washed with 500 ml of 0.1N hydrochloric acid, and then washed with 500 ml of water four times. This was dried with sodium sulfate, evaporated at 75 ° C., and further degassed at 90 ° C. under reduced pressure to give an α-naphthol aralkyl type cyanate ester resin represented by the formula (4) as a brown solid (infrared absorption) In the spectrum, absorption of a cyanate group was confirmed in the vicinity of 2264 cm −1).

(Where n is a mixture of 1 to 5)

Example 1
70 parts by weight of α-naphthol aralkyl-type cyanate ester resin obtained in Synthesis Example 1 and 30 parts by weight of bis (4-maleimidophenyl) methane (BMI-H, Kay Kasei) were melt mixed at 160 ° C. for 10 minutes. The product was poured into a casting mold, vacuum degassed at 165 ° C for 15 minutes, and then heat-cured at 180 ° C for 4 hours, 200 ° C for 4 hours, and 250 ° C for 4 hours. A cured product was obtained. Table 1 shows the physical property measurement results of the obtained cured product.

(Example 2)
An example was prepared by melting and mixing 50 parts by weight of α-naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1 and 50 parts by weight of bis (4-maleimidophenyl) methane (BMI-H) at 160 ° C. for 10 minutes. In the same manner as in Example 1, a cured product was obtained. Table 1 shows the physical property measurement results of the obtained cured product.

(Comparative Example 1)
In Example 1, except that 70 parts by weight of 2,2-bis (4-cyanatephenyl) propane (CX, manufactured by Mitsubishi Gas Chemical) was used instead of 70 parts by weight of naphthol aralkyl-type cyanate ester resin. 1 was performed to obtain a cured product. Table 1 shows the physical property measurement results of the obtained cured product.

(Comparative Example 2)
In Example 2, in the same manner as in Example 1 except that 50 parts by weight of 2,2-bis (4-cyanatephenyl) propane (CX) was used instead of 50 parts by weight of naphthol aralkyl type cyanate ester resin. And a cured product was obtained. Table 1 shows the physical property measurement results of the obtained cured product.

(Measuring method)
1) Change in water absorption and appearance after treatment: Use a 30mm x 30mm x 3mm sample, and comply with JIS C6481 with a pressure cooker tester (Hirayama Seisakusho, PC-3 type) at 121 ° C and 2 atm. The water absorption after time treatment is measured, and the appearance change after water absorption is judged visually.
2) Bending strength, flexural modulus: Measured at room temperature with an autograph (manufactured by Shimadzu Corporation, AG5000B) according to JIS-K6911 using a sample of size 10mm x 60mm x 4mm.
3) Glass transition temperature: Using a sample of size 5mm x 5mm x 3mm, measured with a TMA device (TA Instrumen Model 2940) under a load of 5g and a temperature increase of 10 ° C / min.

Claims (3)

A resin composition comprising a cyanate ester resin (A) represented by the general formula (1) and a maleimide compound (B) as essential components.

(In the formula, R represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50. In addition, a mixture of compounds in which n is different may be used.)   2. The resin composition according to claim 1, wherein the weight blending ratio of the cyanate ester resin (A) and the maleimide compound (B) is in the range of (A) 25 to 95: (B) 5 to 75.   A cured product obtained by curing the resin composition according to claim 1.