WO2014059654A1

WO2014059654A1 - Cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same

Info

Publication number: WO2014059654A1
Application number: PCT/CN2012/083186
Authority: WO
Inventors: 唐军旗
Original assignee: 广东生益科技股份有限公司
Priority date: 2012-10-19
Filing date: 2012-10-19
Publication date: 2014-04-24

Abstract

The present invention relates to a cyanate ester resin composition, and prepreg, laminate, and metal-clad laminate that are fabricated by using the same. The cyanate ester resin composition comprises cyanate ester resin, halogen-free epoxy resin, and an inorganic filler, the structural formula of the cyanate ester resin being as formula (I), wherein R and R₁ represent hydrogen atoms, alkyl, aryl or aralkyl, and n is an integer from 1 to 50. The cyanate ester resin composition of the present invention has desirable mechanical property, heat resistance and fire resistance. Without using the halogen compound or phosphorus compound as the fire retardant, prepreg, laminate, and metal-clad laminate that are fabricated by using the cyanate ester resin composition also have desirable fire resistance, low coefficient of X/Y-direction thermal expansion, and desirable mechanical property, and therefore can be used as the substrate material for high-reliability semiconductor assembly.

Description

Laminate technology

The present invention relates to a resin composition, and more particularly to a cyanate resin composition and a prepreg, a laminate and a metal foil-clad laminate produced using the same. Background technique

With the development of high performance, high functionality and networking of computer, electronic and information communication equipment, higher requirements have been placed on printed circuit boards: high wiring density and high integration. This requires that the metal foil-clad laminate for producing a printed wiring board has more excellent heat resistance, heat and humidity resistance, reliability, and the like.

Cyanate resin has excellent dielectric properties, heat resistance, mechanical properties and processability, and is a commonly used matrix resin in the production of metal foil laminates for high-end printed wiring boards. In recent years, prepregs and laminates prepared using a resin containing a bisphenol A type cyanate resin and a maleimide compound (commonly referred to as a BT resin) have been widely used for high performance in semiconductor packaging. In printed circuit board materials.

The bisphenol A type cyanate resin composition has excellent heat resistance, chemical resistance, adhesion, etc., but the cured product has a problem of high water absorption, insufficient heat and humidity resistance, and mechanical properties such as elastic modulus. Performance does not meet the performance requirements of high-end substrates.

The dicyclopentadiene type cyanate resin composition has excellent dielectric properties, heat resistance, heat and humidity resistance, and good mechanical properties, and is widely used in high-frequency circuit substrates, high-performance composite materials, and the like, and can be used to make up for double The problem that the phenol A type cyanate resin is insufficient in moist heat resistance. However, its flame retardancy is poor and it cannot meet the performance requirements of high-end substrates.

Further, the resin composition for producing a metal foil-clad laminate is generally required to have flame retardancy, and therefore it is generally required to simultaneously use a bromine-containing flame retardant to achieve flame retardancy. However, due to the increased attention to environmental issues in recent years, it is necessary to use a compound-containing compound to achieve flame retardancy. At present, phosphorus compounds are frequently used as flame retardants, but various intermediates and production processes of the tablet compounds have certain toxicity. Phosphorus compounds may generate toxic gases (such as methylphosphine) and toxic substances (such as triphenyl) during combustion. Phosphine, etc.), its waste may pose a potential hazard to the aquatic environment. Therefore, there is a need to develop a laminate which has flame retardancy and high reliability even without using a compound or a phosphorus compound. U.S. Patent (US7655871) uses a phenolic cyanate resin, a biphenyl epoxy resin, a phenolic resin as a matrix resin, a large amount of silicon micropowder as a filler, a glass fiber cloth as a reinforcing material, and a heat resistance. Excellent, achieved no! 3⁄4 flame retardant. However, after the phenolic cyanate resin is cured under the general process conditions, the cured product has a large water absorption rate and poor heat and humidity resistance. Further, the phenolic cyanate resin composition itself has poor flame retardancy, and in order to meet the demand for halogen-free and phosphorus-free flame retardant, it is necessary to add a larger amount of inorganic filler to achieve flame retardancy, which in turn leads to a decrease in workability.

U.S. Patent No. US20060084787 discloses a biphenyl type cyanate resin which has a low water absorption, excellent heat resistance, moist heat resistance and flame retardancy.

Chinese patent (CN200810008694.8) uses naphthol aralkyl cyanate resin, halogen-free epoxy resin as matrix resin, boehmite, silicone resin powder as filler, glass fiber cloth as reinforcing material layer Pressure material; Chinese patent (CN200810132333.4) uses naphthol aralkyl type cyanate resin, epoxy resin as matrix resin, fused silica, silicone rubber powder as filler, glass fiber cloth as reinforcing material Made of laminate. Since the naphthol aralkyl type cyanate resin composition has good flame retardancy, it can be realized without adding a large amount of inorganic filler! 3⁄4 non-phosphorus flame retardant, can solve the problems of heat resistance, poor flame retardancy and processability of the above bisphenol A type, dicyclopentadiene type and phenolic type cyanate resin.

However, with the development of semiconductor packaging technology, higher requirements have been placed on heat resistance and mechanical properties of substrate materials. The biphenyl type cyanate resin and the naphthol aralkyl type cyanate resin have a lower crosslinking density due to the presence of a biphenyl group or an aralkyl group, thereby lowering the mechanical properties of the cyanate resin cured product and Heat resistance, etc. Therefore, there is a need for a non-phosphorus-free flame-retardant cyanate resin composition having excellent heat resistance, flame retardancy and mechanical properties, and a prepreg, a laminate material and a metal foil-clad laminate produced using the same. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyanate resin composition which has good mechanical properties, heat resistance and flame retardancy and can be used for producing a printed wiring board material.

Another object of the present invention is to provide a prepreg, a laminate, and a metal foil-clad laminate produced using the above cyanate resin composition, a laminate and a metal foil-coated layer produced using the prepreg The pressure material also has good flame retardancy, low X, Y direction thermal expansion coefficient, good mechanical properties, and is suitable for high reliability semiconductor packaging without using a compound or a phosphorus compound as a flame retardant. Substrate material.

In order to achieve the above object, the present invention provides a cyanate resin composition comprising a cyanate resin, an epoxy-free epoxy resin, and an inorganic filler material, and the structural formula of the cyanate resin is as follows:

Wherein R is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n is an integer of from 1 to 50. Further, n is an integer of 1 to 10, and when n is in this range, the cyanate resin has a good wettability to the substrate.

The cyanate resin of the present invention is not particularly limited, and is a cyanate resin or a prepolymer thereof having at least two cyanate groups per molecule and as shown in Formula I. The cyanate resin may be used singly or as a mixture of at least two cyanate resins as needed.

The amount of the cyanate resin to be used is not particularly limited, and it preferably accounts for the cyanate resin in the cyanate resin composition and is not present! 10 to 90% by weight, more preferably 20 to 80% by weight, particularly preferably 30 to 70% by weight, based on the total amount of the epoxy resin.

The epoxy resin according to the present invention is an epoxy resin containing at least two epoxy groups per molecule and having no halogen atom in the molecular structure.

In order to improve the heat resistance and flame retardancy of the cyanate resin composition, this is not! 3⁄4 epoxy resin is preferably as shown in the formula II! 3⁄4 epoxy resin:

II

Where R is an O—or

a group, R ₂ is an aryl group, such as phenyl, naphthyl, biphenyl, etc., R ₃ , R 4 are a hydrogen atom, an alkane a group, an aryl group, an aralkyl group or a group represented by the formula: R ₅ , R ₆ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, m is an integer of 0 to 5, and c is 1 to 5 An integer, n is an integer from 1 to 50.

ΠΙ

Wherein R ₇ is an aryl group, a group of _0—or —C—, R ₉ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, i is 0 or 1, and j is 1 or 2.

No! The epoxy resin is further preferably an aralkyl novolac type epoxy resin or an aryl ether type novolac epoxy resin having a structure represented by Formula V:

V

Wherein R, R ₂ are aryl, such as phenyl, naphthyl, biphenyl, etc., R ₃ , R ₅ , R ₆ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and m is 1~ An integer of 5, c is an integer of 1 to 5, and n is an integer of 1 to 50.

The 126-free epoxy resin may be used singly or in combination of plural kinds as needed. The amount of the halogen-free epoxy resin to be used is not particularly limited, and it is preferably 10 to 90% by weight, more preferably 20% by weight based on the total of the cyanate resin and the epoxy resin in the cyanate resin composition. It is -80% by weight, particularly preferably 30 to 70% by weight. The inorganic filler according to the present invention is not particularly limited. Among them, fused silica has a low coefficient of thermal expansion and is excellent in flame retardancy and heat resistance of boehmite.

The amount of the inorganic filler to be used in the present invention is not particularly limited, and the cyanate resin is not contained in the cyanate resin composition! When the total amount of the epoxy resin is 100 parts by weight, the amount of the corresponding inorganic filler is preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, particularly preferably 50 to 150 parts by weight.

The cyanate resin composition of the present invention may further comprise a maleimide compound. The maleimide compound is not particularly limited and is a compound containing at least one maleimide group per molecule. The maleimide compound is further preferably a compound containing at least two maleimide groups per molecule.

The amount of the maleimide compound to be used in the present invention is not particularly limited, and it is preferably 5 to 80% by weight based on the total amount of the cyanate resin and the maleimide compound in the cyanate resin composition. It is particularly preferably 10 to 70% by weight.

The present invention also provides a prepreg produced using the above cyanate resin composition, the prepreg comprising a substrate and a cyanate resin composition adhered to the substrate by impregnation and drying.

The present invention further provides a laminate and a metal foil-clad laminate produced using the above prepreg. The laminate comprises at least one prepreg, which is laminated and cured to obtain a laminate; the metal foil laminate comprises at least one prepreg, and a metal foil is coated on one or both sides of the prepreg , the laminate is cured to obtain a metal foil laminate.

Advantageous Effects of Invention The cyanate resin composition provided by the present invention has good mechanical properties, heat resistance and flame retardancy. The laminate prepared by using the prepreg obtained from the cyanate resin composition and the metal foil-clad laminate have good flame retardancy without using a compound or a phosphorus compound as a flame retardant. Low X, Y direction thermal expansion coefficient, good mechanical properties. The prepreg, the laminate, and the metal foil-clad laminate are suitable for producing a highly reliable substrate material for semiconductor packaging because of the above-described excellent overall performance. detailed description

The present invention provides a cyanate resin composition comprising a cyanate resin, an epoxy-free resin, and an inorganic filler, and the structural formula of the cyanate resin is as follows:

Formula I

The method for synthesizing the cyanate resin is not particularly limited, and it may be selected from a synthetic method of a usual cyanate resin. Specifically, the method for synthesizing the cyanate resin is as follows: in the presence of a basic compound, an α-naphthol phenolic resin or a β-naphthol phenolic acid resin having a structure represented by the following formula IV is reacted with a cyanogen halide. The reaction is carried out in an inert organic solvent to obtain a cyanate resin.

Formula IV

Wherein R is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n is an integer of from 1 to 50. The epoxy resin according to the present invention is an epoxy resin containing at least two epoxy groups per molecule and having no protein atoms in the molecular structure. The epoxy-free epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, trifunctional phenol Epoxy resin, tetrafunctional phenol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, fluorene epoxy resin, phenoxy epoxy resin, norbornene epoxy resin, adamantane Epoxy resin, bismuth epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, aralkyl epoxy resin, aralkyl phenolic epoxy resin, aromatic a compound obtained by epoxidation of a double bond such as a phenolic epoxy resin, an alicyclic epoxy resin, a polyol epoxy resin, a silicon-containing epoxy resin, a nitrogen-containing epoxy resin, or a butadiene, and a shrinkage Glyceramine epoxy resin, glycidyl ester epoxy resin, and the like.

In order to improve the flame retardancy of the cyanate resin composition, the epoxy resin is preferably an epoxy resin having a structure as shown in the formula II:

Formula II

Wherein R is an O- or a group, and R ₂ is an aryl group such as a phenyl group, a naphthyl group, a biphenyl group, etc., R ₃ and R 4 are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a formula The group represented by ΠΙ, R ₅ and R ₆ are a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, m is an integer of 0 to 5, c is an integer of 1 to 5, and n is an integer of 1 to 50.

III

Wherein R ₇ is an aryl group, R ₈ is a _O_ or -C- group, R ₉ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, i is 0 or 1, and j is 1 or 2 _t.

No! The epoxy resin is further preferably an aralkyl phenolic epoxy tree having a structure represented by Formula V Fatty, aryl ether type phenolic epoxy resin:

Formula V

I ⁵

— c—

I

Wherein R is an O- or R ₆ group, R ₂ is an aryl group such as phenyl, naphthyl, biphenyl, etc., R ₃ , R ₅ , R ₆ are a hydrogen atom, an alkyl group, an aryl group Or an aralkyl group, m is an integer of 1 to 5, c is an integer of 1 to 5, and n is an integer of 1 to 50.

Specifically, it is a phenol phenyl aralkyl type epoxy resin, a phenol biphenyl aralkyl type epoxy resin, a phenol naphthyl aralkyl type epoxy resin, a naphthol phenyl aralkyl type epoxy resin. , naphthol biphenyl aralkyl type epoxy resin, naphthol naphthyl aralkyl type epoxy resin, phenol phenyl ether type epoxy resin, phenol biphenyl ether type epoxy resin, phenol naphthyl ether type Epoxy resin, naphthol phenyl ether type epoxy resin, naphthol phenyl ether type epoxy resin, and naphthol naphthyl ether type epoxy resin.

The above-mentioned epoxy resin may be used singly or in combination of plural kinds as needed. The amount of the halogen-free epoxy resin to be used is not particularly limited, and it is preferably 10 to 90% by weight, more preferably 20% by weight based on the total of the cyanate resin and the epoxy resin in the cyanate resin composition. It is -80% by weight, particularly preferably 30 to 70% by weight.

The inorganic filler according to the present invention is not particularly limited, and is specifically silica (for example, crystalline silica, fused silica, amorphous silica, spherical silica, hollow silica, etc.), Metal hydrates (such as aluminum hydroxide, boehmite, magnesium hydroxide, etc.), molybdenum oxide, zinc molybdate, titanium oxide, barium titanate, barium titanate, barium sulfate, boron nitride, aluminum nitride, silicon carbide , alumina, zinc borate, zinc stannate, clay, kaolin, talc, mica, short glass fibers and hollow glass. Among them, fused silica has a low coefficient of thermal expansion and is excellent in flame retardancy and heat resistance of boehmite. The average particle diameter (d50) of the inorganic filler is not particularly limited, but the average particle diameter U50 is preferably from 0.1 to 10 μm, more preferably from 0.2 to 5 μm from the viewpoint of dispersibility. The inorganic filler materials of different types, different particle size distributions or different average particle diameters may be used alone or in combination of plural kinds as needed. The amount of the inorganic filler to be used in the present invention is not particularly limited, and the cyanate resin in the cyanate resin composition is not included! When the total amount of the epoxy resin is 100 parts by weight, the amount of the corresponding inorganic filler is preferably 10 to 300 parts by weight, more preferably 30 to 200 parts by weight, particularly preferably 50 to 150 parts by weight. use. The surface treatment agent is not particularly limited and is selected from surface treatment agents commonly used for inorganic treatment. Specific examples thereof include a tetraethyl orthosilicate compound, an organic acid compound, an aluminate compound, a titanate compound, a silicone oligomer, a macromolecular treatment agent, and a silane coupling agent. The silane coupling agent is not particularly limited, and is selected from a silane coupling agent commonly used for surface treatment of inorganic materials, and is specifically an aminosilane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, and a phenyl group. A silane coupling agent, a cationic silane coupling agent, a mercaptosilane coupling agent, and the like. The wetting and dispersing agent are not particularly limited and are selected from the group consisting of wetting and dispersing agents commonly used in coatings. The present invention may be used alone or in appropriate combination according to the needs of different types of surface treatment agents or wetting and dispersing agents.

The cyanate resin composition of the present invention may further comprise a maleimide compound. The maleimide compound is not particularly limited and is a compound containing at least one maleimide group per molecule. The maleimide compound is further preferably a compound containing at least two maleimide groups per molecule. The maleimide compound is not particularly limited, and is specifically N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl group). Maleimide, N-(2,6-dimethylphenyl)maleimide, bis(4-maleimidophenyl)methane, 2,2-di(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, etc., polyphenylmethane maleimide, A prepolymer of the above maleimide compound or a prepolymer of a maleimide compound and an amine compound. The maleimide compound is preferably bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, Bis(3-ethyl-5-methyl-4-maleimidophenyl)methane. The maleimide compound can be used singly or in combination of plural kinds as needed.

The cyanate resin composition of the present invention may also be used in combination with a cyanate resin other than the cyanate resin represented by Formula I as long as it does not impair the inherent properties of the cyanate resin composition. It may be selected from bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol M type cyanate resin, bisphenol S type cyanate resin, bisphenol E type cyanate resin, bisphenol P-type cyanate Resin, novolac type cyanate resin, cresol novolac type cyanate resin, dicyclopentadiene type cyanate resin, tetramethylbisphenol F type cyanate resin, phenolphthalein type cyanate resin, naphthalene A prepolymer of the above-mentioned cyanate resin, such as a phenolic cyanate resin or an aralkyl type cyanate resin. These cyanate resins may be used singly or in combination of plural kinds as needed.

The cyanate resin composition of the present invention can also be used in combination with various high polymer and organic filler materials as long as it does not impair the inherent properties of the cyanate resin composition. Specifically, it is a different liquid crystal polymer, a thermosetting resin, a thermoplastic resin and oligomers and rubber bodies thereof, different flame retardant compounds or additives, and the like. They can be used singly or in combination of plural kinds as needed. Silicone powders are preferred because they have good flame retardant properties.

The cyanate resin composition of the present invention can also be used in combination with a curing accelerator as needed to control the curing reaction rate. The curing accelerator is not particularly limited, and may be selected from curing accelerators commonly used for promoting curing of cyanate resins, epoxy resins or epoxy-free epoxy resins, specifically copper, zinc, cobalt, nickel, manganese. Organic salts of metals such as imidazole and its derivatives, tertiary amines, and the like.

The present invention further provides a prepreg, a laminate, and a metal foil-clad laminate produced using the above cyanate resin composition. The prepreg includes a substrate and a cyanate resin composition adhered thereto by impregnation and drying. The laminate comprises at least one prepreg which is laminated and cured to provide a laminate. The metal-clad laminate comprises at least one prepreg, and a metal foil is coated on one or both sides of the prepreg, and the metal foil laminate is cured by lamination.

Among them, the laminate and the metal foil-clad laminate prepared by using the prepreg have good heat resistance, low X, Y direction thermal expansion coefficient, good mechanical properties, and do not use a halogen compound or a phosphorus compound as a resistance. In the case of a fuel, it also has good flame retardancy, and is therefore suitable for producing a highly reliable substrate material for semiconductor packaging.

The substrate of the present invention is not particularly limited and may be selected from known substrates for producing various printed wiring board materials. Specifically, it is inorganic fiber (for example, E glass, D glass, M glass, S glass, T glass, NE glass, quartz glass fiber, etc.), organic fiber (such as polyimide, polyamide, polyester, liquid crystal polymer, etc.) . The form of the substrate is usually a woven fabric, a nonwoven fabric, a roving, a staple fiber, a fiber paper or the like. Among the above substrates, the substrate of the present invention is preferably a glass cloth.

The prepreg according to the present invention is produced by combining a cyanate resin composition with a substrate, and the laminate of the present invention can be obtained by laminating and curing using the above prepreg. The metal foil-clad laminate of the present invention is prepared by: placing one of the above prepregs or stacking two or more prepregs, as needed in the prepreg or stacking prepreg A metal foil is placed on one or both surfaces and laminated to obtain a metal foil laminate. Metal foil There is no particular limitation, and it may be selected from metal foils for printed wiring board materials. The lamination conditions can be selected from the general lamination conditions of laminates for printed wiring boards and multilayer boards.

A metal foil-clad laminate made of the cyanate resin composition of the present invention is tested for

X, Y direction thermal expansion coefficient (X-CTE/Y-CTE), flexural modulus, dip resistance and flame retardancy, the test results are further illustrated and described in the following examples.

Synthesis example 1

300 g of chloroform and 0.98 mol of cyanogen chloride were added to the three-necked flask, and the mixture was thoroughly stirred to be uniformly mixed, and the temperature was stabilized at -10 °C:. 67 g (hydroxyl content 0.50 mol) of naphthol phenolic resin (provided by Nippon Kayaku Co., Ltd., as shown in the following formula VI), 0.74 mol of triethylamine dissolved in 700 g of chloroform and mixed, and the solution was The solution was slowly added dropwise to the above-mentioned cyanogen chloride in chloroform at -10 ° C, and the dropwise addition time was longer than 120 min. After the completion of the dropwise addition, the reaction was continued for 3 hours, and the reaction was terminated. The salt formed by the reaction was filtered off with a funnel, and the obtained filtrate was washed with 500 ml of 0.1 mol/L hydrochloric acid, and then washed five times with deionized water to neutral. Sodium sulfate was added to the separated chloroform solution to remove water in the chloroform solution, followed by filtration of sodium sulfate. The chloroform solvent was distilled off at 70 ° C, and then distilled under reduced pressure at 90 ° C to obtain a solid naphthol novolac type cyanate resin, and the structural formula is as shown in the following formula VII. The product was analyzed by infrared spectroscopy and had a strong absorption peak at 2265 cm- ¹ , which is a characteristic peak of cyano infrared absorption.

Formula VI

Synthesis example 1

The naphthol phenolic acid resin (provided by Minghe Chemical Co., Ltd., as shown in the following formula) having a hydroxyl group content of 0.50 mol was used instead of 67 g (hydroxyl content 0.50 mol) of naphthol phenolic acid resin used in Synthesis Example 1, and other synthesis and synthesis were carried out. Example 1 A naphthol novolac type cyanate resin was obtained in the same manner, and the structural formula is shown in the following formula IX. Xinjiang

Example 1

65 parts by weight of a naphthol novolac type cyanate resin obtained in Synthesis Example 2, 35 parts by weight of a naphthol naphthyl ether type epoxy resin (EXA-7311, supplied by DIC Corporation), and 0.02 parts by weight of zinc octoate were dissolved. Butanone and mix well, then add 125 parts by weight of boehmite (APYRAL AOH 30 from Nabaltec), 25 parts by weight of spherical fused silica (SC2050, supplied by Admatechs), and 5 parts by weight of silicone powder (KMP-605) , supplied by Shin-Etsu Chemical), 1 part by weight of an epoxy silane coupling agent (Z-6040, supplied by Dow Corning), 1 part by weight of a dispersant (BYK-W903, supplied by BYK), and adjusted to a suitable viscosity with methyl ethyl ketone, Stir well and mix well to make a glue. The prepreg was prepared by dipping the above glue with a 1078, 2116 glass fiber cloth, and then drying the solvent to remove the solvent. The above prepregs of 2 x 1078, 4 x 2116, and 8 x 2116 were laminated, and 18 μm thick electrolytic copper foil was pressed on both sides thereof, and solidified in a press for 2 hours, and the curing pressure was 45. Kg/cm ² , curing temperature was 220 ° C, and copper clad laminates having thicknesses of 0.1, 0.4, and 0.8 mm were obtained, respectively.

Example 2

35 parts by weight of a naphthol novolac type cyanate resin obtained in Synthesis Example 1, 30 parts by weight of a phenol biphenyl aralkyl type epoxy resin (NC-3000-FH, supplied by Nippon Kayaku Co., Ltd.), 35 A part by weight of naphthol naphthyl ether type epoxy resin (EXA-7311, supplied by DIC Corporation), 0.02 parts by weight of zinc octoate dissolved in methyl ethyl ketone and mixed, and then added 80 parts by weight of boehmite (APYRAL AOH 30, Provided by Nabaltec), 1 part by weight of epoxy silane coupling agent (Z- 6040, supplied by Dow Corning), 1 part by weight of dispersant (BYK-W903, supplied by BYK), adjusted to a suitable viscosity with methyl ethyl ketone, stirred and mixed Evenly, the glue is made. According to the same manufacturing process as in Example 1, a copper-clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained. Example 3

40 parts by weight of the naphthol novolac type cyanate resin obtained in Synthesis Example 1, 15 parts by weight of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70) , supplied by KI Chemical Industry Co., Ltd.), 40 parts by weight of phenol biphenyl aralkyl type epoxy resin (NC-3000FH, supplied by Nippon Kayaku Co., Ltd.), 5 parts by weight of naphthol novolac epoxy resin (HP-4770, supplied by DIC Corporation), 0.02 parts by weight of zinc octoate dissolved in DMF, butanone and mixed uniformly, then added 75 parts by weight of boehmite (APYRAL AOH 30, supplied by Nabaltec), 50 parts by weight of spherical melting Silica (SC2050, supplied by Admatechs), 1 part by weight of epoxy silane coupling agent (Z-6040, supplied by Dow Corning), 1 part by weight of dispersant (BYK-W903, supplied by BYK), and adjusted with methyl ethyl ketone To the proper viscosity, stir and mix well to obtain a glue. According to the same manufacturing process as in Example 1, a copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

Example 4

38 parts by weight of the naphthol novolac type cyanate resin obtained in Synthesis Example 1, 25 parts by weight of bis(3-ethyl-5-methyl-4-maleimidophenyl)methane (BMI-70) , supplied by KI Chemical Industry Co., Ltd.), 32 parts by weight of phenol biphenyl aralkyl type epoxy resin (NC-3000FH, supplied by Nippon Kayaku Co., Ltd.), 5 parts by weight of naphthol phenyl aralkyl Base type epoxy tree (ESN-175, supplied by Tohto Kasei Co., Ltd.), 0.02 parts by weight of zinc octoate dissolved in DMF, butanone and mixed uniformly, then 150 parts by weight of spherical fused silica (SC2050, by Admatechs supplied), 15 parts by weight of silicone powder (KMP-605, supplied by Shin-Etsu Chemical), 10 parts by weight of silicone powder (KMP-597, supplied by Shin-Etsu Chemical), 1.5 parts by weight of dispersant (BYK-W9010, BYK) Provided), adjusted to a suitable viscosity with methyl ethyl ketone, stirred and mixed uniformly to obtain a glue. According to the same manufacturing process as in Example 1, a copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

Comparative example 1

35 parts by weight of a bisphenol A type cyanate resin prepolymer (BA-3000, supplied by LONZA) was used instead of 35 parts by weight of a naphthol novolac type cyanate resin used in Example 2, and the others were the same as in Example 1. The method obtained a copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm.

Comparative example 2

40 parts by weight of a naphthol novolac type cyanate resin used in Example 3 was replaced with 40 parts by weight of a dicyclopentadiene type cyanate resin (DT-4000, supplied by LONZA), and the same method as in Example 3 was carried out. A copper clad laminate having a thickness of 0.1, 0.4, and 0.8 mm was obtained.

The X-Y-direction thermal expansion coefficient (X-CTE/Y-CTE), flexural modulus, dipping resistance and flame retardancy physical property test data of the metal foil-clad laminates prepared in the above Examples and Comparative Examples are shown in Table 1. Place Table 1 Physical property test data of metal foil-clad laminates prepared in the examples and comparative examples

The test methods for physical data in Table 1 are as follows:

Dip resistance: A 50 x 50 mm sample was immersed in a 288 °C tin furnace, and the stratified foaming was observed and the corresponding time was recorded. Test sample thickness: 0.4 mm.

Flame retardancy: Judging according to the UL94 vertical burning test standard. Test sample thickness: 0.4 mm.

X, Y-CTE: Y direction along the direction of the warp of the fiberglass cloth, X direction of the weft direction; Test equipment and conditions: TMA, the temperature rise from room temperature 25 °C to 300 °C at a heating rate of 10 °C / min, determination Thermal expansion coefficient (CTE) in the plane direction from 50 ° C to 150 ° C. Test sample thickness: 0.1 mm.

Flexural modulus: Test equipment and conditions: DMA, the temperature was raised from room temperature 25 °C to 300 °C at a heating rate of 10 °C/min, and the flexural modulus at 50 °C was measured and recorded. Test sample thickness: 0.8 mm.

Physical property analysis:

Compared with the comparative examples, the examples have a flame retardancy of V-0 and a lower X, Y direction thermal expansion coefficient and a good flexural modulus.

In summary, the cyanate resin composition of the present invention has good mechanical properties, heat resistance, flame retardancy, and a laminate made of the prepreg obtained by using the cyanate resin composition. And metal foil-clad laminates, which also have good flame retardancy, low X, Y-direction thermal expansion coefficient, good mechanical properties, and are suitable for high production without using compounds or phosphorus compounds as flame retardants. A reliable substrate material for semiconductor packaging.

The above examples are not intended to limit the content of the composition of the present invention, and any minor modifications, equivalent changes and modifications made to the above examples in accordance with the technical spirit of the present invention or the parts by weight or amount of the composition are still in the present embodiment. Within the scope of the inventive solution.

Claims

Rights request

1. A cyanate ester resin composition, including cyanate ester resin, 12H-free epoxy resin and inorganic filler material. The structural formula of the cyanate ester resin is as follows:

Formula I

Wherein, R is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and n is an integer from 1 to 50.

2. The cyanate ester resin composition according to claim 1, wherein the structural formula of the 1H-free epoxy resin is as follows:

Formula II

Group, R ₂ is an aryl group, R ₃ and R ₄ are a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a group shown in formula III, R ₅ and R ₆ are a hydrogen atom, an alkyl group, Aryl group or aralkyl group, m is an integer from 0 to 5, c is an integer from 1 to 5, and n is an integer from 1 to 50.

Formula III

Among them, R ₇ is an aryl group, R ₈ is a _0_ or - - group, R ₉ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, i is 0 or 1, and j is 1 or 2.

3. The cyanate ester resin composition according to claim 1, wherein the inorganic filler material is silica, boehmite or a mixture of silica and boehmite Hc.

4. The cyanate ester resin composition according to claim 1, wherein the amount of the cyanate ester resin accounts for 10 to 90% by weight of the total amount of the cyanate ester resin and the halogen-free epoxy resin, and the halogen-free ring The amount of oxygen resin accounts for cyanate ester resin and no! ¾ 90~10% by weight of the total amount of epoxy resin.

5. The cyanate ester resin composition according to claim 1, wherein the cyanate ester resin and the cyanate ester resin composition contain no! ¾ When the total amount of epoxy resin is recorded as 100 parts by weight, the corresponding amount of inorganic filler material is 10 to 300 parts by weight.

6. The cyanate ester resin composition of claim 1, further comprising a maleimide compound.

7. The cyanate ester resin composition according to claim 6, wherein the amount of the maleimide compound accounts for 5 to 80% by weight of the total amount of the cyanate ester resin and the maleimide compound.

8. A prepreg made using the cyanate ester resin composition of claim 1, comprising a base material and a cyanate ester resin composition adhered to the base material after being impregnated and dried.

9. A laminated material produced using the prepreg of claim 8, including at least one piece of prepreg, and the laminated material is obtained by lamination and solidification.

10. A metal foil-covered laminated material made of the prepreg according to claim 8, including at least one piece of prepreg, one or both sides of the prepreg being covered with metal foil, and laminating and solidifying to obtain a cladding material. Metal foil laminate.