WO2014036711A1

WO2014036711A1 - Epoxy resin composition, and prepreg and laminated sheet coated with copper foil made from same

Info

Publication number: WO2014036711A1
Application number: PCT/CN2012/081092
Authority: WO
Inventors: 曾宪平; 任娜娜; 周彪
Original assignee: 广东生益科技股份有限公司
Priority date: 2012-09-07
Filing date: 2012-09-07
Publication date: 2014-03-13

Abstract

The present invention relates to an epoxy resin composition, and a prepreg and a laminated sheet coated with copper foil prepared by using the epoxy resin composition. The epoxy resin composition comprises the following components: (A) an epoxy resin containing two or more epoxy groups, (B) an active ester curing agent, and (C) a phosphate compound. According to the epoxy resin composition of the present invention, the epoxy resin having a specific molecular structure is adopted, and functionality is high, such that the resulting cured product has characteristics of high glass transition temperature and low moisture absorption; the active ester is adopted as a curing agent, such that the advantage of the active ester is completely provided, wherein the advantage comprises that no polar group is produced when the active ester reacts with the epoxy resin so as to provide excellent dielectric property and good moisture and heat resistance. In addition, with application of the active ester as the curing agent of the epoxy resin, water absorption of the phosphorous-containing component can be further improved, a water absorption rate and a dielectric loss value of the cured resin material can be reduced, and purposes of no halogen, fire retardation and good moisture and heat resistance can be concurrently achieved; and the prepreg and the laminated sheet coated with copper foil in the present invention have characteristics of no halogen, fire retardation, excellent dielectric property and excellent moisture and heat resistance.

Description

Epoxy resin composition and prepreg and copper clad laminate using the same

The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition and a prepreg and a copper clad laminate produced using the same. Background technique

With the increasing speed and multi-function of electronic product information processing, the frequency of application is increasing, and 3- 6 GHz will become the mainstream. In addition to maintaining higher requirements on the heat resistance of laminate materials, its dielectric constant and medium Loss value requirements will be lower and lower. The existing traditional FR-4 is difficult to meet the high-frequency and high-speed development needs of electronic products, and the substrate material is no longer a mechanical support role in the traditional sense, but will become a PCB and terminal manufacturer together with electronic components. An important way to improve product performance. Because high DK slows the signal transmission rate, high Df converts the signal portion into thermal energy loss in the substrate material, so reducing DK/Df has become a hot pursuit for substrate manufacturers. The traditional FR-4 material uses dicyandiamide as a curing agent. This kind of curing agent has good process operability due to its tertiary amine. However, due to its weak carbon-nitrogen bond, it is easily cracked at high temperature. The cured product has a low heat-resistant decomposition temperature and cannot be adapted to the heat resistance requirements of the lead-free process. In this context, with the wide-scale implementation of the lead-free process in 2006, the industry began to use phenolic resin as a curing agent for epoxy. The phenolic resin has a high-density benzene ring heat-resistant structure, so the epoxy curing system The heat resistance is excellent, but at the same time, the dielectric properties of the cured product tend to deteriorate.

Japanese Patent Laid-Open No. 2002-012650, 2003-082063 proposes to synthesize a series of active ester curing agents containing benzene ring, naphthalene ring or biphenyl structure as curing agents for epoxy resins, such as IAAN, IABN, TriABN, TAAN. The cured product can significantly reduce its dielectric constant and dielectric loss compared to conventional phenolic.

Japanese Patent Laid-Open No. 2003-252958 proposes a biphenyl type epoxy resin and an active ester as a curing agent, which can obtain a cured product which lowers the dielectric constant and the dielectric loss value, but the epoxy resin used is bifunctional and active. The cured crosslink density of the ester is low, the heat resistance of the cured product is low, and the glass transition temperature is low.

Japanese Patent Laid-Open No. 2004-155990, which uses an aromatic carboxylic acid to react with an aromatic phenol to obtain a polyfunctional active ester curing agent. The use of the active ester curing agent to cure a phenolic epoxy can achieve higher heat resistance. A cured product of good dielectric constant and dielectric loss value.

Japanese Patent Laid-Open No. 2009-235165 proposes a new polyfunctional active ester curing agent. Curing an epoxy containing an aliphatic structure results in a cured product having both a higher glass transition temperature and a lower dielectric constant and dielectric loss.

Japanese Patent Laid-Open No. 2009-040919 proposes a thermosetting resin composition having a stable dielectric constant and excellent electrical conductivity, and the main components include an epoxy resin, an active ester hardener, a hardening accelerator, and an organic solvent. The obtained cured product has good copper foil adhesion, dielectric constant and dielectric loss. The amount of epoxy resin and active ester was studied, but the relationship between epoxy resin and active ester structure and properties was not made. the study.

In addition, Japanese Patent Laid-Open No. 2009-242559, JP-A-2009-242560, JP-A-2010-077344, and JP-A-2010-077343 respectively disclose the use of alkylated phenol or alkylated naphthol novolac type epoxy resin, biphenyl. The phenolic epoxy resin, which uses an active ester as a curing agent, can obtain a cured product having low hygroscopicity, low dielectric constant, and dielectric loss tangent.

In the above prior patents, although it is proposed that the use of an active ester as an epoxy resin can improve the moisture resistance of the cured product, reduce the water absorption rate, and lower the dielectric constant and dielectric loss value of the cured product, but the disadvantage is that it is difficult to resist. A good balance between thermal and dielectric properties is achieved, so that the cured product has both a high glass transition temperature and a low dielectric loss tangent, and its dielectric properties are relatively stable with frequency, and the water absorption rate is more low. At the same time, no research has been done on how to achieve halogen-free flame retardancy of the cured product. Summary of the invention

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin composition which can provide excellent dielectric properties, moist heat resistance, and halogen-free flame retardancy required for a copper clad laminate.

Another object of the present invention is to provide a prepreg and a copper-clad laminate produced by using the above epoxy resin composition, which have excellent dielectric properties, moisture and heat resistance, and high glass transition temperature, and lower. The water absorption rate, while achieving no! 3⁄4 flame retardant.

To achieve the above object, the present invention provides an epoxy resin composition comprising the following components:

(A) an epoxy resin containing 2 or more epoxy groups, (B) an active ester curing agent, and (C) a phosphate salt compound;

The structural formula of the epoxy group-on-epoxy resin is as follows:

Xi, X _{2 are the} same or different,

Yi is

Wherein, it is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ₂ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a is an integer value of 1 to 30.

The amount of the component (B) active ester curing agent is calculated by using 100 parts by weight of the epoxy resin having two or more epoxy groups in the component (A), and the amount is calculated according to the epoxy equivalent and the active ester equivalent ratio. , the equivalent ratio is 0.85~1.2.

The component (C) brick ester compound is used in an amount of 5 to 20 parts by weight based on 100 parts by weight of the total of the component (A;), the component (B) and the component (C).

The component (B) active ester curing agent is obtained by a reaction of a phenolic compound linked by an aliphatic cyclic hydrocarbon structure, a difunctional carboxylic acid aromatic compound or an acidic compound, and a monohydroxy compound.

The difunctional carboxylic acid aromatic compound or the acid compound is used in an amount of 1 mol, the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is used in an amount of 0.05 to 0.75 mol, and the monohydroxy compound is used in an amount of 0.25 to 0.95 mol.

Wherein X is a benzene ring or a naphthalene ring, j is 0 or 1, k is 0 or 1 n is 0.25-2.5.

The component (C) salt acid ester compound has the following structural formula:

Equation 1:

Wherein m is 2 or 3; R ₃ and R 4 are an alkane or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and M is a metal atom selected from the group consisting of calcium, magnesium, aluminum, arsenic, and iron. Kind.

Also included are components: a curing accelerator, which is one or a mixture of an imidazole compound and a derivative thereof, a piperidine compound, a Lewis acid, and triphenylphosphine.

Further, it is a component: an organic or inorganic filler; the filler is blended in an amount of 5 to 500 parts by weight based on 100 parts by weight of the total of the component (A), the component (B) and the component (C).

The inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, barium titanate , one or more of barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate and mica; the organic filler is selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone One or more of the powders.

Meanwhile, the present invention provides a prepreg prepared by using the above epoxy resin composition, comprising a reinforcing material and an epoxy resin composition adhered to the reinforcing material by impregnation and drying.

Further, the present invention provides a copper-clad laminate produced using the above prepreg, comprising a plurality of laminated prepregs, and a copper foil laminated on one side or both sides of the laminated prepreg.

Advantageous Effects of Invention: 1 The epoxy resin composition of the present invention is an epoxy resin having a specific molecular structure, which has a high functionality, and the cured product has a low water absorption; 2 The epoxy resin composition of the present invention The active ester is used as a curing agent, which fully exerts the advantage that the active ester does not form a polar group when reacting with the epoxy resin, thereby having the advantages of excellent dielectric properties and good moist heat resistance, and the use of a specific structure of the monument-containing flame retardant The halogen-free flame retardant can be achieved without sacrificing the heat resistance of the original cured product, low water absorption rate, and excellent dielectric properties, and the flame retardancy of the cured product can reach UL94 V-0 level; The prepreg prepared by the epoxy resin composition and the copper-clad laminate thereof have excellent dielectric properties, moist heat resistance, and flame retardancy up to UL94 V-0. detailed description

The epoxy resin composition of the present invention comprises the following components:

(A) an epoxy resin containing two or more epoxy groups, (B) an active ester curing agent, and (C) a phosphate salt compound; The structural formula of the epoxy resin in which the component (A) contains 2 or more epoxy groups is as follows:

The preferred structural formula of the epoxy resin containing the component (A) containing 2 or more epoxy groups is as follows:

In the formula, a is an integer of 1 to 10, and R ₃ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

More specifically can be the following structural formula:

An integer of ~10;

Where a is an integer from 1 to 10.

The preferred structural formula of the epoxy resin containing the component (A) having 2 or more epoxy groups may also be as follows:

Where a is an integer from 1 to 10;

An integer of ~10; a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Where a is an integer from 1 to 10.

In the epoxy resin composition of the present invention, the component (B) active ester curing agent is a phenolic compound, a difunctional carboxylic acid aromatic compound or an acid halide which is linked by an aliphatic cyclic hydrocarbon structure. And a monohydroxy compound obtained by co-reaction. The active ester mainly functions to cure the epoxy resin, and since it does not have secondary hydroxyl groups after curing, the cured product has substantially no hydroxyl polar groups, has good dielectric properties, and has low dielectric properties. Water absorption and good resistance to heat and humidity.

The difunctional carboxylic acid aromatic compound or the acid compound is used in an amount of 1 mol, the passage The amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05 to 0.75 mol, and the amount of the monohydroxy compound is 0.25 to 0.95 mol. The structure of the difunctional hydroxycarboxy group can be defined as follows:

Wherein X is an alkylene group having 1 to 5 carbon atoms.

The structure of the phenolic compound linked by the fatty ring hydrocarbon structure can be defined as follows:

Wherein X is a benzene or naphthalene ring, j is 0 or 1, k is 0 or 1, and n is 0.25-2.5. The active ester curing agent is used in an amount of 100 parts by weight of the epoxy resin having two or more epoxy groups in the component (A), and the amount is calculated according to the epoxy equivalent and the active ester equivalent ratio, and the equivalent ratio is 0.85 to 1.2, the preferred equivalent ratio is 0.9 to 1.1, and the most preferable equivalent ratio is 0.95 to 1.05.

In the epoxy resin composition of the present invention, the component (C) salt ester compound has the following structural formula:

Wherein m is 2 or 3; R ₃ and R 4 are an alkane or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and M is a metal atom selected from the group consisting of calcium, magnesium, aluminum, arsenic, and iron. Kind. M is preferably aluminum or sodium from the viewpoint of lowering its water absorption rate and increasing its phosphorus content, but M is more preferably aluminum if it is further considered to minimize the influence of the flame retardant addition on the dielectric properties after curing of the resin composition. .

More specifically, the structural formula of the salt acid ester salt compound in the present invention is as follows:

The purpose of the inscription salt compound in the present invention is flame retardancy, and the amount thereof is not particularly limited as long as it can satisfy the UL 94 V-0 of the cured product. However, in order to ensure a better overall performance of the cured product, such as heat resistance and hydrolysis resistance, the amount of the ester salt compound is determined by the components (A), (B) and (C). The total amount is 5 to 20 parts by weight, and more preferably 8 to 15 parts by weight, based on 100 parts by weight.

The epoxy resin composition of the present invention may further comprise a component: a curing accelerator. The curing accelerator is not particularly limited as long as it can catalyze the reaction of the epoxy functional group and lower the reaction temperature of the curing system. The degree is preferably a mixture of one or more of an imidazole compound and a derivative compound thereof, a piperidine compound, a Lewis acid, and a triphenylphosphine. The imidazole compound may, for example, be 2-mercaptoimidazole, 2-phenylimidazole or 2-ethyl-4-mercaptoimidazole, and the piperidine compound may be exemplified by 2,3-diaminopiperidine. , 2,5-Diaminopiperidine 2,6-diaminopiperidine, 2,5-diamino-3-indolylpiperidine, 2-amino-4-4hydrazinopiperidine, 2-amino-3- Nitropiperidine, 2-amino-5-nitropiperidine, 4-didecylaminopiperidine. The amount of the curing accelerator is 0.05 to 1.0 part by weight based on 100 parts by weight of the total of the component (A), the component (B) and the component (C).

The epoxy resin composition of the present invention may further comprise a component: an organic or inorganic filler. The filler to be added as needed is not particularly limited, and the inorganic filler may be selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, and boron nitride. , one or more of silicon carbide, aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate, mica, etc.; One or more of polytetrafluoroethylene powder, polyphenylene sulfide, polyethersulfone powder and the like. Further, the shape, particle diameter, and the like of the inorganic filler are also not particularly limited, and usually have a particle diameter of 0.01 to 50 μm, preferably 0.01 to 20 μm, particularly preferably 0.1 to 10 μm, and such a particle size range The inorganic filler is more easily dispersed in the resin liquid. Further, the amount of the filler to be mixed is not particularly limited, and is 5 to 500 parts by weight, preferably 5, based on 100 parts by weight of the total of the component (Α), the component (Β), and the component (C). - 300 parts by weight, more preferably 5 to 200 parts by weight, particularly preferably 15 to 100 parts by weight.

The prepreg prepared using the above epoxy resin composition comprises a reinforcing material and an epoxy resin composition adhered to the reinforcing material by impregnation and drying, and the reinforcing material is a prior art reinforcing material such as a fiberglass cloth or the like.

A copper clad laminate produced using the above prepreg includes a plurality of laminated prepregs, and a copper foil which is laminated on one side or both sides of the laminated prepreg.

The epoxy resin composition of the present invention is made into a certain concentration of a glue, and the prepreg is obtained by impregnating the reinforcing material, then drying at a certain temperature, removing the solvent and semi-curing the resin composition. Then, a plurality of the prepregs are stacked in a certain order, and the copper foil is respectively pressed on both sides of the prepreg which are superposed on each other, and cured in a hot press to obtain a copper clad laminate having a curing temperature of 150. -250 ° C, curing pressure is 25-60 Kg / cm ² .

The embodiments of the present invention are described in detail below, but the present invention is not limited to the scope of the embodiments. Example 1

Take a container and add 100 parts by weight of naphthol novolac epoxy resin NC-7300L (Nippon Chemical Co., Ltd., EEW is 214 g/eq), and then add 105 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC, solid content 65%) Stirring, add flame retardant aluminum phosphate (Clariant, 23% phosphorus) 30 parts by weight, then add 0.075 parts by weight The curing accelerator DMAP, as well as the solvent benzene, continue to stir and become a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 2:

Take a container, add 100 parts by weight of naphthol novolac epoxy resin NC-7000L (Nippon Chemical Co., Ltd., EEW is 232 g/eq), and then add 95 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC, solid content 65%) Stirring, adding flame retardant aluminum phosphate (Clariant, 23% phosphorus content) 30 parts by weight, then adding 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, Continue to stir and hook into a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 3:

Take a container and add 100 parts by weight of naphthol novolac epoxy resin HP-5000 (Japan DIC, EEW is 250 g/eq), then add 90 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC) , solid content of 65%) stir and hook, then add flame retardant aluminum phosphate (Clariant, phosphorus content of 23%) 35 parts by weight, then add 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, continue Stirring is a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 4:

Take a container, add 100 parts by weight of dicyclopentadiene novolac epoxy resin HP-7200H (Japan DIC, EEW is 278 g / eq), and then add 79.6 parts by weight of active ester curing agent HPC-8000-65T ( Japan DIC, 65% solids content) Stirring, adding flame retardant aluminum salt (Clariant, 23% phosphorus) 35 parts by weight, adding 0.075 parts by weight of curing accelerator DMAP, and solvent 曱Benzene, continue to stir and form a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate. The curing temperature is 150-250 ° C, the curing pressure is 25-60 Kg/cm ² , and the curing time is 90 min. Example 5:

Take a container, add 100 parts by weight of aralkyl phenol novolac epoxy resin NC-2000L (Nippon Chemical Co., Ltd., 238 8 9 ), and then add 93.7 parts by weight of active ester curing agent HPC-8000. -65T (Japan DIC, solid content 65%), stir and hook, add flame retardant aluminum phosphate (Clariant, phosphorus content of 23%) 35 parts by weight, and then add 0.075 parts by weight of curing accelerator DMAP, and The solvent is benzene, continue to stir and form a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 6:

Take a container and add 100 parts by weight of biphenyl type phenolic epoxy resin NC-3000H (Nippon Chemical Co., Ltd., EEW is 288 g/eq), and then add 77.5 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC, solid content 65%) Stirring, adding flame retardant aluminum phosphate (Clariant, 23% phosphorus content) 30 parts by weight, then adding 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, Continue to stir and hook into a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 7

Take a container and add 100 parts by weight of naphthol novolac epoxy resin HP-6000 (Japan DIC, EEW is 250 g/eq), then add 90 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC) , solid content 65%) Stir well, add flame retardant aluminum phosphate (Clariant, 23% phosphorus content) 35 parts by weight, then add 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, continue to stir All hooks are glued. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Example 8

Take a container, add 100 parts by weight of naphthol novolac epoxy resin EXA-7318 (Japan DIC, EEW is 250 g / eq), and then add 90 parts by weight of active ester curing agent HPC- 8000-65T (Japan DIC, solid content 65%) Stirring, add flame retardant aluminum phosphate (Clariant, 23% phosphorus) 35 parts by weight, then add 0.075 parts by weight of curing accelerator DMAP, And the solvent benzene, continue to stir and hook into a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Comparative Example 1 :

Take a container, add 100 parts by weight of phenol novolac type epoxy resin N690 (Japan DIC, EEW is 205 g / eq), and then add 108.9 parts by weight of active ester curing agent HPC- 8000-65T (Japan DIC, solid content 65%) Stirring, add 30 parts by weight of flame retardant aluminum phosphate (Clariant, 23% phosphorus), then add 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, continue to stir Serve as a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm) and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Comparative Example 2:

Take a container, add 50 parts by weight of phenol novolac type epoxy resin N690 (Japan DIC, EEW is 205 g/eq), and 50 parts by weight of high bromine epoxy resin BREN-105 (Nippon Chemical Co., Ltd., bromine content 35%), then add 96.9 parts by weight of active ester curing agent HPC-8000-65T (Japan DIC, solid content 65%), stir evenly, add 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, continue to stir All hooks are glued. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Comparative Example 3:

Take a container, add 100 parts by weight of biphenyl type phenolic epoxy resin NC-3000H (Nippon Chemical Co., Ltd., EEW is 288 g/eq), and then add 36.5 parts by weight of linear phenolic curing agent TD-2090 (Japan DIC, Hydroxyl equivalent 105 g / eq ) Stirring, adding flame retardant aluminum phosphate (Clariant, 23% phosphorus content) 30 parts by weight, then adding 0.075 parts by weight of curing accelerator DMAP, and solvent benzene, Continue to stir and hook into a glue. Dip the above glue with a glass cloth (model 2116, thickness 0.08 mm) and control to a suitable thickness, The solvent is removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Comparative Example 4:

Take a container, add 100 parts by weight of biphenyl type phenolic epoxy resin NC-3000H (Nippon Chemical Co., Ltd., EEW is 288 g/eq), and then add 77.5 solid parts by weight of active ester curing agent HPC-8000-65T ( Japan DIC, solid content of 65%) Stirring, add flame retardant phosphate PX-200 (Da Ba Chemical Co., phosphorus content of 9%) 53.1 parts by weight, then add 0.075 parts by weight of curing accelerator DMAP, and The solvent is benzene, continue to stir and form a glue. The above-mentioned glue was impregnated with a glass cloth (model 2116, thickness 0.08 mm), and controlled to a suitable thickness, and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are laminated on each other, and a copper foil is laminated on both sides thereof, and cured in a hot press to obtain a copper-clad laminate having a curing temperature of 150-250 ° C, curing The pressure is 25-60 Kg/cm ² and the curing time is 90 min.

Table 1. Physical properties of each of the examples and comparative examples

Table 2. Physical property data of each of the examples and comparative examples (continued)

From the physical property data of Tables 1 and 2, it is known that the phenol type novolac epoxy resin is used in Comparative Example 1-2. When the active ester is cured, the dielectric loss tangent is high relative to Examples 1 to 8; when the epoxy resin having the same structure in Comparative Example 3 is cured with phenol, the dielectric properties of the cured product are poor, and the comparative examples are 4 The used flame retardant is used, but the obtained cured product has a low glass transition temperature, and at the same time, due to the large hygroscopicity of the flame retardant itself, the wet heat resistance is poor.

As described above, the copper-clad laminate of the present invention has superior dielectric properties, high glass transition temperature, and high heat and humidity resistance as compared with a conventional copper foil substrate, and is suitable for high frequency applications.

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 embodiments in accordance with the technical spirit or composition or content of the composition of the present invention still belong to the present technology. Within the scope of the program.

Claims

Rights request

An epoxy resin composition comprising the following components: (A) an epoxy resin containing 2 or more epoxy groups, (B) an active ester curing agent, and C) a tartrate salt compound;

The structural formula of the epoxy resin containing two or more epoxy groups of the component (A) is as follows:

Yi is

The epoxy resin composition according to claim 1, wherein the component (B) active ester curing agent is used in an amount of 2 or more epoxy groups containing the component (A). Calculated based on 100 parts by weight of the resin, the amount is calculated according to the epoxy equivalent and the active ester equivalent ratio, and the equivalent ratio is 0.85 to 1.2.

The epoxy resin composition according to claim 2, wherein the component (C) is a salt ester compound, and the component (A), the component (B), and the component (C) are used. The total amount of 100 parts by weight is 5 to 20 parts by weight.

The epoxy resin composition according to claim 1, wherein the component (C) salt compound is a metal ion-substituted salt of the salt having the following structural formula:

Wherein m is 2 or 3; R ₃ and R 4 are an alkane or an aromatic hydrocarbon group having 1 to 6 carbon atoms, and M is a metal atom selected from the group consisting of calcium, magnesium, aluminum, arsenic, and iron. One.

The epoxy resin composition according to claim 1, wherein the component (B) active ester curing agent is a phenol compound linked by an aliphatic cyclic hydrocarbon structure, and a difunctional carboxylic acid aromatic group. A compound or an acidic compound and a monohydroxy compound are reacted together.

The epoxy resin composition according to claim 5, wherein the amount of the difunctional carboxylic acid aromatic compound or the acid compound is 1 mol, and the amount of the phenolic compound linked by the aliphatic cyclic hydrocarbon structure is 0.05. ~0.75 mol, the monohydroxy compound is used in an amount of 0.25 to 0.95 mol.

The epoxy resin composition according to claim 1, wherein the component (B) active ester

Wherein X is a benzene ring or a naphthalene ring, j is 0 or 1, k is 0 or 1 and n is 0.25-2.5.

8. The epoxy resin composition according to claim 1, further comprising a component: a curing accelerator, wherein the curing accelerator is an imidazole compound and a derivative thereof, a piperidine compound, a Lewis acid, and a triphenylphosphine. One or more mixtures.

9. The epoxy resin composition according to claim 1, further comprising a component: an organic or inorganic filler; a compounding amount of said filler, relative to component (A), component (B), and component (C) The total amount of 100 parts by weight is 5 to 500 parts by weight.

The epoxy resin composition according to claim 9, wherein the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, and aluminum nitride. And one or more of boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, aluminum oxide, barium sulfate, talc, calcium silicate, calcium carbonate and mica; The filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide, and polyethersulfone powder.

11. A prepreg produced using the epoxy resin composition of claim 1; A reinforcing material and an epoxy resin composition attached to the reinforcing material by impregnation drying are included.

12. A copper clad laminate produced using the prepreg according to claim 11 comprising a plurality of laminated prepregs and a copper foil laminated to one or both sides of the laminated prepreg.