TW201504325A - High-dielectric-constant resin composition and application thereof - Google Patents

Abstract

The invention relates to a high-dielectric-constant resin composition, as well as a prepreg and a copper-clad laminate (CCL) which are manufactured thereby. The prepreg manufactured by the high-dielectric-constant resin composition comprises high-dielectric-constant glass fiber fabric and a high-dielectric-constant resin composition subjected to impregnation drying and then attached to the high-dielectric-constant glass fiber fabric. The CCL manufactured by the high-dielectric-constant resin composition comprises at least one overlapped prepreg and copper foils pressed and coated on both sides of the overlapped prepregs. The CCL manufactured by the high-dielectric-constant resin composition has the performances of high dielectric constant, low dielectric loss, high glass transition temperature, high peel strength and the like and can meet the performance requirement of the high-dielectric-constant antenna substrate.

Description

High dielectric constant resin composition and use thereof

The invention belongs to the technical field of electronic materials, relates to a resin composition and use thereof, and particularly to a high dielectric constant resin composition and use thereof, and more particularly to a high dielectric constant composite material and a prepreg prepared using the same With a copper clad laminate, a prepreg and a copper clad laminate made of the high dielectric constant composite material can be applied to an antenna substrate.

With the development of new micro-machining technologies such as microelectronics and micro-mechanics, not only digital, baseband circuit modules, and even RF modules have been successfully designed and produced for miniaturization and wafer processing. As an important RF front-end device, the antenna is increasingly demanding. The miniaturization, built-in, multi-band and intelligentization are the development trend of small antennas for mobile terminals. Since the size of the printed antenna is inversely proportional to the relative dielectric constant of the substrate, a dielectric substrate having a high dielectric constant is used to reduce the antenna size.

The electric wave in the high frequency field requires that the energy loss or the transmission loss of the electronic device is small. The transport loss is consumed as thermal energy in the electronic device, which causes the electronic device to generate heat. The transmission loss is proportional to the dielectric loss tangent of the substrate. Therefore, in order to reduce the transmission loss, it is necessary to make the dielectric loss tangent small, that is, to ensure that the dielectric loss of the dielectric substrate is small.

Chinese patent CN100348661 discloses a composite dielectric layer formed of an organic insulating material and a dielectric ceramic powder. The organic insulating material is a cured resin formed by curing reaction of an epoxy resin and an active ester, and the obtained composite dielectric layer has a high dielectric constant. And lower dielectric loss, but the composite dielectric layer has a very low glass transition temperature of only 131 to 135 °C. This patent uses an active ester as a curing agent, although the cured product has a lower dielectric loss, but the glass transition temperature is lower.

Chinese patent CN101974205 discloses a high dielectric constant resin composition comprising an epoxy resin, at least one phenolic oxygen resin or a terminal carboxylated nitrile rubber, a biphenyl type phenolic resin or a naphthalene type phenolic resin, a high dielectric constant filler, although a cured product It has a high dielectric constant and a high glass transition temperature ( _Tg reaches 156 ° C), but the dielectric loss of the cured product is too large, up to 0.038.

In the high dielectric constant copper clad laminate, in order to make the dielectric constant high, the content of the high dielectric constant filler is high, so that the peel strength of the copper clad laminate is lowered. Meanwhile, in a high dielectric constant copper clad laminate, an E-type glass fiber cloth is generally used as a reinforcing material, but an E-type glass fiber cloth has a low dielectric constant, and it is difficult to make a high dielectric constant copper clad laminate. The dielectric constant value is higher.

In view of the above problems, the present invention proposes a high dielectric constant composite material for an antenna having a higher dielectric constant, a lower dielectric loss, a higher glass transition temperature, and a higher peel strength.

One of the objects of the present invention is to provide a high dielectric constant tree A fat composition capable of providing excellent dielectric properties, high glass transition temperature, and high peel strength required for a copper clad laminate.

In order to achieve the above object, the present invention adopts the following technical solution: a high dielectric constant resin composition comprising: ( _a ) a flexible epoxy resin having the following chemical structural formula: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, and n ₄ represents an average repeating unit of 0.25 to 1.25.

Another object of the present invention is to provide a high dielectric constant composite material comprising a high dielectric constant resin composition as described above and a high dielectric constant glass fiber cloth.

A third object of the present invention is to provide a prepreg which is produced using the above high dielectric constant resin composition.

A fourth object of the present invention is to provide a copper clad laminate comprising at least one prepreg as described above and a copper foil covering both sides of the laminated prepreg.

Compared with the prior art, the invention has the following beneficial effects: 1 using a dicyclopentadiene type epoxy resin, a dicyclopentadiene type cyanate resin and an active ester resin to reduce dielectric loss, a dicyclopentadiene type ring Oxygen resin and dicyclopentadiene type cyanate resin have low dielectric loss, and active ester and epoxy do not form polar groups and have excellent dielectric properties; 2 use high dielectric constant filler and high dielectric Constant glass fiber In order to increase the dielectric constant, in a high dielectric constant copper clad laminate, in order to make the dielectric constant high, a high dielectric constant filler is usually used, but only a high dielectric constant filler is used, and the dielectric constant is difficult to reach one. At a higher level, the present invention simultaneously uses a high dielectric constant filler and a high dielectric constant glass fiber cloth to further increase the dielectric constant; 3 uses a flexible epoxy resin to improve the peel strength in a high dielectric constant copper clad laminate In order to make the dielectric constant high, the content of the high dielectric constant filler is high, so that the peeling strength of the copper clad laminate is lowered, and the present invention uses a flexible epoxy resin to improve the peel strength; The copper-clad laminate prepared by the electric constant composite material can simultaneously achieve high dielectric constant, low dielectric loss, high glass transition temperature, high peel strength and the like, and the comprehensive performance is excellent, and the prior art is prevented from improving in a certain performance. At the same time, it brings about another problem of performance degradation, which can meet the performance requirements of high dielectric constant antenna substrate materials.

The contents of the present invention will be described in detail below:

[High dielectric constant resin composition]

According to the present invention, the dielectric constant is more than 10, that is, the high dielectric constant resin composition of the present invention.

According to the present invention, the flexible epoxy resin refers to an epoxy resin having the structure described in the following structural formula. The BPA skeleton of the epoxy resin of this structure maintains the heat resistance of the epoxy resin, and the long-chain skeleton of the hydrocarbon structure is improved. The flexibility of the epoxy resin, especially after curing, still has excellent flexibility while improving the peel strength of the copper clad laminate. Exemplary commercial epoxy resins having such a structure include EXA-4816, EXA-4822, EXA-4850-150, and EXA-4850-100, all of which are manufactured by Dainippon Ink Chemical Industry Co., Ltd., and these flexible rings. The oxyresin may be used singly or in combination of two or more different resins. The chemical structure of flexible epoxy resin is as follows:

Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~ C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10.

According to the present invention, the dicyclopentadiene type novolac epoxy resin refers to an epoxy resin having a structure of the following structural formula, and the epoxy resin of this structure is compared with a general bisphenol A type epoxy resin. In addition to the benzene ring, the molecular structure also has an alicyclic structure of dicyclopentadiene, thereby improving the heat resistance of the product and reducing the water absorption of the resin. The epoxy resin of this structure has excellent heat resistance and low hygroscopicity. Low dielectric loss and high peel strength. In addition, the epoxy resin of this structure has a high residual carbon ratio at a high temperature, and can also achieve a good flame retardant effect. The representative product is the HP-7200 series produced by Dainippon Ink Chemical Industry Co., Ltd. The order of the equivalents from small to large is HP-7200L, HP-7200, HP-7200H and HP-7200HH. In addition, Nippon Chemical Co., Ltd.'s XD-1000 resin is similar to HP-7200H and is widely used in the CCL industry. . These biscyclopentadiene type novolac epoxy resins may be used singly or in combination of two or more different resins.

The chemical structural formula of the dicyclopentadiene type phenolic epoxy resin is as follows:

n ₂ represents an average repeating unit of 1 to 10.

According to the present invention, the difunctional epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, naphthalene ring epoxy resin And any one or a mixture of at least two of the isocyanate modified epoxy resins. The mixture is, for example, a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, a mixture of a bisphenol S type epoxy resin and a biphenyl type epoxy resin, a naphthalene ring type epoxy resin and an isocyanate modified ring. Mixture of oxyresin, mixture of bisphenol A epoxy resin, bisphenol F epoxy resin and bisphenol S epoxy resin, biphenyl type epoxy resin, naphthalene ring type epoxy resin and isocyanate modified epoxy a mixture of resins.

In order to make the copper clad laminate flame retardant, the bisphenol A type epoxy resin can be selected from the bromine bisphenol A type epoxy resin EPICLON 153-60M produced by Wuxi Di'aisheng Epoxy Co., Ltd., and the bromine content is 46%~50%. Its chemical structure is as follows:

Wherein n ₅ represents an average repeating unit of 0 to 10.

According to the present invention, the polyfunctional epoxy resin is a functional group Epoxy resin with a degree greater than 2.

According to the present invention, the polyfunctional epoxy resin is any one of a novolac epoxy resin, a trisphenol methane type epoxy resin, and a tetraphenol ethylethane type epoxy resin, or a mixture of at least two.

According to the present invention, the phenolic epoxy resin is a phenol type novolac epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A type novolac epoxy resin, a biphenyl type novolac epoxy resin, and a naphthalene ring type phenolic epoxy resin. Any one of the resins or a mixture of at least two. The mixture is, for example, a mixture of a phenolic novolac epoxy resin and an o-cresol novolac epoxy resin, a mixture of a bisphenol A type novolac epoxy resin and a biphenyl type novolac epoxy resin, a naphthalene ring type novolac epoxy resin and a phenol a mixture of phenolic epoxy resins, a mixture of o-cresol novolac epoxy resin and bisphenol A novolac epoxy resin, a mixture of a biphenyl type novolac epoxy resin and a naphthalene ring type novolac epoxy resin. For the phenol type phenolic epoxy resin, N-740, N-770, N-775, N-865 series resin such as Nippon Ink Chemical Industry Co., Ltd. or PNE177 resin produced by Taiwan Changchun Artificial Resin Factory Co., Ltd. For the cresol novolac epoxy resin, N-660, N-665, N-670, N-673, N-680, N-695, etc., or Nippon Chemical Co., Ltd., manufactured by Dainippon Ink Chemical Industry Co., Ltd. EOCN-1020 series resin, bisphenol A type phenolic epoxy resin can be selected from EPR627MEK80 resin produced by American HEXION company, and biphenyl type phenolic epoxy resin can be selected from NC-3000 and NC-3000 produced by Nippon Kayaku Co., Ltd. H series resin, naphthalene ring type phenolic epoxy resin can be selected from Nippon Chemical Co., Ltd. NC-7300-L, NC-7300-2L and other series of resins.

The trisphenol methane type epoxy resin and the tetraphenol ethane type epoxy resin can increase the crosslinking density of the resin and increase the heat resistance and glass transition temperature of the sheet. The trisphenol-based methane epoxy resin can be selected from the series of resins such as EPPN-501H, EPPN-501HY, and EPPN-502H manufactured by Nippon Kayaku Co., Ltd., and its chemical structure is as follows:

Wherein n ₆ represents an average repeating unit of 0 to 5.

The tetraphenol ethane type epoxy resin can be selected from EPON 1031 resin produced by MOMENTIVE, USA, and its chemical structure is as follows:

According to the present invention, the dicyclopentadiene type cyanate resin refers to a cyanate resin having a structure of the following structural formula, wherein the cyanate resin of this structure uses dicyclopentadiene as a spacer to increase the main chain The length can further reduce the dielectric loss of the cyanate resin. The dielectric loss of cyanate resin is between 0.002 and 0.008, which is much lower than the dielectric loss of epoxy resin of 0.018~0.030. Moreover, cyanate resin is higher temperature, humidity and wider frequency than other thermosetting resins. The dielectric loss is kept low in the range, and the excellent dielectric properties make the cyanate resin have great advantages in the design circuit and microwave transmission. A typical cyanate resin currently used as a high performance circuit board is XU-71787 cyanate resin produced by DOW Chemical Co., Ltd., and XU-71787 cyanate resin is a dicyclopentadiene type cyanate resin. The chemical structural formula of the dicyclopentadiene type cyanate resin is as follows:

Wherein n ₃ represents an average repeating unit of 0 to 5.

According to the present invention, the active ester resin refers to a structurally active ester resin having the following structural formula, the active ester of this structure is used as a curing agent for an epoxy resin, and two or more of the active ester curing agent molecules are present. The ester group with higher activity can be cured with epoxy resin, and forms a grid without secondary hydroxyl groups when reacting with epoxy resin, so the cured product has lower dielectric loss and water absorption, which is Conventional curing agents, such as amine curing agents and phenolic curing agents, can achieve the resulting copper clad laminates with low water absorption, low dielectric loss, and excellent resistance to moist heat. The structurally active ester resin having the following structural formula may be EXB-9460S-65T active ester or HPC-8000-65T active ester manufactured by Dainippon Ink and Chemicals Co., Ltd. The chemical structural formula of the active ester resin is as follows:

Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, and n ₄ represents an average repeating unit of 0.25 to 1.25.

Preferably, the high dielectric constant resin composition further comprises a high dielectric constant filler.

According to the invention, the high dielectric constant filler refers to a filler having a dielectric constant greater than 10.

Preferably, the high dielectric constant filler is preferably a high dielectric constant inorganic particle having a perovskite crystal structure or a composite perovskite crystal structure, and further preferably barium titanate, barium titanate, magnesium titanate, titanic acid Calcium, barium titanate, barium calcium titanate, lead titanate, lead zirconate titanate, lead zirconate titanate, barium titanate, zirconium titanate, titanium dioxide, germanium dioxide, lead magnesium niobate, barium magnesium Acid bismuth, lithium niobate, potassium citrate, aluminum bismuth ruthenate, bismuth potassium citrate, bismuth ruthenate, lead bismuth citrate, titanium bismuth citrate, bismuth citrate, strontium titanate, strontium titanate and Any one or a mixture of at least two of calcium copper titanate. The mixture such as a mixture of barium titanate and barium titanate, a mixture of magnesium titanate and calcium titanate, a mixture of barium titanate and barium calcium titanate, a mixture of lead titanate and lead zirconate titanate, zirconium titanate a mixture of bismuth lead and barium titanate, a mixture of zirconium titanate and titanium dioxide, a mixture of cerium oxide and lead lanthanum magnesium oxide, a mixture of barium magnesium silicate and lithium niobate, potassium citrate and aluminum bismuth citrate a mixture, a mixture of bismuth potassium citrate and bismuth ruthenate, a mixture of bismuth ruthenate and titanium ruthenate, a mixture of bismuth ruthenate, strontium titanate, strontium titanate and copper calcium titanate.

The non-volatile components of the components (a), (b), (c), (d) and (e) in the resin composition are in parts by mass, and the component (a) is 5 to 15 parts by mass. The component (b) is 15 to 40 parts by mass, the component (c) is 10 to 25 parts by mass, and the component (d) is 10 to 25 parts by mass, the component (e) is 20 to 40 parts by mass.

The mass fraction of the component (a) is, for example, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, and 14 parts by mass.

The mass fraction of the component (b) is, for example, 16 parts by mass, 18 parts by mass, 20 parts by mass, 22 parts by mass, 24 parts by mass, 26 parts by mass, 28 parts by mass, 30 parts by mass, 32 parts by mass, 34 Parts by mass, 36 parts by mass, 38 parts by mass.

The parts by mass of the component (c) are, for example, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass, 20 parts by weight. Parts by mass, 21 parts by mass, 22 parts by mass, 23 parts by mass, and 24 parts by mass.

The mass fraction of the component (d) is, for example, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass, 20 parts by weight. Parts by mass, 21 parts by mass, 22 parts by mass, 23 parts by mass, and 24 parts by mass.

The parts by mass of the component (e) are, for example, 21 parts by mass, 22 parts by mass, 24 parts by mass, 26 parts by mass, 28 parts by mass, 30 parts by mass, 32 parts by mass, 34 parts by mass, 36 parts by mass, 38 parts by weight. Parts by mass.

In a high dielectric constant copper clad laminate, the dielectric constant must be such that the content of the high dielectric constant filler must be a certain amount, and the high dielectric constant resin composition is not volatile. The mass of the component is 100% by weight, and the mass of the high dielectric constant filler is 60 to 85 wt%, for example, 62 wt%, 65 wt%, 68 wt%, 72 wt%, 75 wt%, 78 wt%, 82 wt%, 84 wt%.

The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the resin composition. In addition, the "include" of the present invention may also be replaced by a closed "for" or "consisting of".

The high dielectric constant resin composition of the present invention can also be used in combination with various high polymers as long as it does not impair the intrinsic properties of the high dielectric constant resin composition. Specifically, for example, it may be a liquid crystal polymer, a thermosetting resin, a thermoplastic resin, a different flame retardant compound or an additive or the like. They can be used singly or in combination of plural kinds as needed.

Further, the high dielectric constant resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like.

As a preparation method of one of the resin compositions of the present invention, the (a) flexible epoxy resin, (b) dicyclopentadiene type novolac epoxy resin, (c) may be blended, stirred and mixed by a conventional method. a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above, (d) a dicyclopentadiene type cyanate resin, and (e) an active agent Prepared by ester resin.

A high dielectric constant resin composition comprising: (a) a flexible epoxy resin having the following chemical structural formula: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, n ₄ represents an average repeating unit of 0.25 to 1.25; and components (a), (b), (c), (d) and The non-volatile component of (e) is 5 parts by mass or less, the component (a) is 5 to 15 parts by mass, the component (b) is 15 to 40 parts by mass, and the component (c) is 10 parts by mass. ~25 parts by mass, the component (d) is 10 to 25 parts by mass, and the component (e) is 20 to 40 parts by mass; (f) a high dielectric constant filler, a high dielectric constant resin composition The mass of the non-volatile component is 100% by weight, and the mass of the high dielectric constant filler is 60 to 85% by weight. That is, the mass of the high dielectric constant filler accounts for 60 to 85 wt% of the mass of the nonvolatile component of the high dielectric constant resin composition.

[High dielectric constant composite]

The mass of the high dielectric constant composite is 100 wt%, and the mass of the high dielectric constant glass fiber cloth is 10 to 40 wt%, for example, 11 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 30 wt%, 37 wt%. , 39wt%. The mass percentage of high dielectric constant glass fiber cloth can be controlled by the following methods: 1 different types (such as 106 glass cloth, 1037 glass cloth, 1065 glass cloth, 1078 glass cloth, 2313 glass cloth) , high dielectric constant glass fiber cloth of 3313 fiberglass cloth, 1080 glass fiber cloth, 2116 glass fiber cloth, 7628 fiberglass cloth, etc.; 2 adjust the pinch gap of the glue machine to control the high dielectric constant resin composition The thickness after immersion in the high dielectric constant glass fiber cloth.

The high dielectric constant glass fiber cloth of the present invention refers to a glass fiber cloth having a dielectric constant of more than 10.

A high dielectric constant composite material comprising (1) a high dielectric constant resin composition and (2) a high dielectric constant glass fiber cloth, the high dielectric constant composite material having a mass of 100% by weight, the high dielectric constant glass The mass of the fiber cloth is 10 to 40% by weight; wherein, (1) the high dielectric constant resin composition comprises: (a) a flexible epoxy resin having a chemical structural formula as follows: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, n ₄ represents an average repeating unit of 0.25 to 1.25; and components (a), (b), (c), (d) and The non-volatile component of (e) is 5 parts by mass or less, the component (a) is 5 to 15 parts by mass, the component (b) is 15 to 40 parts by mass, and the component (c) is 10 parts by mass. ~25 parts by mass, the component (d) is 10 to 25 parts by mass, and the component (e) is 20 to 40 parts by mass; (f) a high dielectric constant filler, a high dielectric constant resin composition The mass content of the non-volatile component is 100% by weight, and the mass of the high dielectric constant filler is 60 to 85% by weight.

The invention also provides a prepreg and copper clad laminate prepared by using the above high dielectric constant composite material, which has high dielectric constant, low dielectric loss, high glass transition temperature and high peeling. strength.

[Prepreg]

The prepreg comprises a high dielectric constant glass fiber cloth and a high dielectric constant resin composition as described above adhered to the high dielectric constant glass fiber cloth by impregnation drying.

According to the present invention, the high dielectric constant glass fiber cloth is woven from lead-containing glass fiber or non-lead glass fiber, and the main components of the lead-containing glass are PbO, SiO ₂ and Al ₂ O ₃ , and non-lead glass. The main component is titanium citrate.

High dielectric constant glass fiber cloth with lead content can be selected from high dielectric constant glass fiber cloth developed by Nitto Dye. The dielectric constant of the fiber cloth is 12-15, which is much higher than the dielectric constant of the ordinary E-glass fabric. The high dielectric constant glass fiber cloth of the titanium bismuth silicate component can be selected from the high dielectric constant glass fiber cloth developed by Matsushita Electric Industrial Co., Ltd. and the Kyoto University Engineering Department and Japan Electric Glass Co., Ltd., which is made of non-lead titanium silicate glass. As a raw material, the dielectric constant was 11.6. The aluminoborosilicate glass fiber used in the ordinary copper clad laminate has a dielectric constant of 6.5, and the dielectric constant of the titanium niobate glass fiber is greatly improved, and the titanium niobate glass fiber is not only The dielectric constant is greatly improved, and it has the advantages of being lead-free, harmless to the human body, causing no pollution when discarded, low dielectric loss tangent (media loss tangent is 0.003), and good chemical resistance.

The preparation method of the prepreg of the present invention is not particularly limited as long as it is a method of preparing a prepreg by combining the high dielectric constant resin composition of the present invention with a high dielectric constant glass fiber cloth. An exemplary prepreg is prepared by forming the high dielectric constant resin composition of the present invention into a certain concentration of a glue liquid, impregnating the high dielectric constant glass fiber cloth, and then drying at a certain temperature to remove The solvent is semi-cured to obtain a prepreg.

In the above-described high dielectric constant resin composition for preparing a prepreg, an organic solvent may be used as needed, and the organic solvent is not particularly limited as long as it is a solvent compatible with each component of the resin composition, and the solvent serves as a solvent. Specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, diethylene glycol diethyl ether, and diethylene glycol butyl ether. Ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatics such as toluene, xylene, and mesitylene Hydrocarbons, esters such as ethoxyethyl acetate, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone Such as nitrogen-containing solvents. These solvents may be used alone or in combination of two or more.

[Copper-clad laminate]

Each of the prepregs includes a high dielectric constant glass fiber cloth and a high dielectric constant resin composition as described above adhered to the high dielectric constant glass fiber cloth by impregnation and drying.

The preparation method of the copper-clad laminate according to the present invention can be prepared by a conventional method, for example, the high dielectric constant resin composition of the present invention is made into a certain concentration of glue, and the impregnation is high. The dielectric constant glass fiber cloth is then dried at a certain temperature, the solvent is removed and semi-cured to obtain a prepreg. Then, one or more 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. The curing temperature is 150~250 ° C, and the curing pressure is 25~60 Kgf/cm ² .

In order to better explain the present invention and to facilitate understanding of the technical solution of the present invention, a typical but non-limiting embodiment of the present invention is as follows: for the high dielectric constant copper clad laminate produced above, the dielectric constant thereof, Dielectric loss, glass transition temperature, peel strength, etc. The following examples are further described and described in detail, wherein the parts by mass of the organic resin are based on parts by mass of the organic solids.

Example 1

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4816, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of phenol novolac epoxy resin PNE177, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 26.8 parts by mass of active ester resin, and an appropriate amount of solvent are stirred for a certain period of time, and then added with appropriate amount The zinc octoate and the 4-dimethylaminopyridine were further stirred uniformly. Finally, 415 parts by mass of barium titanate high dielectric constant filler BT-300 was added, and the mixture was thoroughly stirred and emulsified and dispersed to form a glue. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to a mass content of 10%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 1.

Example 2

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4822, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of trisphenol methane type epoxy resin EPPN-501H, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 27.3 parts by mass of activity The ester resin and the appropriate amount of solvent are stirred for a certain period of time, and then an appropriate amount of promoter zinc octoate and 4-dimethylaminopyridine are added, and the stirring is continued uniformly. Finally, 416 parts by mass of barium titanate high dielectric constant filler BT-300 is added. , thoroughly stirred, and emulsified and dispersed to form a glue. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (the mass content of the high dielectric constant glass fiber cloth was controlled to 40%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 1.

Example 3

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4816, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of tetraphenol ethane type epoxy resin EPON 1031, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 25.8 parts by mass of active ester resin, and an appropriate amount of solvent are stirred for a certain period of time, and then Then add appropriate amount of promoter zinc octoate and 4-dimethylaminopyridine, continue to stir evenly, and finally add 411 parts by mass of barium titanate high dielectric constant filler BT-300, stir well, and emulsify and disperse into glue . The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to have a mass content of 20%), and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are superposed on each other, and a copper foil is pressed on both sides thereof and placed in a hot press to be cured to form the high dielectric constant. Copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 1.

Example 4

Take a suitable container, add 15 parts by mass of flexible epoxy resin EXA-4822, 40 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of trisphenol methane type epoxy resin EPPN-501H, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 40 parts by mass of active ester resin, and an appropriate amount of solvent are stirred for a certain period of time, then Add appropriate amount of promoter zinc octoate and 4-dimethylaminopyridine, continue to stir evenly, and finally add 218 parts by mass of barium titanate high dielectric constant filler BT-300, stir well, and emulsify and disperse into glue. . The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to a mass content of 10%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 1.

Example 5

Take a suitable container, add 5 parts by mass of flexible epoxy resin EXA-4816, 15 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of phenol novolac epoxy resin PNE177, 10 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 20 parts by mass of active ester tree The fat and the appropriate amount of solvent are stirred for a certain period of time, and then an appropriate amount of the promoter zinc octoate and 4-dimethylaminopyridine are added, and the stirring is continued uniformly. Finally, 425 parts by mass of barium titanate high dielectric constant filler BT-300 is added. Stir well and emulsify and disperse into a glue. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to a mass content of 10%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 1.

Example 6

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4816, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 10 parts by mass of tetraphenol ethane type epoxy resin EPON 1031 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 21.6 parts by mass of active ester resin, and an appropriate amount of solvent are stirred for a certain period of time, and then an appropriate amount of promoter zinc octoate and 4-dimethylamino group are added. The pyridine was continuously stirred uniformly, and finally 343 parts by mass of barium titanate high dielectric constant filler BT-300 was added, and the mixture was thoroughly stirred, and emulsified and dispersed to form a dope. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to a mass content of 10%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. Glue formulation and copper foil layer The pressure plate material data table is shown in Table 1.

Comparative example 1

Take a suitable container, add 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 parts by mass of phenol type novolac epoxy resin PNE177, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, 24 parts by mass of active ester resin, and a suitable amount of solvent for stirring for a certain period of time Then, add appropriate amount of promoter zinc octoate and 4-dimethylaminopyridine, continue to stir evenly, and finally add 369 parts by mass of barium titanate high dielectric constant filler BT-300, stir well, and emulsifie and disperse Glue. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to a mass content of 10%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 2.

Comparative Example 2:

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4822, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 The mass fraction of trisphenol-based epoxy resin EPPN-501H, 54.6 parts by mass of the active ester resin, and the appropriate amount of solvent are stirred for a certain period of time, and then an appropriate amount of the promoter 4-dimethylaminopyridine is added, and the stirring is continued evenly. Finally, 425 parts by mass of barium titanate high dielectric constant filler BT-300 was added, and the mixture was thoroughly stirred and emulsified and dispersed to form a gum solution. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (the mass content of the high dielectric constant glass fiber cloth was controlled to 40%), and then the solvent was removed by drying to obtain a prepreg. The prepregs obtained by using a plurality of sheets are superposed on each other on both sides Each of the copper foils was laminated and cured in a hot press to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 2.

Comparative example 3

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4816, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of tetraphenol ethane type epoxy resin EPON 1031, 24.3 parts by mass of novolac TD-2090-60M, and a suitable amount of solvent for a certain period of time, then add appropriate amount of promoter 2-methylimidazole, continue to stir Evenly, 317 parts by mass of barium titanate high dielectric constant filler BT-300 was finally added, and the mixture was thoroughly stirred and emulsified and dispersed to form a gum solution. The above-mentioned glue was impregnated with a high dielectric constant glass fiber cloth and controlled to a suitable thickness (controlling the high dielectric constant glass fiber cloth to have a mass content of 20%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 2.

Comparative example 4

Take a suitable container, add 10 parts by mass of flexible epoxy resin EXA-4816, 30 parts by mass of dicyclopentadiene novolac epoxy resin HP-7200L, 15 parts by mass of bromine-containing epoxy resin EPICLON 153-60M, 10 Parts by mass of tetraphenol ethane type epoxy resin EPON 1031, 25 parts by mass of dicyclopentadiene type cyanate resin XU-71787, activity of 25.8 parts by mass The ester resin and an appropriate amount of solvent are stirred for a certain period of time, and then an appropriate amount of promoter zinc octoate and 4-dimethylaminopyridine are added, and stirring is continued uniformly. Finally, 411 parts by mass of barium titanate high dielectric constant filler BT-300 was added, and the mixture was thoroughly stirred and emulsified and dispersed to form a gum solution. The above-mentioned glue was impregnated with a common E-type glass fiber cloth and controlled to a suitable thickness (controlling the mass content of the ordinary E-type glass fiber cloth to 20%), and then the solvent was removed by drying to obtain a prepreg. A plurality of prepared prepregs were laminated on each other, and a copper foil was laminated on both sides thereof and placed in a hot press to be cured to form the high dielectric constant copper clad laminate. The composition of the glue formulation and the physical properties of the copper-clad laminate are shown in Table 2.

The materials listed in Tables 1 and 2 are as follows: EXA-4816: a flexible epoxy resin having a long chain of a hydrocarbon structure, an epoxy equivalent of 400 g/eq, produced by Nippon DIC Co., Ltd.; and EXA-4822: a long chain containing a hydrocarbon structure and A flexible epoxy resin having an ester bond at both ends of a long hydrocarbon chain, an epoxy equivalent of 390 g/eq, manufactured by Nippon DIC Co., Ltd.; HP-7200L: a dicyclopentadiene type novolac epoxy resin, epoxy equivalent of 247 g/eq, Japan DIC Co., Ltd.; EPICLON 153-60M: bromine-containing epoxy resin, epoxy equivalent 400g/eq, bromine content 46%~50%, produced by Wuxi Di'aisheng Company; PNE177: phenolic novolac epoxy resin, epoxy equivalent 177g /eq, Taiwan Changchun Synthetic Resin Factory; EPPN-501H: Trisphenol-based methane epoxy resin, epoxy equivalent 166g/eq, produced by Nippon Kayaku Co., Ltd.; EPON 1031: tetraphenol-ethane-type epoxy resin, ring Oxygen equivalent 210g / eq, produced by MOMENTIVE, USA; XU-71787: dicyclopentadiene type cyanate resin, produced by DOW Chemical Co., USA; HPC-8000-65T: active ester resin, active ester equivalent 223g / eq, Japan DIC Co., Ltd. production; TD-2090-60M: Resole phenolic resin, hydroxyl equivalent 105g/eq, produced by Japan DIC Co., Ltd.; BT-300: barium titanate filler, produced by Shandong Guohua Functional Materials Co., Ltd.

The test methods for the above characteristics are as follows:

(1) Dielectric property Dk/Df: The dielectric constant Dk and the dielectric loss Df of the sheet at 1 GHz were measured by a flat panel capacitance method.

(2) Glass transition temperature T _g : Measured according to the DMA method specified in IPC-TM-650 2.4.24.

(3) Peel strength PS: The peel strength of the sheet was tested in accordance with the "after thermal stress" experimental conditions in the IPC-TM-650 2.4.8 method.

Physical property analysis:

It can be seen from Table 1 and Table 2 that the flexible epoxy resin is not used in the resin formulation of Comparative Example 1, and the peel strength is small; the active ester resin curing agent is used alone in the resin formulation of Comparative Example 2, although the dielectric loss is relatively low, However, the glass transition temperature was low; the resin formulation of Comparative Example 3 used a novolac resin as a curing agent, and although the dielectric constant was high, the dielectric loss was excessive; the resin formulation of Comparative Example 4 and the resin formulation of Example 3. The same is true, but the high dielectric constant glass fiber cloth is used in the embodiment 3, and the ordinary E type glass fiber cloth is used in the comparative example 4. The dielectric constant of the comparative example 4 is better than the examples from Tables 1 and 2. 3 is low.

According to the above results, the copper-clad laminate produced by the high dielectric constant composite material of the present invention can simultaneously achieve high dielectric constant, low dielectric loss, high glass transition temperature, high peel strength and the like, and comprehensive performance. It is very excellent, avoiding the problem of the performance degradation of the prior art at the same time as a certain performance improvement, and can meet the performance requirements of the material of the high dielectric constant antenna substrate.

The above is only a preferred embodiment of the present invention, and is not intended to limit the content of the composition of the present invention. For those skilled in the art, various other corresponding arrangements may be made according to the technical solutions and technical concepts of the present invention. Any alterations, modifications, and modifications of the above-described embodiments in accordance with the technical spirit of the present invention or the composition or content of the composition are all within the scope of the present invention.

Claims (10)

A high dielectric constant resin composition comprising: (a) a flexible epoxy resin having the following chemical structural formula: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, and n ₄ represents an average repeating unit of 0.25 to 1.25. The high dielectric constant resin composition according to claim 1, wherein the high dielectric constant resin composition further comprises a high dielectric constant filler. The high dielectric constant resin composition according to claim 1 or 2, wherein the difunctional epoxy resin is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy Any one or a mixture of at least two of a resin, a biphenyl type epoxy resin, a naphthalene ring type epoxy resin, and an isocyanate modified epoxy resin. The high dielectric constant resin composition according to any one of claims 1 to 3, wherein the polyfunctional epoxy resin is a novolac epoxy resin, a trisphenol methane epoxy resin, and a tetraphenolyl group Any one or a mixture of at least two of the alkyl type epoxy resins; preferably, the novolac epoxy resin is a phenol type novolac epoxy resin, an o-cresol novolac epoxy resin, a bisphenol A type novolac epoxy resin Any one or a mixture of at least two of a biphenyl type novolac epoxy resin and a naphthalene ring type novolac epoxy resin. The high dielectric constant resin composition according to any one of claims 1 to 4, wherein the high dielectric constant filler is preferably a high dielectric having a perovskite crystal structure or a composite perovskite crystal structure. The constant inorganic particles are more preferably barium titanate, barium titanate, magnesium titanate, calcium titanate, barium titanate, barium calcium titanate, lead titanate, lead zirconate titanate, lead zirconate titanate, barium titanate Barium, zirconium titanate, titanium dioxide, germanium dioxide, lead magnesium niobate, barium magnesium strontium silicate, lithium niobate, potassium citrate, aluminum bismuth citrate, bismuth potassium citrate, bismuth citrate, strontium Any one or a mixture of at least two of lead bismuth citrate, titanium strontium ruthenate, strontium ruthenate, barium titanate, barium titanate, and calcium calcium titanate; preferably, a group of high dielectric constant resin compositions The non-volatile components of parts (a), (b), (c), (d) and (e) are in parts by mass, and the component (a) is 5 to 15 parts by mass, the component (b) ) is 15 to 40 parts by mass, the component (c) is 10 to 25 parts by mass, the component (d) is 10 to 25 parts by mass, and the component (e) is 20 to 40 parts by mass; Preferably, the mass of the non-volatile component of the high dielectric constant resin composition is 100% by weight, and the mass of the high dielectric constant filler is 60 to 85% by weight. The high dielectric constant resin composition according to any one of claims 1 to 5, wherein the high dielectric constant resin composition comprises: (a) a flexible epoxy resin having a chemical structural formula as follows: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, n ₄ represents an average repeating unit of 0.25 to 1.25; and components (a), (b), (c) in the high dielectric constant resin composition (d) and (e) non-volatile components in parts by mass, the component (a) is 5 to 15 parts by mass, and the component (b) is 15 to 40 parts by mass, the component ( c) is 10 to 25 parts by mass, the component (d) is 10 to 25 parts by mass, and the component (e) is 20 to 40 parts by mass; (f) high dielectric constant filler, high dielectric constant The mass of the nonvolatile component of the resin composition is 100% by weight, and the mass of the high dielectric constant filler is 60 to 85% by weight. A high dielectric constant composite material comprising the high dielectric constant resin composition according to any one of claims 1 to 6 and a high dielectric constant glass fiber cloth. The high dielectric constant composite material according to claim 7, wherein the high dielectric constant composite material has a mass of 100% by weight, and the high dielectric constant glass fiber cloth has a mass of 10 to 40% by weight; preferably, the The high dielectric constant composite material comprises (1) a high dielectric constant resin composition and (2) a high dielectric constant glass fiber cloth, the high dielectric constant composite material has a mass of 100% by weight, and the high dielectric constant glass fiber cloth The mass is 10 to 40% by weight; wherein, (1) the high dielectric constant resin composition comprises: (a) a flexible epoxy resin having a chemical structural formula as follows: Wherein R represents a long chain group of a hydrocarbon structure or a group having a long chain of a hydrocarbon structure and an ester bond at both ends of the long chain of the hydrocarbon structure, and the long chain of the hydrocarbon structure is selected from a C ₂ - C ₂₀ linear alkyl group, C ₂ ~C ₂₀ branched alkyl, n ₁ represents an average repeating unit of 1 to 10; (b) dicyclopentadiene type novolac epoxy resin, the chemical structural formula is as follows: Wherein n ₂ represents an average repeating unit of from 1 to 10; (c) a difunctional epoxy resin or/and a polyfunctional epoxy resin other than the epoxy resins described in (a) and (b) above; (d) Dicyclopentadiene type cyanate resin, whose chemical structural formula is as follows: Wherein n ₃ represents an average repeating unit of 0 to 5; (e) an active ester resin having a chemical structural formula as follows: Wherein R ₁ is a benzene ring or a naphthalene ring, k is 0 or 1, n ₄ represents an average repeating unit of 0.25 to 1.25; and components (a), (b), (c) in the high dielectric constant resin composition (d) and (e) non-volatile components in parts by mass, the component (a) is 5 to 15 parts by mass, and the component (b) is 15 to 40 parts by mass, the component ( c) is 10 to 25 parts by mass, the component (d) is 10 to 25 parts by mass, and the component (e) is 20 to 40 parts by mass; (f) high dielectric constant filler, high dielectric constant The non-volatile component of the resin composition has a mass of 100% by weight, and the mass of the high dielectric constant filler is 60 to 85 wt%; preferably, the high dielectric constant glass fiber cloth is lead-containing glass fiber or non-lead glass fiber. Braided. A prepreg comprising a high dielectric constant glass fiber cloth and a high dielectric constant resin composition according to any one of claims 1 to 6 which is attached to a high dielectric constant glass fiber cloth by impregnation and drying. A copper clad laminate comprising at least one prepreg according to claim 9 and a copper foil applied to both sides of the laminated prepreg.