CN1908063A - High-dielectric organic/inorganic hybrid material composition with flexibility and high heat resistance and its cured product - Google Patents

Abstract

The present invention discloses an organic/inorganic hybrid material composition useful for preparing a high dielectric adhesive layer having flexibility, high heat resistance, which comprises a high glass transition temperature (Tg) epoxy resin system; (b) the ferroelectric ceramic powder contains two or more particle size distributions, wherein one type of the ferroelectric ceramic powder must contain one type of nano powder; (c) conductive powder such as conductive carbon black; (d) at least one polymeric softener; (e) a polymeric dispersant; (f) other additives, such as diluents (diluents), adhesion promoters (adhesion promoters), hardeners, hardening accelerators, organic solvents, and the like.

Description

High-dielectric organic/inorganic hybrid material composition with flexibility and high heat resistance and its cured product

technical field

The invention relates to a high dielectric organic/inorganic hybrid material composition, which can be used to prepare a high dielectric bonding layer with flexibility and high heat resistance.

Background technique

U.S. Patent Publication US2002/0048137A1 discloses a capacitor foil for making a two-layered embedded capacitor, which includes a conductive layer and a high dielectric material formed on the conductive layer. Partially hardened bonding layer of electrical constant, wherein the bonding layer is formed by epoxy resin added with capacitive ceramic particles. Bonding the adhesive layer of the capacitor foil to a substrate with a patterned copper foil can prepare a printed circuit board intermediate product with an embedded capacitor, wherein the patterned copper foil is a ground plane of the capacitor ( ground plane), and the conductive layer is the power plane (powerplane).

US Patent No. 6274224 discloses a passive electrical article (passive electrical article), which includes a first substrate, a second substrate and an electrically insulating or conductive layer containing a polymer therebetween. One embodiment of this patent is an in-cell capacitor in which an epoxy resin composition dispersed with ceramic powder is used as an intermediate layer. The epoxy resin used in the composition may be a blend of bisphenol-A epoxy resin and novolac epoxy resin, and the ceramic powder may be barium titanate. The composition can be prepared by mixing barium titanate powder, an organic solution of epoxy resin and a dispersant. The dispersant is preferably an anionic dispersant, such as a copolymer of polyester and polyamine, commercially available from ICI Americas, Wilmington, Del. under the trade name "Hypermer PS3". The epoxy resin composition of this patent still has room for further improvement.

U.S. Patent Publication No. 2003/0006402 A1 discloses a high dielectric polymer composite material and a manufacturing method thereof. The high-dielectric polymer composite material has a dielectric constant greater than 200, which includes a polymer resin and a conductive material, wherein the conductive material can be transition metal powder, transition metal alloy powder, carbon black , carbon fiber or graphite. However, the high-dielectric polymer composite material of this patent has a very large dispersion factor (Dissipation factor), especially when the frequency is above 1MHz, and its dependence on frequency is too high, so it has no use value. And this patent application does not describe the heat resistance, adhesiveness and processability of the high dielectric polymer composite material. Therefore, there is still room for further improvement.

Contents of the invention

The focus of the present invention is to emphasize the compound material formulation technology of polymer resin and ceramic powder, so that the material has high dielectric properties, high heat resistance, good adhesion and excellent processability (flexibility), etc. at the same time.

The present invention will disclose the important material formulation technology that has not been mentioned before, to solve the problems that may occur in the mixture of epoxy resin/high dielectric ceramic powder/conductive material, including improving heat resistance, Brittleness, adhesion to copper foil, large dispersion factor, and compatibility with traditional (existing) PCB manufacturing processes, etc. The methods used include: 1) choosing the appropriate composition of epoxy resin to balance the heat resistance and adhesion at the same time; 2) filling the epoxy resin with a high dielectric ceramic powder to increase the dielectric constant of the mixture, And there are at least two or more particle size distributions, and one kind of nanopowder must be contained in it, which is expected to have good flowability during processing under high dielectric properties to ensure the quality of the substrate material; 3 ) Epoxy resin reacts with part of the conductive powder (carbon black with functional groups on the surface) to form a part of epoxy resin coated carbon black to reduce the dispersion factor (Dissipation factor); 4) Select an appropriate polymer dispersant, On the one hand, it can improve the low heat resistance of low-molecular-weight dispersion, especially the solder resistance of the substrate. On the other hand, it can also greatly improve the reliability of future product applications. It adheres to the surface of inorganic powder, has excellent compatibility with organic resin and even has a little reactivity, which can effectively solve the shortcomings of low molecular dispersants; 5) Add appropriate softener to solve the problem of excessive ceramic powder (in order to effectively Increase the dielectric constant) the disadvantage that the substrate is too brittle and cannot be processed; and 6) Add other additives in time to improve the viscosity problem or further enhance the adhesion. The obtained high dielectric compound can be prepared by traditional glass fiber cloth impregnation method, precision coating technology or screen/stencil printing technology. It has a high glass transition temperature (Tg > 180 ℃), and has excellent adhesion to copper foil. (>4lb/in) adhesive layer (bonding layer). The built-in capacitor manufactured by the present invention has a dielectric constant of 30-150 at a frequency of 1 MHz, and a dispersion factor of 0.02-0.07.

An organic/inorganic hybrid material composition completed according to the content of the present invention, comprising:

a) A high Tg epoxy resin system comprising an epoxy resin with the following structure:

其中n为0～10；

where n is 0-10;

b) A ferroelectric ceramic powder containing two or more particle size distribution ranges, wherein a first particle size distribution range is 1 to 100 nm, and a second particle size distribution range is 300 nanometers to 5 microns; and

c) a conductive powder.

Preferably, the conductive powder comprises transition metal powder, transition metal alloy powder, carbon black, or carbon fiber, wherein the conductive powder accounts for 0.01-20% by weight of the total solid content of the composition. More preferably, the conductive powder is carbon black. Optimally, the carbon black includes a conductive carbon black and a carbon black with carboxyl or hydroxyl groups on the surface.

Preferably, the ferroelectric ceramic powder contains two main particle size distribution ranges, wherein the first particle size distribution range is 50-100 nanometers, and the second particle size distribution range is 0.3-5 microns , and the ferroelectric ceramic powder in the first particle size distribution range accounts for 1-40% by weight of all the ferroelectric ceramic powder.

Preferably, the ferroelectric ceramic powder accounts for 50-95% by weight of the total solid content of the composition.

Preferably, the ferroelectric ceramic powder is BaTiO ₃ , SrTiO ₃ , Ba(Sr)TiO ₃ , or their implanted metal ions.

Preferably, the epoxy resin system further comprises one or more epoxy resins selected from the group consisting of bisphenol-A epoxy resins, cycloaliphatic epoxy resins, naphthalene ring-containing epoxy resins, bisphenol-A epoxy resins, Composed of phenyl epoxy resin and novolac (Novolac) epoxy resin.

Preferably, the epoxy resin system further comprises a polymer dispersant. More preferably, the polymer dispersant is polyester, polyamide, or their copolymers, and the polymer dispersant accounts for 0.1-5.0% by weight of the total solid content of the composition.

Preferably, the epoxy resin system further includes a polymer softener. More preferably, the polymer softener is polyester, polyamide, polyamide-imide, polyvinyl butyral, synthetic rubber, polyethylene Polycaprolactone, or aliphatic chain epoxy resin, and the polymer softener accounts for 0.5-20% by weight of the total solid content of the composition.

Preferably, the epoxy resin system further comprises a diluent or an adhesion promoter. Preferably, the diluent or bonding agent is as follows

Preferably, the epoxy resin system further includes a hardener, which can be polyamine, phenol resin or acid anhydride. The hardener is used in approximately the same equivalent amount as the epoxy resin system.

Preferably, the high epoxy resin system further includes a hardening accelerator. Preferably, the hardening accelerator accounts for 0.01-5% by weight of the hardening agent.

Preferably, the epoxy resin system further includes a silane coupling agent to improve the dispersion and compatibility of the dielectric ceramic powder in the composition. More preferably, the silane coupling agent is epoxysilane or aminosilane.

Preferably, the high epoxy resin system further comprises a catalyst. More preferably, the catalyst comprises a phenylphosphine compound, and the catalyst accounts for 0.01-5% by weight of the total solid content of the composition.

Preferably, the epoxy resin system further comprises an organic solvent.

The present invention also provides a hardened organic/inorganic hybrid material, which is hardened from the composition of the present invention. Preferably, the hardening is performed by heating the composition. More preferably, the heating is carried out at 160-200° C. for 2-6 hours. Preferably, the catalyst-containing high-Tg epoxy resin system reacts with the carbon black having carboxyl or hydroxyl groups on the surface at 100-130° C. for 3-6 hours before the hardening.

Implementation

The gist of the present invention is to manufacture substrate materials with high dielectric constant, low dissipation factor and high heat resistance (high Tg), which can be applied to high-frequency and high-speed communication, information or digital home appliances, including the manufacture of embedded capacitors . The raw materials used include (a) a high Tg epoxy resin system; (b) a ferroelectric ceramic powder containing two or more particle size distributions, and must contain a nanopowder; ( c) carbon black, which may contain one or more different types of carbon black, including conductive carbon black and carbon black with -COOH or -OH functional groups; (d) at least one polymer softener; ( e) polymer dispersant; (f) other additives such as initiator (initiator), diluent (diluent), adhesion promoter (adhesion promoter), catalyst and organic solvent, etc.

The manufacturing procedure is as follows:

1. Put the epoxy resin and the solvent in the reactor and heat it to 90-95°C to dissolve it completely.

2. Add an appropriate amount of carbon black to the dissolved epoxy resin, and use a high-speed mixer to disperse the carbon black at high speed. After dispersion, add a catalyst and raise the temperature to 100-130°C, and react for 3-6 hours.

3. Add appropriate amount of hardener and hardening accelerator, after fully dissolved, then add appropriate amount of dispersant, softener and other additives.

4. Add an appropriate amount of high-dielectric powders with different size and particle size ratios to the above solution, and then stir evenly at high speed. The content of the added high dielectric powder accounts for about 20-70% by volume or 50-95% by weight of the total solid content, and the ratio of large particle size (0.3-5μm) to small particle size (<100nm) is 100: 1～60:40.

5. Disperse the obtained organic-inorganic mixture with a ball mill for 12-36 hours to obtain a well-dispersed mixture coating solution.

6. Make the above-mentioned coating solution into a substrate to measure the electrical properties. There are three ways of making it:

(1) Glass fiber cloth impregnation process: first prepare the glass fiber cloth and coating liquid prepreg material, and then go through the pressing process at 200°C for about three hours to obtain the copper foil substrate.

(2) Precise coating process: first process adhesive-backed copper foil (RCC), and then press it with copper foil to form a copper foil substrate.

(3) The coating solution is printed on the substrate by the screen/steel printing process, and then the metal layer is laminated or cured at high temperature, and then the metal layer is plated to form a substrate with upper and lower electrodes.

7. After electrical measurement of the prepared substrate, the range of dielectric constant value obtained according to different material components is about 30-150 at a frequency of 1 MHz, and the dispersion factor is about 0.02-0.07.

8. In terms of thermal properties, in addition to passing the solder resistance test at 288°C, the Tg is also in the range of 180-220°C.

Typical raw materials used in the present invention are as follows:

◆Epoxy resin

where n is 0-10;

(b) Bisphenol-A epoxy resin (Diglycidyl ether of bisphenol A epoxy)

(c) Tetrabromo bisphenol A diglycidyl etherepoxy

(d) Cyclo aliphatic epoxy resin

For example, dicyclopentadiene epoxy resin

(e) Naphthalene epoxy resin

(f) Diphenylene epoxy resin

(g) Phenolic novolac epoxy resin

(h) o-cresol Novolac epoxy resin

◆Hardener

(a) Diamine: H ₂ NR ₁ -NH ₂

_R can be aromatic, aliphatic, cycloaliphatic or silane-containing aliphatic, for example

R ₂ : -, CH ₂ , SO ₂ , O, S, or C(CH ₃ ) ₂

R ₃ to R ₁₀ : H, CH ₃ , C ₂ H ₅ , C ₃ H ₇ , or C(CH ₃ ) ₃

(b) Phenol resin (phenol resin)

Phenolic resin

For example

Naphthol based resin

For example

Terpene phenol resin

Dicyclopentadiene resin

4，4’，4”-乙缩醛三苯酚(4，4’，4”-Ethylidene trisphenol)

4,4',4"-Ethylidene trisphenol (4,4',4"-Ethylidene trisphenol)

Tetraphenylolethane

Tetraxylenol ethane

四甲酚乙烷(Tetracresololethane_

Tetracresololethane (Tetracresololethane_

◆hardening accelerator

(a) Cationic catalyst

Boron trifluoride compound, such as RNH ₂ BF ₃ , R ₂ NH BF ₃ , R ₃ N BF _{3 ,} etc., where R can be aromatic, aliphatic or cycloaliphatic

(b) Anion catalyst

Coordination anion catalysts of tertiary amines, metal hydroxides, and monoepoxides, such as R ₃ N, NCH ₂ CC(NH)-N(CH ₃ ) _2, etc., where R can be aromatic, aliphatic or cyclic fat base

(c) Imidazole

1-methylimidazole (1-methylimidazole)

1,2-Dimethylimidazole (1,2-dimethyllimidazole)

2-pentadecylimidazole (2-heptadecylimidazole)

2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole)

◆Catalyst

Phenylphosphine compounds

Triphenylphosphine

◆Carbon black

1. Conductive carbon black

2. Carbon black with COOH or OH functional groups

◆Inorganic filler

It is mainly ferroelectric ceramic powder with high dielectric strength, such as BaTiO ₃ , SrTiO ₃ , Ba(Sr)TiO ₃ , BaTiO ₃ implanted with metal ions, SrZrO _{3 ,} etc.

◆Softener

The softening agent that can be applied to the present invention includes polyester (polyester), polyamide (polyamide), polyamide-imide (polyamide-imide), polyvinyl butyral (polyvinyl Butyral), artificial rubber (such as Carboxyl- Terminated Butadiene Acrylonitrile, CTBN), polycaprolactone (polycaprolactone, (R-[-O[-CO(CH ₂ ) ₅ -O-] _n -] _f ), aliphatic chain epoxy resin, etc.

Aliphatic chain epoxy resin:

The above different types of softeners have different reactivity and compatibility with the resin system due to structural differences, and also have different gains in flexibility, so they can also be used in combination to achieve the purpose of softening , in order to take into account both the processability during manufacturing and the heat resistance of the final copper foil substrate, including solder resistance and Tg temperature.

◆Dispersant

The polymer dispersant used in the present invention has good adhesion with inorganic powder, and has excellent compatibility and slight reactivity with organic resin, which can greatly improve the heat resistance and reliability of the substrate. Usable polymeric dispersants include copolyester-amides, polyesters or polyamides, and the like.

◆Other additives

□稀释剂(diluent)与增黏结剂(adhesion promoter)

□ diluent and adhesion promoter

□硅烷类偶合剂(Silane Coupling agent)，如环氧硅烷(epoxysilane)

□Silane coupling agent (Silane Coupling agent), such as epoxysilane (epoxysilane)

or aminosilane (Aminosilane), etc.

The present invention will be further understood from the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.

Detailed ways

Embodiment and comparative example:

Use different raw materials to form, and its content is as shown in Table 1, the way of embodiment 1 and 2 first adds appropriate amount of epoxy resin in the reactor, comprises bisphenol-A epoxy resin (bisphenol-A diglycidylether) (Epoxy 1) (code name 188EL, Changchun Resin Company, Taiwan, China), tetrabromo bisphenol-A epoxy resin (tetrabromo disphenol-A diglcidyl ether) (Epoxy 2) (code name BEB-350, Changchun Company, China Taiwan), cycloaliphatic Epoxy resin (cyclo aliphatic epoxy) (Epoxy 3) (code name HP-7200, DIC company, Japan), multifunctional epoxy resin (Multifunctional epoxy) (Epoxy4) (the aforementioned epoxy resin (a), purchased from Nippon Chemical Pharmaceutical Co., Ltd.), add an appropriate amount of dimethylformamide (dimethylformamide; DMF), and then heat to 90 ° C ~ 95 ° C to completely dissolve the epoxy resin. Add appropriate amount of carbon black (the code name XE-2B carbon black that Degussa company produces, and the code name M800 carbon black that Cabot company produces, the weight ratio of these two kinds of carbon blacks is 1: 1 by the epoxy resin after dissolving ), using a high-speed mixer to stir and disperse carbon black at a high speed, add 0.1% by weight of triphenylphosphine after dispersion, heat up to 105°C, and react for 4 hours. Then add an appropriate amount of hardening agent 4,4'-methylenedianiline (4,4'-Methylenedianiline) (ACROS company, the U.S.), and a suitable hardening accelerator 2-ethyl-4-methylimidazole (2- Ethyl-4-methylimidazole) (ACROS company, USA). When the hardener and the hardening accelerator are completely dissolved in the epoxy resin solution, add an appropriate amount of polymer dispersant Hypermer (Uniqema company, U.S.), and different softeners such as polyvinylbutyral (polyvinylButyral) (PVB, Changchun Resin Company, Taiwan, China) (softening agent 1), CTBN (ZEON Chemical Company, the U.S.) (softening agent 2), make it dissolve completely and then drop to room temperature. Then add an appropriate amount of high-dielectric fillers with different sizes and ratios (such as BaTiO ₃ A: the average particle size of BaTiO ₃ is 0.8 μm; BaTiO ₃ B: the average particle size of BaTiO ₃ is 60 nm), and stir evenly at high speed to form a resin/BaTiO ₃ / carbon black mixed solution.

The mixed solutions of Comparative Examples 1 to 5 were prepared using steps similar to Examples 1 and 2 but according to the formula in Table 1. The carbon black in Comparative Example 4 was directly added to the resin without heating at high temperature to react with the epoxy resin.

Mixed solutions with different proportions and different compositions prepared in Table 1 were dispersed using a ball mill, and then the organic/inorganic mixed solutions formed after dispersion were coated on copper foil with a scraper, and heated and baked to remove the solvent (100 ° C, 3 Hours), to partially harden it (partially cure) to form the so-called RCC (Resin Coated Copper), and press these back-adhesive copper foils and copper foils to harden at high temperature (pressing temperature is about 200 ° C, 2.5 hours ) to form an organic/inorganic hybrid copper foil substrate material, and finally tested its physical properties, which are listed in Table 2.

Table I composition Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Example 1 Example 2 Epoxy 1 (g) 7.22 6.63 7.73 8.28 8.90 8.28 8.00 Epoxy 2 (g) 5.18 4.95 5.77 6.18 6.80 6.18 5.97 Epoxy 3 (g) 1.05 1.04 1.21 1.30 1.92 1.30 1.26 Epoxy 4 (g) 1.50 1.50 1.75 1.88 0 1.88 1.82 Hardener (g) 3.78 3.42 3.99 4.28 4.1 4.28 4.14 Hardening Accelerator (g) 0.06 0.06 0.06 0.07 0.07 0.07 0.07 Dispersant (g) 3.60 3.61 4.20 4.50 4.50 4.50 4.32 Carbon black (g) 0 0 0 0.88 0 0.88 1.71 Softener 1(g) 0 0 0 1.50 1.50 1.50 0 Softener 2(g) 0 1.00 1.41 0 0 0 1.45 BaTiO ₃ A(g) 120.00 120.00 120.00 128.56 128.45 128.56 124.28 BaTiO ₃ B(g) 0 0 20.00 21.43 21.41 21.43 20.72

Table II characteristic Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Example 1 Example 2 Tg(°C) 203 197 189 186 158 192 189 Dielectric constant (1Mz) 30.02 33.12 35.53 118.52 37.62 58.86 102.65 Dispersion factor (1Mz) 0.0232 0.0243 0.0252 0.152 0.0262 0.0287 0.042 Peel Strengtha ⁾ (lb/in) 2.2 3.6 5.2 4.1 5.8 5.3 4.8 Flexibility ^b) Difference excellent excellent excellent excellent excellent excellent Processability of PCB process ^c) Brittle good good good good good good Solder resistance ^d) Untested fail qualified fail qualified qualified qualified

^a) Peel strength measured according to IPC-650 method

^b) Flexibility is evaluated according to IPC-650 method

^c) Current PCB process processing

^d) Solder resistance is tested at 2atm, 110°C for 2 hours and then tested at 288°C for 3 minutes

Comparative examples 1 and 2 use a single particle size of BaTiO ₃ without adding BaTiO ₃ nanopowder. Under the same ratio of BaTiO ₃ , the processability of the process is poor and the peeling strength (peeling strength) is not good; if an appropriate amount of softener can be added (Comparative Example 2), the flexibility and processability can be improved, but the peel strength is still not good, which is mainly caused by insufficient glue flow. The addition of BaTiO ₃ with different particle sizes can increase the bulk density of BaTiO ₃ , increase the dielectric constant, and because of the increase of BaTiO ₃ nano-powder, it can increase the flow rate and increase the bonding. In addition, the solder resistance is also improved, which can be obtained from the comparative example 2, 3 can be seen. Of course, an important factor for the increase of Tg is the choice of epoxy resin system. In principle, the addition of multifunctional epoxy resin can greatly increase Tg. In addition, in Comparative Example 4, the carbon black was directly added to the resin without heating at high temperature to react with the epoxy resin, and its dispersion factor was much higher than that of Examples 1 and 2. Therefore, pre-reaction of carbon black and epoxy resin can reduce the dissipation factor.

From the above results, we know that in order to obtain a kind of "high heat resistance and high dielectric organic/inorganic hybrid" with good processing applicability, the formula must contain high Tg epoxy resin, carbon black, carbon Pre-reaction of black and epoxy resin, appropriate softener, polymer dispersant, and high dielectric ceramic powder with at least two particle sizes, and must contain a nano-powder, etc., so that a It is a kind of high dielectric substrate material with real application value.

The present invention has been described above, and those skilled in the art can still make various changes and modifications without departing from the scope of the following claims.

Claims (25)

1. An organic/inorganic hybrid material composition, comprising: a) A high Tg epoxy resin system comprising an epoxy resin with the following structure:

where n is 0-10; b) A ferroelectric ceramic powder containing two or more particle size distribution ranges, wherein a first particle size distribution range is 1 to 100 nm, and a second particle size distribution range is 300 nanometers to 5 microns; and c) a conductive powder. 2. The composition according to claim 1, wherein the conductive powder comprises transition metal powder, transition metal alloy powder, carbon black, or carbon fiber, wherein the conductive powder accounts for the total of the composition 0.01 to 20% by weight of solid content. 3. The composition as claimed in claim 2, wherein the conductive powder is carbon black. 4. The composition as claimed in claim 3, wherein the carbon black comprises a conductive carbon black and a carbon black having carboxyl or hydroxyl groups on the surface. 5. The composition as claimed in claim 1, wherein the ferroelectric ceramic powder contains two main particle size distribution ranges, wherein the first particle size distribution range is 50-100 nm, and the second The particle size distribution range is 0.3-5 microns, and the ferroelectric ceramic powder in the first particle size distribution range accounts for 1-40% by weight of all the ferroelectric ceramic powder. 6. The composition according to any one of claims 5, wherein the ferroelectric ceramic powder accounts for 50-95% by weight of the total solid content of the composition. 7. The composition according to any one of claims 1, wherein the ferroelectric ceramic powder is BaTiO ₃ , SrTiO ₃ , Ba(Sr)TiO ₃ , or their implanted metal ions. 8. The composition of any one of claims 1, wherein the epoxy resin system further comprises one or more epoxy resins selected from the group consisting of bisphenol-A epoxy resins, cycloaliphatic It is composed of epoxy resin containing naphthalene ring, bisphenyl epoxy resin, and novolac (Novolac) epoxy resin. 9. The composition of any one of claims 1, wherein the epoxy resin system further comprises a polymeric dispersant. 10. The composition of claim 9, wherein the epoxy resin system further comprises a polymeric softener. 11. The composition of claim 10, wherein the epoxy resin system further comprises a diluent or an adhesion promoter. 12. The composition of claim 10, wherein the epoxy resin system further comprises a hardener which is polyamine, phenol resin or acidanhydride. 13. The composition as claimed in claim 9, wherein the polymer dispersant is polyester, polyamide, or a copolymer thereof, and the polymer dispersant accounts for 0.1 to 5.0 weight of the total solid content of the composition %. 14. The composition as claimed in claim 10, wherein the macromolecular softening agent is polyester (polyester), polyamide (polyamide), polyamide-imide (polyamide-imide), polyvinyl butyral ( polyvinyl Butyral), synthetic rubber, polycaprolactone (polycaprolactone), or aliphatic chain epoxy resin, and the polymer softener accounts for 0.5-20% by weight of the total solid content of the composition. 15. The composition of claim 11, wherein the diluent or adhesion promoter is as follows 16. The composition as claimed in claim 10, wherein the epoxy resin system further comprises a silane coupling agent (Silane Coupling agent), to improve the dispersion and compatibility of the dielectric ceramic powder in the composition sex. 17. The composition as claimed in claim 10, wherein the silane coupling agent is epoxysilane or aminosilane. 18. The composition as claimed in claim 12, wherein the high epoxy resin system further comprises a hardening accelerator, wherein the hardening accelerator accounts for 0.01 to 5% by weight of the hardener, and the amount of the hardener is the same as that of the hardener Epoxy resin systems have the same equivalent weight. 19. The composition of claim 4, wherein the high epoxy resin system further comprises a catalyst of a phenylphosphine compound, and the catalyst accounts for 0.01-5% by weight of the total solid content of the composition. 20. The composition of claim 10, wherein the epoxy resin system further comprises an organic solvent. 21. A hardened organic/inorganic hybrid material, which is hardened from the composition according to any one of claims 1 to 20. 22. The hardened organic/inorganic hybrid material as claimed in claim 21, wherein the hardening is performed by heating the composition. 23. The hardened organic/inorganic hybrid material as claimed in claim 22, wherein the heating is performed at 160-200° C. for 2-6 hours. 24. The organic/inorganic hybrid material of hardening as claimed in claim 21, wherein before carrying out this hardening, the epoxy resin system of the high Tg of this catalyzer containing phenylphosphine compound and this surface have carboxyl group or the carbon black of hydroxyl group React at 100-130°C for 3-6 hours. 25. The hardened organic/inorganic hybrid material according to claim 21, which has a dielectric constant of 30-150 at a frequency of 1 MHz, a dispersion factor of 0.02-0.07, and a high glass transition temperature of 170-230 ℃.