阅读说明：本技术 一种高频高速覆铜板用无卤树脂组合物及其制备方法和应用 (Halogen-free resin composition for high-frequency high-speed copper-clad plate and preparation method and application thereof ) 是由 秦伟峰 陈长浩 郑宝林 付军亮 杨永亮 刘俊秀 史晓杰 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种高频高速覆铜板用无卤树脂组合物,由固形物和溶剂组成,按重量份数计,包括以下组分：苯乙烯-马来酸酐共聚物10-60份,含苯并噁嗪环化合物20-100份,含磷环氧树脂10-100份,含磷阻燃剂5-50份,DDS固化剂0.5-5份,固化促进剂0.005-0.1份,无机填料5-50份,溶剂10-100份。本发明还公开了上述无卤树脂组合物的制备方法及其在高频高速覆铜板中的应用。本发明制作的高频高速覆铜板电性能良好,其玻璃化转变温度Tg≥170℃、热膨胀系数CTE≤2.3％、介电常数Dk≤3.5、介质损耗Df≤0.008,适用于高频高速印制线路板(PCB)的制作。(The invention discloses a halogen-free resin composition for a high-frequency high-speed copper-clad plate, which consists of a solid matter and a solvent, and comprises the following components in parts by weight: 10-60 parts of styrene-maleic anhydride copolymer, 20-100 parts of benzoxazine-ring-containing compound, 10-100 parts of phosphorus-containing epoxy resin, 5-50 parts of phosphorus-containing flame retardant, 0.5-5 parts of DDS curing agent, 0.005-0.1 part of curing accelerator, 5-50 parts of inorganic filler and 10-100 parts of solvent. The invention also discloses a preparation method of the halogen-free resin composition and application of the halogen-free resin composition in a high-frequency high-speed copper-clad plate. The high-frequency high-speed copper-clad plate manufactured by the invention has good electrical performance, the glass transition temperature Tg of the high-frequency high-speed copper-clad plate is more than or equal to 170 ℃, the coefficient of thermal expansion CTE of the high-frequency high-speed copper-clad plate is less than or equal to 2.3%, the dielectric constant Dk is less than or equal to 3.5, and the dielectric loss Df is less than or equal to 0.008, and the high-frequency high-speed copper-clad plate is suitable for manufacturing a high-frequency high-speed Printed Circuit Board (PCB).)

1. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate comprises a solid matter and a solvent, and is characterized by comprising the following components in parts by weight:

2. the halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the weight percentage of the solid is 45-75%, and the balance is organic solvent.

3. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the glass transition temperature Tg of the high-frequency and high-speed copper-clad plate manufactured by using the halogen-free resin composition is not less than 170 ℃, the coefficient of thermal expansion CTE is not more than 2.3%, the dielectric constant Dk is not more than 3.5, and the dielectric loss Df is not more than 0.008.

4. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the styrene-maleic anhydride copolymer is one or a combination of more than two of SMA1000, 2000,3000, EF30, EF40, EF-60 and EF-80.

5. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the benzoxazine ring-containing compound is at least one of bisphenol A benzoxazine resin, bisphenol F benzoxazine resin, allyl bisphenol A benzoxazine resin and 4, 4' -diaminodiphenylmethane benzoxazine resin.

6. The halogen-free resin composition for the high-frequency high-speed copper-clad plate according to claim 1, wherein the phosphorus-containing epoxy resin is one or a combination of any two or more of DOPO type epoxy resin, ODOPB type epoxy resin, DOPO-HQ type epoxy resin, DOPO-NQ type epoxy resin, phosphate ester epoxy resin, cyclic phosphate ester epoxy resin, phosphazene epoxy resin and phosphorus-silicon epoxy resin, and the epoxy equivalent weight of the phosphorus-containing epoxy resin is 170-260 g/eq.

7. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the phosphorus-containing flame retardant is Pasteur MELAPUR 200.

8. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the curing accelerator is one or a combination of two of 2-ethyl-4-methylimidazole, 2-undecylimidazole and 2-phenylimidazole.

9. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the inorganic filler is spherical silica micropowder with the particle size of 1-5 microns.

10. The halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to claim 1, wherein the solvent is one or a composition of more than two of butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, acetone and dimethylformamide.

11. The preparation method of the halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to any one of claims 1 to 10, which is characterized by comprising the following steps:

weighing the components in parts by weight, adding the DDS curing agent, the curing accelerator and the solvent into a reaction kettle, stirring for 30-90min, adding the rest components into the reaction kettle, and emulsifying and shearing at high speed for 1-6h to obtain the DDS curing agent.

12. The application of the halogen-free resin composition for the high-frequency and high-speed copper-clad plate according to any one of claims 1 to 10 in the high-frequency and high-speed copper-clad plate.

Technical Field

The invention belongs to the technical field of copper-clad plates, and particularly relates to a halogen-free resin composition for a high-frequency high-speed copper-clad plate, and a preparation method and application thereof.

Background

In recent years, with the rapid development of electronic technologies, information processing of electronic products such as mobile communications, servers, and mainframe computers has been continuously developed toward "high frequency and high speed digitization of signal transmission", and the demand of various high frequency electronic devices widely used in the communication field has also been rapidly increased, the signal processing and transmission frequency of electronic devices has been greatly increased, which has been advanced from megahertz (MHz) to gigahertz (GHz), and the application frequency has been continuously increased by a novel technology represented by a large network workstation, mobile phone wireless communications, car satellite navigation, and bluetooth technology, and tends to the high frequency or ultra high frequency field, and the high frequency and high speed of signal transmission has made a demand for an electronic circuit substrate for signal transmission to have high frequency and high speed characteristics. In order to maintain the transmission rate and the integrity of transmission signals, the substrate material of the circuit board must have a low dielectric constant and dielectric loss, and meanwhile, in order to maintain the normal operation function of the electronic component in high temperature and high humidity environment, the circuit board must also have high reliability such as heat resistance, low thermal expansion coefficient, low water absorption and the like.

A Copper Clad Laminate (CCL) is a plate-like material, which is simply called a Copper Clad Laminate, prepared by impregnating electronic glass fiber cloth or other reinforcing materials with resin, coating Copper foil on one or both surfaces, and performing hot pressing. The traditional copper-clad plate for the printed circuit mainly adopts brominated epoxy resin as a base material of the printed circuit, and realizes the flame retardant function of the plate through bromine. In recent years, however, carcinogenic substances such as dioxin and dibenzofuran have been detected in combustion products of electronic and electrical equipment waste containing halogen such as bromine and chlorine, and there is a possibility that the halogen-containing products release hydrogen halide, which is a highly toxic substance, during combustion. The european union formally implements a WEEE instruction (a scrap electronic and electrical equipment instruction) and a RoHS instruction (an instruction for limiting the use of certain harmful substances in electronic and electrical equipment) in 2006, 7, 1, prohibits the use of lead, polybrominated biphenyls (PBB) and polybrominated diphenyl ethers (PBDE) in the electronic and electrical equipment, and the global electronics industry enters the lead-free welding era. The issue of the two instructions, along with the promotion of market competition and the improvement of human environmental awareness, the non-halogenated copper-clad plate becomes an important research subject in the industry.

However, the electrical performance of the non-halogenated copper clad laminate in the prior art cannot meet the use requirements of high frequency, high speed and high reliability, and cannot meet the manufacture of a high frequency and high speed Printed Circuit Board (PCB).

Disclosure of Invention

In view of the above problems, one of the objectives of the present invention is to provide a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, which has good electrical properties, a glass transition temperature Tg of not less than 170 ℃, a coefficient of thermal expansion CTE of not more than 2.3%, a dielectric constant Dk of not more than 3.5, and a dielectric loss Df of not more than 0.008, and is suitable for the manufacture of high-frequency and high-speed Printed Circuit Boards (PCBs).

In order to solve the technical problems, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, which consists of a solid matter and a solvent, and comprises the following components in parts by weight:

according to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein the weight percentage of solid matters is 45-75%, and the balance is organic solvent.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein the glass transition temperature Tg of the high-frequency and high-speed copper-clad plate manufactured by adopting the halogen-free resin composition is more than or equal to 170 ℃, the coefficient of thermal expansion CTE is less than or equal to 2.3%, the dielectric constant Dk is less than or equal to 3.5, and the dielectric loss Df is less than or equal to 0.008.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein the styrene-maleic anhydride copolymer is one or the combination of more than two of SMA1000, 2000,3000, EF30, EF40, EF-60 and EF-80. Styrene in the structure of styrene maleic anhydride has lower dielectric constant and dielectric loss, and anhydride groups have enough reactivity to be used as a curing agent to be crosslinked and cured with epoxy resin, and the styrene maleic anhydride is used as a component of the halogen-free resin composition of the invention to reduce the generation of secondary polar groups, so that the product of the cured epoxy also has lower dielectric loss factor and dielectric constant.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein the benzoxazine ring-containing compound is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, allyl bisphenol A type benzoxazine resin and 4, 4' -diaminodiphenylmethane type benzoxazine resin. The benzoxazine ring-containing compound has high heat resistance, high glass transition temperature, almost zero curing shrinkage, low water absorption and excellent dielectric property.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency high-speed copper-clad plate, wherein the phosphorus-containing epoxy resin is one or the combination of more than two of DOPO type epoxy resin, ODOPB type epoxy resin, DOPO-HQ type epoxy resin, DOPO-NQ type epoxy resin, phosphate ester epoxy resin, cyclic phosphate ester epoxy resin, phosphazene epoxy resin and phosphorus-silicon epoxy resin with the epoxy equivalent of 170-260 g/eq.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, and the phosphorus-containing flame retardant is Pasteur MELAPUR 200.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein the curing accelerator is one or a combination of two of 2-ethyl-4-methylimidazole, 2-undecylimidazole and 2-phenylimidazole.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, and the inorganic filler is spherical silicon micropowder with the particle size of 1-5 microns.

According to another specific embodiment of the invention, the embodiment of the invention discloses a halogen-free resin composition for a high-frequency and high-speed copper-clad plate, wherein a solvent is one or a composition of more than two of butanone, cyclohexanone, propylene glycol methyl ether, ethylene glycol methyl ether, acetone and dimethylformamide.

The invention also provides a preparation method of the halogen-free resin composition for the high-frequency high-speed copper-clad plate, which comprises the following steps:

weighing the components in parts by weight, adding the DDS curing agent, the curing accelerator and the solvent into a reaction kettle, stirring for 30-90min, adding the rest components into the reaction kettle, and emulsifying and shearing at high speed for 1-6h to obtain the DDS curing agent.

The invention also provides the application of the halogen-free resin composition for the high-frequency high-speed copper-clad plate in the high-frequency high-speed copper-clad plate.

Compared with the prior art, the invention has the following technical effects:

the preparation method comprises the steps of selecting a styrene-maleic anhydride copolymer and a benzoxazine ring-containing compound as reaction components, and preparing the halogen-free resin composition for the high-frequency high-speed copper-clad plate through matching with other components; the high-frequency high-speed copper-clad plate prepared by using the halogen-free resin composition has high glass transition temperature (Tg is more than or equal to 170 ℃), excellent heat resistance, low coefficient of thermal expansion (CTE is less than or equal to 2.3%), low dielectric constant (Dk is less than or equal to 3.5) and low dielectric loss (Df is less than or equal to 0.008), and is suitable for manufacturing high-frequency high-speed Printed Circuit Boards (PCBs).

Detailed Description

The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure. While the invention will be described in conjunction with the preferred embodiments, it is not intended that features of the invention be limited to these embodiments. On the contrary, the invention is described in connection with the embodiments for the purpose of covering alternatives or modifications that may be extended based on the claims of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be practiced without these particulars. Moreover, some of the specific details have been left out of the description in order to avoid obscuring or obscuring the focus of the present invention. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.

Example 1

A halogen-free resin composition for a high-frequency high-speed copper-clad plate comprises the following components in parts by weight:

the preparation method of the halogen-free resin composition for the high-frequency high-speed copper-clad plate comprises the following steps:

weighing the components according to the weight parts, adding a DDS curing agent, a curing accelerator, butanone and cyclohexanone into a reaction kettle, and stirring for 90min at normal temperature until the DDS curing agent, the curing accelerator, the butanone and the cyclohexanone are completely dissolved;

adding styrene-maleic anhydride copolymer SMA1000, bisphenol A benzoxazine resin, phosphorus-containing epoxy resin, phosphorus-containing flame retardant and inorganic filler into a reaction kettle, continuously stirring, starting an emulsifying and high-speed shearing device, and emulsifying for 2 hours to obtain the halogen-free resin composition for the high-frequency high-speed copper-clad plate.

Example 2

A halogen-free resin composition for a high-frequency high-speed copper-clad plate comprises the following components in parts by weight:

the preparation method of the halogen-free resin composition for the high-frequency high-speed copper-clad plate comprises the following steps:

weighing the components in parts by weight, adding a DDS curing agent, a curing accelerator, cyclohexanone, propylene glycol methyl ether and ethylene glycol methyl ether into a reaction kettle, and starting and stirring at normal temperature for 90min until the DDS curing agent, the curing accelerator, the cyclohexanone, the propylene glycol methyl ether and the ethylene glycol methyl ether are completely dissolved;

adding a styrene-maleic anhydride copolymer EF40, allyl bisphenol A benzoxazine resin, phosphorus-containing epoxy resin, a phosphorus-containing flame retardant and an inorganic filler into a reaction kettle, continuously stirring, starting an emulsifying and high-speed shearing device, and emulsifying for 2 hours to obtain the halogen-free resin composition for the high-frequency and high-speed copper-clad plate.

The copper-clad plate prepared from the halogen-free resin composition for the high-frequency high-speed copper-clad plate obtained in the example 1-2 and the existing high-speed copper-clad plate were subjected to performance tests, and the results are shown in table 1.

TABLE 1 Properties of the halogen-free resin compositions of examples 1-2 and copper clad laminates made of conventional halogen-free resins

	Example 1	Example 2	Existing products
				Tg/(DSC),℃	177	178	170
Z-CTE,％	2.05	2.10	2.5
				Dk	3.15	3.20	3.4
Df	0.0070	0.0065	0.008

As can be seen from the data in Table 1, the copper-clad plate made of the halogen-free resin composition for the high-frequency and high-speed copper-clad plate has improved glass transition temperature, thermal expansion coefficient, dielectric constant, dielectric loss and the like.

While the invention has been described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing is a more particular description of the invention than is possible with reference to the specific embodiments, which are not to be construed as limiting the invention. Various changes in form and detail, including simple deductions or substitutions, may be made by those skilled in the art without departing from the spirit and scope of the invention.