阅读说明：本技术 一种应用于多层高频覆铜板粘结片的组合物及其应用 (Composition applied to multilayer high-frequency copper-clad plate bonding sheet and application thereof ) 是由 陈功田 李海林 邓万能 刘俊琨 付尧 刘明 于 2021-07-20 设计创作，主要内容包括：本发明公开了一种应用于多层高频覆铜板粘结片的组合物,所述组合物由以下重量份的原料混合制备而成：(1)热固性碳氢树脂20-40份；(2)陶瓷粉20-35份；(3)有机阻燃剂5-15份；(4)有机溶剂10-30份；(5)引发剂1-5份。本发明制得的粘结片介电性能低,粘结片与高频板多层压合后不会产生空洞与裂缝,避免产品长期使用后引起的各种电气性能失效。(The invention discloses a composition applied to a multilayer high-frequency copper-clad plate bonding sheet, which is prepared by mixing the following raw materials in parts by weight: (1) 20-40 parts of thermosetting hydrocarbon resin; (2) 20-35 parts of ceramic powder; (3) 5-15 parts of an organic flame retardant; (4) 10-30 parts of an organic solvent; (5) 1-5 parts of an initiator. The bonding sheet prepared by the invention has low dielectric property, and no cavity or crack is generated after the bonding sheet is laminated with a high-frequency plate in a multi-layer manner, so that various electrical property failures caused by long-term use of the product are avoided.)

1. The composition applied to the multilayer high-frequency copper-clad plate bonding sheet is characterized by being prepared by mixing the following raw materials in parts by weight:

(1) 20-40 parts of thermosetting hydrocarbon resin;

(2) 20-35 parts of ceramic powder;

(3) 5-15 parts of an organic flame retardant;

(4) 10-30 parts of an organic solvent;

(5) 1-5 parts of an initiator.

2. The composition of claim 1, wherein the thermosetting hydrocarbon resin is one or a mixture of two or more of a maleic anhydride-adducted polybutadiene, a maleic anhydride-modified polybutadiene styrene copolymer, an epoxidized hydroxyl-terminated polybutadiene resin, a methacrylated polybutadiene, a butadiene styrene copolymer, and a hydrogenated hydroxyl-terminated polyolefin resin.

3. The composition according to claim 1, wherein the ceramic powder is one or a mixture of two or more of nano-silica, nano-titania, nano-barium titanate, and nano-strontium titanate.

4. The composition as claimed in claim 1, wherein the organic flame retardant is one or a mixture of more than two of decabromodiphenylethane, ethylenebistetrabromophthalimide and bisDOPO ethane.

5. The composition according to claim 1, wherein the organic solvent is one or a mixture of two or more of toluene, xylene, mineral spirits and perchloroethylene.

6. The composition of claim 1, wherein the initiator is one or a mixture of two or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) -3-hexyne.

7. Use of the composition according to any one of claims 1 to 6 for preparing a multilayer high-frequency copper-clad plate bonding sheet.

8. Use according to claim 7, characterized in that the process for preparing said bonding sheet comprises the following steps:

the method comprises the following steps: firstly, adding thermosetting hydrocarbon resin into a container, respectively adding ceramic powder, an organic flame retardant and an organic solvent into the thermosetting hydrocarbon resin, and uniformly mixing to prepare glue;

step two: taking out the glue prepared in the step one, and putting the glue into a ball mill for dispersing;

step three: taking the glue in the second step out of the ball mill, and then dipping the glue by using non-fiber-opening glass fiber cloth;

step four: and (3) taking out the fiber glass fiber cloth impregnated with the glue in the third step, putting the fiber glass fiber cloth into an oven, and adjusting the temperature of the oven to 100-150 ℃ for drying to obtain the bonding sheet.

9. A multilayer high-frequency copper-clad plate, which is characterized by being manufactured by using the bonding sheet prepared in the claim 8.

10. The preparation method of the multilayer high-frequency copper-clad plate according to claim 9, wherein the method comprises the following steps: and placing the bonding sheet in the middle of the pressed high-frequency plate, repeatedly laminating the plurality of layers at intervals, and pressing for 60-90min under the conditions of vacuum and 220 ℃ of a laminating machine to obtain the multilayer high-frequency copper-clad plate.

Technical Field

The invention relates to the technical field of high-frequency copper-clad plates, in particular to a composition applied to a multilayer high-frequency copper-clad plate bonding sheet and application thereof.

Background

The copper-clad plate is a common material for a printed circuit board substrate of electronic equipment, but as the substrate of the printed circuit board of outdoor electronic equipment, the copper-clad plate needs to have stronger flame-retardant aging-resistant performance and moisture-resistant and moisture-proof performance, and in the big data era, the information processing of electronic products continuously develops towards the direction of high-frequency and high-speed digitization of signal transmission. If the electronic product is required to have good signal transmission quality under the condition of high-frequency signal transmission, the transmission line in the conductive copper foil of the copper-clad plate needs to be in an impedance matching state with the electronic element connected with the transmission line, so that the phenomena of signal reflection, scattering, attenuation, delay and the like are avoided, and the dielectric constant of the adhesive layer material in the flexible circuit board, which is in contact with the conductive circuit, is an important factor influencing the impedance matching of the high-frequency transmission. In order to realize impedance matching of high-frequency signal transmission, the adhesive layer generally needs to be made of a material with a low dielectric constant.

The existing high-frequency bonding sheet applied to the high-frequency copper-clad plate has high dielectric property and poor fluidity, and can generate holes and cracks after lamination.

Disclosure of Invention

The invention aims to provide a composition applied to a multilayer high-frequency copper-clad plate bonding sheet and application thereof, and aims to solve the problems that the existing high-frequency bonding sheet applied to the high-frequency copper-clad plate in the background art is high in dielectric property, poor in fluidity and capable of generating cavities and cracks after being pressed.

In order to achieve the purpose, the invention adopts the following technical scheme:

the composition is prepared by mixing the following raw materials in parts by weight:

(1) 20-40 parts of thermosetting hydrocarbon resin;

(2) 20-35 parts of ceramic powder;

(3) 5-15 parts of an organic flame retardant;

(4) 10-30 parts of an organic solvent;

(5) 1-5 parts of an initiator.

Preferably, the thermosetting hydrocarbon resin is one or a mixture of two or more of maleic anhydride-adducted polybutadiene, maleic anhydride-modified polybutadiene styrene copolymer, epoxidized hydroxyl-terminated polybutadiene resin, methacrylated polybutadiene, butadiene styrene copolymer, and hydrogenated hydroxyl-terminated polyolefin resin.

Preferably, the ceramic powder is one or a mixture of more than two of nano-scale silicon dioxide, nano-scale titanium dioxide, nano-scale barium titanate and nano-scale strontium titanate.

Preferably, the organic flame retardant is one or a mixture of more than two of decabromodiphenylethane, ethylene bistetrabromophthalimide and bis-DOPO ethane.

Preferably, the organic solvent is one or a mixture of more than two of toluene, xylene, solvent oil and perchloroethylene.

Preferably, the initiator is one or a mixture of more than two of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, dicumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -3-hexyne.

The invention also discloses application of the composition in preparation of a multilayer high-frequency copper-clad plate bonding sheet.

Further, the preparation method of the bonding sheet comprises the following steps:

the method comprises the following steps: firstly, adding thermosetting hydrocarbon resin into a container, respectively adding ceramic powder, an organic flame retardant and an organic solvent into the thermosetting hydrocarbon resin, and uniformly mixing to prepare glue;

step two: taking out the glue prepared in the step one, and putting the glue into a ball mill for dispersing;

step three: taking the glue in the second step out of the ball mill, and then dipping the glue by using non-fiber-opening glass fiber cloth;

step four: and (3) taking out the fiber glass fiber cloth impregnated with the glue in the third step, putting the fiber glass fiber cloth into an oven, and adjusting the temperature of the oven to 100-150 ℃ for drying to obtain the bonding sheet.

A multilayer high-frequency copper-clad plate is manufactured by using the bonding sheet prepared by the method.

A preparation method of a multilayer high-frequency copper-clad plate comprises the following steps: and placing the bonding sheet in the middle of the pressed high-frequency plate, repeatedly laminating the plurality of layers at intervals, and pressing for 60-90min under the conditions of vacuum and 220 ℃ of a laminating machine to obtain the multilayer high-frequency copper-clad plate.

Compared with the prior art, the invention has the beneficial effects that: through the common or synergistic effect of the thermosetting hydrocarbon resin, the organic flame retardant, the ceramic powder and the organic solvent, firstly, the thermosetting hydrocarbon resin which is obtained by adding maleic anhydride, anhydrizing maleic anhydride, epoxidizing, esterifying methacrylic acid and hydrogenating is used, the resin fluidity is enhanced, and the interlayer adhesive force of the multilayer board is better; secondly, the nano-scale ceramic powder is used, so that the particle size is small and the filling effect is better; thirdly, non-fiber-opening glass fiber cloth is used for impregnation, so that the surface glue of the bonding sheet is distributed more uniformly; and meanwhile, the high-frequency bonding sheet is endowed with very low dielectric property, and the prepared bonding sheet and a high-frequency plate are laminated in a multi-layer manner without generating cavities and cracks, so that various electrical property failures caused by long-term use of the product are avoided.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention relates to a resin composition applied to a bonding sheet for laminating multiple layers of high-frequency copper-clad plate substrates, which is prepared by mixing thermosetting hydrocarbon resin, ceramic powder, an organic flame retardant and an organic solvent, wherein the preparation of the resin composition is further detailed by a plurality of examples and comparative examples, and the following table 1 shows that:

TABLE 1 EXAMPLES 1-9 AND COMPARATIVE EXAMPLES 1-2 Components AND amounts

TABLE 2 test results of examples 1-9 and comparative examples 1-2

The resin mixtures prepared in the above examples 1-9 and comparative examples 1-2 were made into glue, dispersed by a ball mill, impregnated with non-split fiberglass cloth, dried at 100 ℃ and 150 ℃ to make a bonding sheet, and mixed with a high-frequency substrate to make a multilayer high-frequency copper clad laminate, and the following data were obtained:

TABLE 2 test data for each of the examples and comparative examples

The test method comprises the following steps:

1. interlayer adhesion: measured according to the method described in IPC-TM-6502.4.8;

2. dielectric constant: the dielectric constant at 10GHz was measured by the SPDR method;

3. dielectric loss: measuring the dielectric loss at 10GHz by using an SPDR method;

4. and (3) a wick effect: and (4) making a test pattern, a test method and conditions according to related requirements of IPC-610G, and judging according to test data of all samples, wherein pass (pass) is judged when the wick is less than 4mil (0.1mm), and fail (NG) is judged when the wick is greater than or equal to 4mil (0.1 mm).

5. Tin immersion and heat resistance: a copper-free sample of 50mm X50 mm was immersed in solder at 288 ℃ for 10 seconds, taken out, and then layered or not was confirmed, and the immersion was repeated 6 times, wherein the layered abnormality was pass (pass) and the layered abnormality was not pass (NG).

6. CAF test: test patterns and test methods and conditions are made according to related requirements of IPC-TM-6502.6.25, and the test environment with the temperature of 85 +/-2 ℃ and the humidity of 87+ 3/-2% RH is subjected to 1000-hour super-heating by adding 100VDC polarization, wherein pass is adopted if no abnormity occurs and fail is adopted if abnormity occurs.

7. Adhesive sheet filling property: a bonding sheet filling test board (patterns are etched on a substrate with 2OZ copper foils on the upper and lower surfaces and contain different line widths and line distances) is taken, and the prepreg is laminated up and down and then pressed. The obtained core plate was treated with PCT for 6 hours, then immersed in a tin furnace at 288 ℃ for 10 seconds, and taken out to observe whether or not there was any abnormality such as swelling, white spots, etc., and if there was no abnormality, the core plate was evaluated as good, and if there was any abnormality, the core plate was evaluated as bad.

As can be seen from the data in Table 2, the bonding sheet prepared by applying the resin composition obtained in the embodiment of the invention has excellent interlayer adhesion, dielectric property, heat resistance, CAF resistance and bonding sheet filling property and good wick effect after being laminated with a high-frequency board into a multilayer board, and is very suitable for being applied to the field of high-frequency multilayer boards.

The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.