WO2023124484A1 - Resin composition and use thereof - Google Patents

Abstract

The present invention provides a resin composition and use thereof. The resin composition comprises a combination of resin and hollow glass microspheres, said hollow glass microspheres comprising the following components in percentage by mass: 89-93% of silicon dioxide, 5-10% of boron oxide, 0.3-1% of calcium oxide and 0.05-0.5% of sodium oxide. The hollow glass microspheres with specific components are compounded with the resin, so that the resin composition has low-dielectric-constant/low-dielectric-loss performance and good compressive strength, thereby meeting process requirements of glue mixing dispersion and lamination, and avoiding microsphere breakage risk. The resin composition and a metal foil-clad plate containing the resin composition have excellent low-dielectric-constant/low-dielectric-loss performance, and the temperature coefficient of dielectric constant is small, thus fully meeting the performance requirements of a high-frequency and high-speed substrate.

Description

A kind of resin composition and its application technical field

The invention belongs to the technical field of copper clad laminates, and in particular relates to a resin composition and its application.

Background technique

The development of modern high-frequency communication puts forward higher and higher requirements for the low dielectric performance of the plate. In general, the effective dielectric constant of a composite material can be approximated as the weighted sum of the dielectric constant of each component and its volume fraction occupied in the composite material. Since most of the volume of the hollow packing is occupied by gas, it has a low dielectric constant. In order to reduce the dielectric constant of the board, it is an effective method to add hollow fillers with low dielectric constants to the resin glue.

Hollow glass microspheres are a very typical hollow filler, usually composed of silica, boron oxide, sodium oxide and calcium oxide and other raw materials. The preparation process of hollow glass microspheres is: (1) SiO2, boron oxide , sodium oxide, calcium oxide and foaming agent and other eutectic powders are mixed evenly, melted at high temperature, and then cold crushed to obtain glass powder; (2) the crushed glass powder with a certain particle size is foamed at high temperature Bubble and classify to obtain hollow glass microspheres with a certain particle size.

Hollow glass microspheres have a low dielectric constant and are introduced into the preparation of printed circuit boards. For example, CN105453705A discloses a circuit assembly, including a conductive metal layer and a dielectric substrate layer, the composition of the dielectric substrate layer includes: 30-90% polymer matrix material, 5-70% hollow borosilicate Salt microspheres; the hollow borosilicate microspheres are treated with lye, which can reduce the sodium oxide content in the hollow borosilicate microspheres, thereby contributing to the improvement of the dielectric constant/dielectric loss performance, but the dielectric substrate The dielectric constant and dielectric loss of the layer are still high, which cannot meet the application requirements of high-frequency plates.

CN101429337A discloses a preparation method of low dielectric loss cyanate resin, comprising the steps of: first heating the cyanate resin above the melting point, after it is converted into a liquid state, adding a silane coupling agent and dried hollow glass Microbeads, mixed and stirred at 130-145°C until the silane coupling agent diffuses well and couples on the surface of hollow glass microspheres; then add catalyst to the above mixed system, stir to dissolve, and use resin transfer molding process to obtain products. The modified cyanate resin reduces the dielectric constant and dielectric loss of the cyanate resin, and improves heat resistance, but the compressive strength of the material is low, and the hollow glass microspheres have a large The risk of breaking the ball will lead to a decrease in the dielectric constant/dielectric loss performance of the material after the ball is broken.

CN207947948U discloses a light double-sided glass fiber laminated PCB copper clad board, including a PCB board and a copper foil board arranged at its upper and lower ends, the middle part of the upper and lower ends of the PCB board is provided with a glass fiber laminated board, and the inner cavity is filled with nano-scale The hollow glass bead layer has positioning grooves at the corners of the upper and lower ends; the middle part of one side of the copper foil plate is provided with a groove for placing a glass fiber laminate, and the corners of the end face are provided with positioning protrusions for inserting into the positioning groove . The copper-clad laminate uses a hollow glass bead layer instead of the traditional filler, which can reduce the density and improve the dielectric constant/dielectric loss and insulation of the board under the same quality. However, the commonly used hollow glass microspheres have a large ball breaking rate in sheet manufacturing, resulting in a decrease in dielectric constant/dielectric loss performance.

Generally speaking, compared with ordinary fillers, hollow glass microspheres have better dielectric constant/dielectric loss performance, and are light in weight, which is conducive to the development of light weight boards; but conventional hollow glass microspheres have lower compressive properties. Poor, broken balls are prone to occur, which brings certain difficulties to the manufacture and use of the board; moreover, the hollow glass microspheres will cause the dielectric performance of the board to deteriorate after the ball is broken. In order to avoid the risk of broken balls, sodium oxide and calcium oxide are tried in the prior art. The introduction of these two components is to reduce the melting temperature of the eutectic powder and the glass powder during foaming, and improve the clarity of the glass melt. , reduce the defects of the ball wall after the hollow glass microspheres are formed, and improve the compressive strength of the hollow glass microspheres, but the introduction of sodium oxide and calcium oxide will lead to an increase in the dielectric constant/dielectric loss of the hollow glass microspheres, thus making them lose The advantages in terms of dielectric constant/dielectric loss performance cannot meet the performance requirements of high-frequency plates.

Therefore, it is an urgent problem to be solved in this field to develop a composite material with excellent compressive strength and dielectric constant/dielectric loss performance to meet the use requirements of high-frequency and high-speed plates.

Contents of the invention

Aiming at the deficiencies of the prior art, the object of the present invention is to provide a resin composition and its application. By compounding the resin with specific hollow glass microspheres, the resin composition not only has low dielectric constant and dielectric loss , and the dielectric constant coefficient of variation with temperature (TCDk) is small, and has sufficient compressive strength, which can fully meet the process requirements of glue mixing and lamination during board processing.

For reaching this purpose, the present invention adopts following technical scheme:

In a first aspect, the present invention provides a resin composition, which includes resin and hollow glass microspheres; the hollow glass microspheres include the following components in terms of mass percentage: silicon dioxide 89-93% , boron oxide 5-10%, calcium oxide 0.3-1%, sodium oxide 0.05-0.5%.

The mass percentage of silicon dioxide in the hollow glass microspheres is 89-93%, for example, it can be 89%, 89.5%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5% or 93% , and the specific point values between the above-mentioned point values, due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values included in the range. Silica is the skeleton structure that forms the hollow glass microspheres of the present invention, and its content is 89-93%, which can make the hollow glass microspheres have both excellent low dielectric constant/dielectric loss and high compression resistance; if its content If it is less than 89%, the low dielectric loss performance of the hollow glass microspheres cannot be guaranteed. If the content is higher than 93%, the melting point of the eutectic powder is too high, and the prepared hollow glass microspheres have many wall defects and are resistant to compression. Decreased intensity.

The mass percentage of boron oxide in the hollow glass microspheres is 5-10%, such as 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9% or 9.5%, As well as the specific point values between the above-mentioned point values, due to space limitation and for the sake of brevity, the present invention will not exhaustively list the specific point values included in the range. Boron oxide has a fluxing effect in the preparation process of the hollow glass microspheres, and its content is in the range of 5-10%, which endows the hollow glass microspheres with excellent low dielectric constant/dielectric loss and compression resistance; if the hollow glass microspheres The content of boron oxide in the beads is less than 5%, the melting point of the eutectic powder is too high, the hollow microspheres have many defects, and the risk of breaking the ball is high; if the content of boron oxide is higher than 10%, the melting point of the melt powder Increased dielectric constant/dielectric loss.

The mass percentage of calcium oxide in the hollow glass microspheres is 0.3-1%, such as 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, 0.8%, 0.85%, 0.9% or 0.95%, and the specific point values between the above-mentioned point values, limited in space and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values included in the range; the above-mentioned content range Calcium oxide makes the hollow glass microspheres have low dielectric constant/dielectric loss and high compression resistance. If the content of calcium oxide is less than 0.3%, the melting point of the eutectic powder will be too high, and the defects of the ball wall will increase. , the hollow glass microspheres are easily broken; if the content of calcium oxide is higher than 1%, the dielectric constant/dielectric loss of the hollow glass microspheres will increase.

The mass percentage of sodium oxide in the hollow glass microspheres is 0.05-0.5%, such as 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45%, and the above points The specific point values between the values are limited to space and for the sake of brevity, the present invention no longer exhaustively enumerates the specific point values included in the range; the sodium oxide in the above content range makes the hollow glass microspheres have a low dielectric constant, Low dielectric loss and high compressive strength, if the content of sodium oxide is lower than 0.05%, the melting point of the eutectic powder will be too high, and the breaking rate of hollow glass microspheres will increase; if the content of sodium oxide is higher than 0.5% %, will cause the dielectric constant/dielectric loss of hollow glass microspheres to increase.

In the resin composition provided by the present invention, the hollow glass microspheres contain the above-mentioned specific contents of silicon dioxide, boron oxide, calcium oxide and sodium oxide, so that they have a relatively low dielectric constant and low dielectric loss while Good compressive strength can meet the processing requirements of rubber mixing dispersion and lamination (lamination pressure is usually ≤500PSI), avoiding the risk of ball breaking. The hollow glass microspheres are compounded with the resin, so that the resin composition and the metal-clad laminate comprising it have excellent low dielectric constant/dielectric loss performance, and the coefficient of variation of the dielectric constant with temperature (TCDk) is small, fully satisfying High frequency and high speed substrate requirements.

Preferably, the hollow glass microspheres further include three elements with a mass percentage ≤0.1% (such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%) Aluminum oxide, more preferably ≤0.05% aluminum oxide.

Preferably, the hollow glass microspheres also include oxides with a mass percentage of ≤0.1% (such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%) Magnesium, more preferably ≤0.05% magnesium oxide.

As a preferred technical solution of the present invention, the hollow glass microspheres also include a small amount of aluminum oxide and magnesium oxide, which are usually introduced because the raw materials for preparing hollow glass microspheres contain impurities; in order to ensure that the hollow glass microspheres It has excellent low dielectric constant/dielectric loss performance, high compressive strength and stable product quality, and the contents of the aluminum oxide and magnesium oxide are independently ≤0.1%, more preferably ≤0.05%.

Preferably, the hollow glass microspheres also include oxides with a mass percentage of ≤0.1% (such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%) Potassium, more preferably ≤0.05% potassium oxide.

The potassium oxide is usually introduced by the raw material of the hollow glass microspheres containing impurities, and the high content of potassium oxide will cause the dielectric constant/dielectric loss performance of the hollow glass microspheres to deteriorate; in order to make the hollow glass microspheres have excellent Low dielectric constant/dielectric loss performance, high compressive strength and stable product quality, wherein the mass percentage of potassium oxide is ≤0.1%, more preferably ≤0.05%.

Preferably, the hollow glass microspheres also include iron with a mass percentage of ≤0.1% (such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%) Oxides, more preferably ≤0.05% iron oxides.

Preferably, the iron oxide includes ferric oxide and/or ferrous oxide.

The iron oxide (including ferric oxide and/or ferrous oxide) is introduced by the raw materials for preparing hollow glass microspheres containing these impurities or by friction between the material and the production process equipment. Iron oxide is a conductive substance and may Problems leading to insufficient insulating properties of the board. In order to ensure that the hollow glass microsphere has excellent compressive performance, low dielectric constant/dielectric loss performance and stable product quality, the mass percentage of iron oxide is ≤0.1%, more preferably ≤0.05%.

As a preferred technical solution of the present invention, the hollow glass microspheres include the following components in terms of mass percentage: 89-93% of silicon dioxide, 5-10% of boron oxide, 0.3-1% of calcium oxide, and 0.05% of sodium oxide. -0.5%, aluminum oxide 0.001-0.1%, magnesium oxide 0.001-0.1%, potassium oxide 0.001-0.1%, iron oxide 0.001-0.1%.

In the present invention, the hollow glass microspheres may optionally include other known or unknown components and/or impurities in addition to the above substances.

Exemplarily, the content of each component in the hollow glass microspheres in the present invention can be measured by an inductively coupled plasma optical emission spectrometer (ICP-OES).

Preferably, the pressure resistance of the hollow glass micro beads is ≥6000PSI. For example, it can be 6500PSI, 7000PSI, 7500PSI, 8000PSI, 8500PSI, 9000PSI, 10000PSI, 10500PSI, 11000PSI, etc., preferably 7000-10000PSI Essence

Preferably, the true density of the hollow glass microspheres is 0.35-0.55g/cm ³ , such as 0.38g/cm ³ , 0.40g/cm ³ , 0.42g/cm ³ , 0.45g/cm ³ , 0.48g /cm ³ , 0.50g/cm ³ , 0.52g/cm ³ or 0.54g/cm ³ , and the specific point values between the above-mentioned point values, due to space limitation and for the sake of simplicity, the present invention will not exhaustively list the above-mentioned Specific point values included in the range are further preferably 0.40-0.45 g/cm ³ .

Preferably, the average particle diameter of the hollow glass microspheres is 5-25 μm, for example, it can be 8 μm, 10 μm, 12 μm, 14 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm or 24 μm, and specific points between the above values Due to space limitation and for the sake of brevity, the present invention does not exhaustively enumerate the specific point values included in the range, more preferably 10-20 μm.

Exemplarily, the average particle size of the hollow glass microspheres in the present invention is obtained by testing with a Malvern 3000 laser particle size analyzer.

Preferably, the resin composition includes the following components in terms of mass percentage: resin 20-90%, hollow glass microspheres 1-30%.

In the present invention, the mass percentage of resin in the resin composition is preferably 20-90%, for example, it can be 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, and the specific point values between the above-mentioned point values, due to space limitation and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

In the present invention, the mass percentage of hollow glass microspheres in the resin composition is preferably 1-30%, for example, it can be 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, as well as specific point values between the above-mentioned point values, are limited in space and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range. The hollow glass microspheres of the above content are compounded with the resin, so that the resin composition and the metal-clad laminate containing it have excellent low dielectric constant/dielectric loss, compression resistance, heat and humidity resistance and stability; if it If the content is too low, it will be difficult to effectively exert the low dielectric constant/dielectric loss properties of the hollow glass microspheres; if the content of the hollow glass microspheres is too high, the water absorption rate of the resin composition and the board may increase, and the heat and humidity resistance performance may decrease.

Preferably, the resin includes epoxy resin, polyphenylene ether resin, cyanate resin, triallyl isocyanate resin, butadiene-based polymer, isoprene-based polymer, vinyl silicone resin, elastic Any one or at least two combinations of block copolymers, bismaleimide compounds, polyimides, benzoxazine resins or polytetrafluoroethylene; But not limited to: the combination of epoxy resin and polyphenylene ether resin, the combination of polyphenylene ether resin and butadiene-based polymer, the combination of polyphenylene ether resin and vinyl silicone resin, the combination of polyphenylene ether resin and elastomer embedded The combination of segment copolymers, the combination of polyphenylene ether resin and bismaleimide compounds, the combination of epoxy resin, polyphenylene ether resin and butadiene-based polymer, the combination of epoxy resin, polyphenylene ether resin and elastic A combination of bulk block copolymers, a combination of epoxy resin, polyphenylene ether resin and bismaleimide compounds.

Preferably, the polyphenylene ether resin includes a polyphenylene ether resin containing unsaturated bonds, more preferably a methacrylate-terminated polyphenylene ether resin and/or a vinylbenzyl ether-terminated polyphenylene ether resin.

Preferably, the butadiene-based polymer comprises butadiene homopolymer and/or butadiene copolymer.

Preferably, the butadiene copolymers include butadiene-styrene copolymers, styrene-butadiene-styrene triblock copolymers, hydrogenated styrene-butadiene-styrene triblock copolymers Or any one or a combination of at least two of the hydrogenated butadiene-styrene copolymers.

Preferably, the isoprene-based polymer comprises isoprene homopolymer and/or isoprene copolymer.

Preferably, the hollow glass microspheres include surface-treated hollow glass microspheres.

Since the hollow glass microsphere is an inorganic material, it has poor compatibility with the organic resin matrix; as a preferred technical solution of the present invention, the hollow glass microsphere needs to be surface-treated with a surface treatment agent to increase its Compatibility with the resin, and then play a role to the greatest extent.

Preferably, the reagents for surface treatment include silane coupling agents, titanate coupling agents, cationic surfactants, anionic surfactants, amphoteric surfactants, neutral surfactants, stearic acid, Any one or a combination of at least two of oleic acid, lauric acid, phenolic resin, silicone oil, hexamethyldisilane amine or polyethylene glycol, more preferably silane coupling agent, titanate coupling agent, organic Any one or a combination of at least two of silicone oil or hexamethyldisilazane.

Preferably, based on the mass of hollow glass microspheres to be treated as 100%, the mass of the surface-treated reagent is 0.05-1.0%, such as 0.06%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, etc.

Preferably, the resin composition also includes 1-30% crosslinking agent in terms of mass percentage, for example, the mass percentage of crosslinking agent can be 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%, and the specific point values between the above-mentioned point values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific points included in the range. pip value.

Preferably, the crosslinking agent includes any one or a combination of at least two of amine crosslinking agents, acid anhydride crosslinking agents, phenolic resins, ester crosslinking agents, isocyanate crosslinking agents or polythiols, More preferred are amine crosslinking agents and/or phenolic resins.

Preferably, the resin composition further includes 0.01-10% accelerator by mass percentage, for example, the mass percentage of accelerator can be 0.05%, 0.1%, 0.5%, 1%, 2%, 3% , 4%, 5%, 6%, 7%, 8% or 9%, and the specific point values between the above-mentioned point values, limited by space and for the sake of simplicity, the present invention will no longer exhaustively list the ranges included specific point value.

Preferably, the accelerator includes an imidazole accelerator and/or a free radical initiator.

Preferably, the imidazole accelerator includes any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole or at least A combination of the two.

Preferably, the free radical initiator includes any one or a combination of at least two of organic peroxides, azo compounds or carbon-based free radical initiators.

Preferably, the resin composition also includes 10-60% non-hollow filler in terms of mass percentage, for example, the mass percentage of non-hollow filler can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%, and specific point values between the above-mentioned point values, limited by space and for the sake of brevity, the present invention will not exhaustively list the specific points included in the range. pip value.

Preferably, the non-hollow filler includes SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , SrTiO ₃ , AlN, BN, Si ₃ N ₄ , SiC, CaTiO ₃ , ZnTiO ₃ , BaSnO ₃ , chopped glass fiber Or any one or at least two combinations of chopped quartz fibers.

As a preferred technical solution of the present invention, the resin composition includes the following components in terms of mass percentage: 20-90% resin, 1-30% hollow glass microspheres, 10-60% non-hollow filler, accelerator 0.01-10%.

As another preferred technical solution of the present invention, the resin composition includes the following components in terms of mass percentage: 20-90% of resin, 1-30% of crosslinking agent, 1-30% of hollow glass microspheres, non- Hollow filler 10-60%, accelerator 0.01-10%.

Exemplarily, the hollow glass microspheres of the present invention can be purchased from the market, or can be prepared by conventional methods, and the preparation method includes the following steps:

(1) mix quartz sand, soda ash, feldspar, calcite, boric acid, sodium chloride, etc. according to the required proportion to obtain a mixture;

(2) Melt the mixture obtained in step (1) at a high temperature of 1200-1800°C (such as 1300°C, 1400°C, 1500°C, 1600°C, 1700°C, etc.), pour the molten glass into water to quench Water quenching in the tank to obtain amorphous glass frit;

(3) Grinding the glass frit obtained in step (2) to obtain glass powder;

(4) Put the glass powder obtained in step (3) into a beading furnace at 1400-1600°C (such as 1450°C, 1500°C, 1550°C, etc.) to make the dissolved gas overflow and foam, and the molten glass powder is Form into balls under the action of surface tension, and then cool and collect to obtain the hollow glass microspheres.

A solvent can also be added to the above resin composition, and the amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition can reach a suitable viscosity for impregnation and coating of the resin composition. . In the subsequent steps of drying, semi-curing or full curing, the solvent in the resin composition will be partially or completely volatilized.

As the solvent of the present invention, it is not particularly limited, generally, ketones such as acetone, butanone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate can be used alone, or Can be used in combination of two or more. Preferable are ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene.

The resin composition provided by the present invention is prepared by the following method. The preparation method includes: mixing resin, hollow glass microspheres, optional solvent, cross-linking agent and accelerator, stirring and dispersing to obtain the resin composition.

In a second aspect, the present invention provides a resin film or a resin-coated copper foil, wherein the material of the resin film or resin-coated copper foil includes the resin composition as described in the first aspect.

Preferably, the resin film is prepared by coating the resin composition on a release material and drying and/or baking.

Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and drying and/or baking.

In a third aspect, the present invention provides a prepreg, which includes a reinforcing material and the resin composition as described in the first aspect attached to the reinforcing material.

Preferably, the resin composition is attached to the reinforcing material after being impregnated and dried.

Preferably, the reinforcing material includes any one or a combination of at least two of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass fiber cloth, non-woven fabric, quartz cloth, and the like.

In a fourth aspect, the present invention provides a metal-clad board, the metal-clad board includes a metal foil, and at least one of the resin film as described in the second aspect or the prepreg as described in the third aspect .

In a fifth aspect, the present invention provides a printed circuit board, which includes the resin film as described in the second aspect, the prepreg as described in the third aspect, or the coating as described in the fourth aspect. At least one of the metal foil plates.

Compared with the prior art, the present invention has the following beneficial effects:

In the resin composition provided by the present invention, hollow glass microspheres of specific components are compounded with resin, so that it has low dielectric constant/dielectric loss performance, and also has good compressive strength, which can meet the requirements of rubber mixing. Process requirements for dispersion and lamination, avoiding the risk of broken balls. The resin composition and the metal clad plate comprising it have excellent low dielectric constant/dielectric loss properties, the dielectric constant at 10 GHz is as low as 2.65-3.38, the dielectric loss factor at 10 GHz is ≤0.0030, and the dielectric constant varies with temperature ( TCDk)≤66ppm/℃, with excellent stability, which fully meets the performance requirements of high-frequency and high-speed substrates.

Detailed ways

The technical solutions of the present invention will be further described below through specific embodiments. It should be clear to those skilled in the art that the examples are only for helping to understand the present invention, and should not be regarded as specific limitations on the present invention.

The materials involved in the following examples of the present invention and comparative examples include:

(1) Resin

Polyphenylene ether resin, MX9000, American SABIC;

Polybutadiene resin, B3000, Nippon Soda;

Butadiene-styrene copolymer, Ricon 100, number average molecular weight 4500, 1,2-vinyl content 70%, American Sartomer;

Styrene-butadiene-styrene copolymer, D1118, number average molecular weight 80000, vinyl content 15%, American Kraton;

Vinyl silicone resin, GV08, number average molecular weight is 1300, vinyl content is 8%, Zhejiang Sichuang Company.

(2)Hollow glass microspheres

The numbering (A1-A5, E1-E4), component (mass percentage, %) and index of hollow glass microspheres are as shown in Table 1:

Table 1

In Table 1, the hollow glass microspheres A1-A5, E1-E4 are all purchased through market channels and purchased from 3M; wherein, the test method of the mass percentage content of each component is an inductively coupled plasma optical emission spectrometer (ICP-OES ) test; the compressive strength is tested by the method recorded in the standard ASTM D-3102-72; the true density is obtained by the true density analyzer test, which meets the standard of GB/T 21782.2.

(3) Accelerator

Dicumyl peroxide, DCP, Shanghai Gaoqiao;

2,3-Dimethyl-2,3-diphenylbutane, Perkadox 30, AkzoNobel.

(4) Non-hollow packing

Spherical silica, DQ2028L, Jiangsu Ruilian.

Example 1

A resin composition comprising the following components in terms of mass percentage: polyphenylene ether resin (MX9000) 17.75%, butadiene-styrene copolymer (Ricon 100) 17.75%, accelerator (DCP) 0.5%, Hollow glass microsphere A1 10%, non-hollow filler (DQ2028L) 54%.

A metal foil clad plate, the preparation method is as follows:

(1) Place the resin composition provided by this embodiment in methyl ethyl ketone according to the formula quantity, stir mechanically, and disperse evenly to obtain a resin glue with a solid content of 65%;

(2) impregnating the glass fiber cloth with the resin glue obtained in step (1), heating and drying to form a prepreg, placing copper foils on both sides, and pressing and heating to obtain the metal foil-clad board.

Example 2-5

A kind of resin composition, its difference with embodiment 1 is only, hollow glass microsphere is respectively hollow glass microsphere A2 (embodiment 2), A3 (embodiment 3), A4 (embodiment 4) and A5 (implementation Example 5); other components and consumption are the same as in Example 1.

The resin compositions provided in Examples 2-6 were used to prepare metal foil-clad boards, and the preparation method was the same as that of Example 1.

Example 6

A resin composition, comprising the following components in terms of mass percentage: polyphenylene ether resin (MX9000) 54.73%, vinyl silicone resin (GV08) 29.47%, accelerator (DCP) 0.8%, hollow glass microspheres A1 5%, non-hollow filler (DQ2028L) 10%.

A metal foil-clad board is prepared by using the resin composition provided in this example, and the preparation method is the same as that in Example 1.

Example 7

A kind of resin combination, comprises following component by mass percentage composition: polybutadiene resin (soda B3000) 38.35%, styrene-butadiene-styrene copolymer (D1118) 20.65%, accelerator ( Perkadox30) 1.0%, hollow glass microspheres A1 30%, non-hollow filler (DQ2028L) 10%.

A metal foil-clad board is prepared by using the resin composition provided in this example, and the preparation method is the same as that in Example 1.

Comparative example 1-4

A kind of resin composition, its difference with embodiment 1 is only, hollow glass microsphere is respectively hollow glass microsphere B1 (comparative example 1), B2 (comparative example 2), B3 (comparative example 3), B4 (comparative example Ratio 4); Other components and consumption are all identical with embodiment 1.

The resin compositions provided in Comparative Examples 1-4 were used to prepare metal foil-clad boards, and the preparation method was the same as that of Example 1.

The metal clad boards provided by Examples 1-7 and Comparative Examples 1-4 were evaluated as follows:

(1) Dielectric constant (Dk) and dielectric loss factor (Df): SPDR (split post dielectric resonator) method is used for testing, the test condition is A state, and the frequency is 10GHz;

(2) Ball breaking evaluation of hollow glass microspheres

Cut the metal foil-clad plate into slices, cast and polish it, put it on the conductive glue, and spray gold to make a test piece for observation. Observe with a scanning electron microscope (SEM), observe the broken ball situation of the hollow glass microspheres in the resin, and evaluate it, the broken ball rate ≤ 1%, is excellent ◎; 1% < broken ball rate ≤ 5%, is Good ○; 5% < broken ball rate ≤ 10%, it is medium △; broken ball rate > 10% is poor ×;

(3) Dielectric constant coefficient of change with temperature (TCDk)

The SPDR (split post dielectric resonator) method is used for testing, and the frequency is 10GHz. Put the test system into a high and low temperature oven, test the dielectric constant at -55°C and 85°C respectively, and calculate the coefficient of change of dielectric constant with temperature (TCDk) according to the following publicity:

TCDk(ppm/℃)=1000000×(Dk(85℃)-Dk(-55℃))/((85+55)×Dk(25℃));

The test results are shown in Table 2:

Table 2

the Dk(10GHz) Df(10GHz) breaking ball situation TCDk(ppm/℃) Example 1 2.91 0.0027 ◎ 55 Example 2 2.88 0.0026 ◎ 50 Example 3 2.90 0.0028 ◎ 52 Example 4 2.95 0.0027 ◎ 56 Example 5 2.96 0.0029 ◎ 57 Example 6 3.38 0.0029 ◎ 66 Example 7 2.65 0.0030 ◎ 58 Comparative example 1 3.20 0.0033 ◎ 80 Comparative example 2 3.19 0.0034 ◎ 83 Comparative example 3 3.18 0.0032 ◎ 81 Comparative example 4 2.80 0.0025 x 50

It can be seen from Table 2 that in the resin compositions provided by Examples 1-7 of the present invention, the hollow glass microspheres with a specific component content are compounded with the resin to prepare a metal clad board with excellent low dielectric constant/ Dielectric loss performance, the dielectric constant is 2.65-3.38, and the dielectric loss is 0.0026-0.0030, which can meet the processing requirements of stirring dispersion and lamination. Electron microscope analysis does not cause broken balls, and the compressive strength is good. At the same time, the dielectric constant of the metal-clad plate is 50-66ppm/°C with a temperature variation coefficient, and the stability is good.

Although the hollow glass microspheres in Comparative Examples 1-3 have good compressive properties, the amount of components used exceeds the limit of the present invention, especially the high content of calcium oxide and sodium oxide, resulting in the resin composition containing it and The dielectric constant and dielectric loss factor of the metal clad board are high, and the coefficient of dielectric constant variation with temperature is 80-83ppm/℃, and the stability is poor.

Although the hollow glass microspheres in Comparative Example 4 have good low dielectric constant/dielectric loss properties, the amount of components used exceeds the limit of the present invention, especially the content of calcium oxide and sodium oxide is too small, resulting in the hollow microspheres prepared The compressive strength is low, even if it is dispersed by stirring, there is also the problem of broken balls.

The applicant declares that the present invention illustrates a resin composition of the present invention and its application through the above-mentioned examples, but the present invention is not limited to the above-mentioned examples, that is, it does not mean that the present invention can only be implemented depending on the above-mentioned examples. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (10)

A resin composition, characterized in that the resin composition includes resin and hollow glass microspheres; the hollow glass microspheres include the following components in terms of mass percentage: silicon dioxide 89-93%, boron oxide 5-10%, calcium oxide 0.3-1%, sodium oxide 0.05-0.5%. The resin composition according to claim 1, characterized in that, the hollow glass microspheres further comprise aluminum oxide with a mass percentage of ≤0.1%, preferably ≤0.05% aluminum oxide; Preferably, the hollow glass microspheres also include magnesia with a mass percentage of ≤0.1%, more preferably ≤0.05% of magnesia; Preferably, the hollow glass microspheres also include potassium oxide with a mass percentage of ≤0.1%, more preferably ≤0.05% of potassium oxide; Preferably, the hollow glass microspheres also include iron oxides with a mass percentage of ≤0.1%, more preferably ≤0.05% of iron oxides; Preferably, the iron oxide includes ferric oxide and/or ferrous oxide. The resin composition according to claim 1 or 2, wherein the compressive strength of the hollow glass microspheres is ≥6000PSI; Preferably, the true density of the hollow glass microspheres is 0.35-0.55g/cm ³ , more preferably 0.40-0.45g/cm ³ ; Preferably, the average particle diameter of the hollow glass microspheres is 5-25 μm, more preferably 10-20 μm. The resin composition according to any one of claims 1-3, characterized in that, the resin composition comprises the following components in terms of mass percentage: resin 20-90%, hollow glass microspheres 1-30% . The resin composition according to any one of claims 1-4, wherein the resin comprises epoxy resin, polyphenylene ether resin, cyanate resin, triallyl isocyanate resin, butadiene polymer isoprene-based polymers, vinyl silicone resins, elastomeric block copolymers, bismaleimide compounds, polyimides, benzoxazine resins, or polytetrafluoroethylene one or a combination of at least two; Preferably, the hollow glass microspheres include surface-treated hollow glass microspheres; Preferably, the reagents for surface treatment include silane coupling agents, titanate coupling agents, cationic surfactants, anionic surfactants, amphoteric surfactants, neutral surfactants, stearic acid, Any one or a combination of at least two of oleic acid, lauric acid, phenolic resin, silicone oil, hexamethyldisilane amine or polyethylene glycol, more preferably silane coupling agent, titanate coupling agent, organic Any one or a combination of at least two of silicone oil or hexamethyldisilazane. The resin composition according to any one of claims 1-5, characterized in that, the resin composition further comprises 1-30% crosslinking agent in terms of mass percentage; Preferably, the crosslinking agent includes any one or a combination of at least two of amine crosslinking agents, acid anhydride crosslinking agents, phenolic resins, ester crosslinking agents, isocyanate crosslinking agents or polythiols, Further preferred amine crosslinking agent and/or phenolic resin; Preferably, the resin composition further includes 0.01-10% accelerator by mass percentage; Preferably, the accelerator includes an imidazole accelerator and/or a free radical initiator; Preferably, the resin composition further includes 10-60% non-hollow filler in terms of mass percentage; Preferably, the non-hollow filler includes SiO ₂ , Al ₂ O ₃ , TiO ₂ , BaTiO ₃ , SrTiO ₃ , AlN, BN, Si ₃ N ₄ , SiC, CaTiO ₃ , ZnTiO ₃ , BaSnO ₃ , chopped glass fiber Or any one or at least two combinations of chopped quartz fibers. A resin film or resin-coated copper foil, characterized in that the material of the resin film or resin-coated copper foil comprises the resin composition according to any one of claims 1-6; Preferably, the resin film or resin-coated copper foil is prepared by coating the resin composition on a release material or copper foil and drying and/or baking. A prepreg, characterized in that the prepreg comprises a reinforcing material and the resin composition according to any one of claims 1-6 attached to the reinforcing material. A metal-clad board, characterized in that the metal-clad board comprises metal foil, and at least one of the resin film as claimed in claim 7 or the prepreg as claimed in claim 8 . A printed circuit board, characterized in that the printed circuit board comprises the resin film as claimed in claim 7, the prepreg as claimed in claim 8 or the metal clad board as claimed in claim 9 at least one of the