TWI644983B - Thermosetting vinyl organic enamel resin composition and application thereof in high frequency circuit board - Google Patents

Abstract

The present invention relates to a thermosetting vinyl organic tantalum resin composition comprising: any one of a linear vinyl organic tantalum resin, a cyclic vinyl organic tantalum resin, and a three-dimensional random network structure MQ vinyl organic tantalum resin. Or a combination of at least two vinyl organic oxime resins; a vinyl modified polyphenylene ether resin; and a free radical initiator. The present invention also provides a high frequency circuit substrate prepared using the resin composition as described above and an application thereof. The high-frequency circuit substrate of the invention has low dielectric constant, low dielectric loss, low water absorption, and the interlayer adhesion can meet the requirements of the adhesion between the layers of the copper-clad layer, and can realize the halogen-free and phosphorus-free V-0 flame retardant.

Description

Thermosetting vinyl organic enamel resin composition and application thereof in high frequency circuit board

The present invention relates to a composition of a vinyl organic oxime resin, and more particularly to a thermosetting vinyl phthalocyanine resin composition and its use in a high frequency circuit substrate.

In recent years, with the rapid development of wireless communication technology and electronic products, electronic circuits have entered the stage of high-speed information processing and high-frequency signal transmission. However, when the frequency is greater than 300MHz or even above GHz, the electrical performance of the substrate will be seriously affected. The characteristics of electronic circuits thus place higher demands on substrate performance.

For dielectric constant on performance, high-frequency circuits, signal transmission rate and the relationship between the insulating material is a dielectric constant D _k: the lower the dielectric constant D _k dielectric material, the faster the rate of signal transmission. Therefore, in order to speed up the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the frequency of the signal increases, the loss of the signal in the substrate can no longer be ignored. The relationship between the signal loss and the frequency, the dielectric constant D _k , and the dielectric loss D _{f is} such that the smaller the substrate dielectric constant D _{k is, the} smaller the dielectric loss D _{f is, and the} smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D _k and a low dielectric loss D _f has become a research and development direction common to CCL manufacturers.

At present, the olefin resin used in the high-frequency electronic circuit substrate is mainly a polybutadiene resin, a styrene-butadiene copolymer or the like. Using the resin system, the prepared substrate has a dielectric constant and The mass loss is low, but such a resin has a low thermal decomposition temperature in a hot oxygen environment, is easily aging by thermal oxygen, and has a problem that the dielectric constant of the substrate and the dielectric loss increase as the degree of thermal oxygen aging increases.

The vinyl organic oxime resin does not contain a polar group, and imparts excellent low dielectric constant, low dielectric loss, and low water absorption performance to the resin. The main chain of vinyl organic bismuth resin is Si-O-Si as the main chain, and the thermal decomposition temperature is high, which gives the resin excellent thermal and aging resistance, thus ensuring the long-term medium of the substrate prepared by using the resin. Constant and dielectric loss stability.

CN105086417A discloses a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin and a vinyl MQ resin as a crosslinking agent. The vinyl MQ resin is 10-100 parts by weight based on 100 parts by weight of the vinyl modified polyphenylene ether resin, and the prepared substrate has low dielectric constant, low dielectric loss, high glass transition temperature, and high heat resistance. , comprehensive performance such as low water absorption.

CN102993683A discloses a resin composition comprising a vinyl-modified polyphenylene ether resin as a host resin, a linear vinyl resin or a cyclic vinyl resin as a crosslinking agent. The substrate has a low dielectric constant, a low dielectric loss, and a high glass transition, based on 100 parts by weight of the vinyl-modified polyphenylene ether resin, and a linear vinyl resin or a cyclic vinyl resin of 10 to 90 parts by weight. Comprehensive properties such as temperature, high heat resistance and low water absorption.

The dielectric constant and dielectric loss performance of the vinyl modified polyphenylene ether resin are inferior to those of the vinyl organic resin. The above two patents all use vinyl modified polyphenylene ether resin as the main resin, and vinyl organic oxime resin as the crosslinking agent. The dielectric loss of the prepared substrate is still not low enough to meet the market demand for high frequency substrate dielectric loss. Low demand.

If a vinyl organic oxime resin is used as the entire resin, the prepared substrate is It has lower dielectric constant and dielectric loss, but the adhesion between the substrate layers is poor, which cannot meet the requirements of the adhesion between the copper-clad laminates.

In view of the problems of the prior art, it is an object of the present invention to provide a thermosetting vinyl organic tantalum resin composition. The substrate prepared by using the resin composition has a low dielectric constant, a low dielectric loss, a low water absorption rate, and the interlayer adhesion force can satisfy the requirement of the adhesion between the layers of the copper clad laminate.

To this end, the present invention employs the following technical means: The present invention provides a thermosetting vinyl organic tantalum resin composition comprising: (1) a vinyl organic tantalum resin; the vinyl organic tantalum resin is a linear vinyl organic germanium Any one or a mixture of at least two of a resin, a cyclic vinyl organic oxime resin, a three-dimensional random network structure MQ vinyl organic oxime resin; (2) a vinyl-modified polyphenylene ether resin; (3) a radical-induced The weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight based on 100 parts by weight of the vinyl organic oxime resin.

The invention adopts the vinyl organic bismuth resin as the main resin in the field of copper clad laminates, and since the structure does not contain polar groups, the prepared substrate has low dielectric constant, low dielectric loss and low water absorption performance; Because of the vinyl organic bismuth resin backbone Si-O-Si is the main chain and has a high thermal decomposition temperature, which gives the resin excellent thermal and aging resistance, thereby ensuring long-term dielectric constant and dielectric loss stability of the substrate prepared by using the resin.

In the invention, a vinyl organic bismuth resin is used as a main resin, and a vinyl modified polyphenylene ether resin is used as a substrate interlaminar adhesion modifier. Compared with a pure vinyl organic oxime resin system, the prepared substrate has a large interlaminar adhesion. The increase in amplitude can meet the requirements of the adhesion between the copper-clad laminates on the substrate; at the same time, the inventors have unexpectedly found that the substrates prepared are consistent with the pure vinyl organic germanium system in terms of dielectric constant and dielectric loss performance, that is, The invention adopts vinyl modified polyphenylene ether as the interlaminar adhesion modifier, without impairing the dielectric constant and dielectric loss performance of the substrate, and the technology achieves the unpredictable effect in the field which is generally not known.

In addition, the present invention can realize halogen-free and phosphorus-free V-- using a vinyl-organophthalene resin as a host resin and a vinyl-modified polyphenylene ether resin as a substrate interlayer adhesion modifier without using a flame retardant. Grade 0 flame retardant.

In the present invention, the weight of the vinyl-modified polyphenylene ether resin is 10 to 30 parts by weight, for example, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, based on 100 parts by weight of the vinyl organic oxime resin. 22, 25, 28 or 30 parts, etc.

Desirably, the structure of the aforementioned linear vinyl organic tantalum resin is:

Wherein at least one of R ₁ , R ₂ and R ₃ is a substituted or unsubstituted C 2 -C 10 (for example C2, C3, C4, C5, C6, C7, C8, C9 or C10, etc.) containing C=C a group; the other two are independently selected from substituted or unsubstituted C1~C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1~ C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C2~C10 (eg C2, C3, C4, C5) , C6, C7, C8, C9 or C10, etc.) any of the groups containing C=C, and 5 m 100 (for example, m is 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.).

A typical, but non-limiting example of the foregoing linear vinyl organoanthraquinone resin is the trade name DMS-V05 from Gelestd, wherein R ₁ , R ₂ , and R ₃ are each a methyl group, a vinyl group, and a methyl group. For the DMS-V05 resin, the molecular weight contained therein is a distribution, and the molecular weight is large or small. In a strict sense, the m values corresponding to the different molecular weights are different, and are a range rather than a value. In the laboratory, the molecular weight of the polymer is generally determined by a gel chromatography GPC, and the number average molecular weight Mn, or the weight average molecular weight Mw, or the viscosity average molecular weight Mp is a relative value. Therefore, for the DMS-V05 resin, the m value corresponding to the molecular weight of the resin cannot be given. The detection was carried out by a GPC apparatus using toluene as a mobile phase, and the molecular weight of the resin was Mn = 800. The same applies to the three-dimensional random network structure MQ vinyl organic resin.

Desirably, the structure of the aforementioned cyclic vinyl organic tantalum resin is:

Wherein R _{4 is} selected from a substituted or unsubstituted C1 to C12 (eg, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) linear alkyl group or substituted or unsubstituted C1 to C12 (for example, C1, C2, C3, C4, C5, C6, C7, C8, C10 or C12, etc.) branched alkyl; 2 n 10, n is a natural number (for example, n is 2, 3, 4, 5, 6, 7, 8, 9, or 10, etc.).

A typical, but non-limiting example of the foregoing cyclic vinyl organic oxime resin is the trade name WD-V4 of Wuda organic ruthenium, wherein R ₄ is methyl and n=2.

Desirably, the structure of the aforementioned three-dimensional random network structure MQ vinyl organic tantalum resin is: (R ₅ R ₆ R ₇ SiO _1/2 ) _x (SiO _4/2 ) _y

Among them, 3 x 100 (for example, x is 3, 5, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 6 y 100 (for example, x is 6, 10, 20, 25, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 9 x+y 200 (for example, 9 x+y 14,15 x+y 30, 40 x+y 52, 55 x+y 68, 70 x+y 82, 89 x+y 105, 121 x+y 153,157 x+y 175, 182 x+y 193, 195 x+y 200, etc.), and 0.1 x/y 4 (for example, x/y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 1.8, 2.0, 2.3, 2.5, 2.8, 3.0, 3.3, 3.5, 3.8 or 4.0 And the like; at least one of R ₅ , R ₆ , and R ₇ is a group containing an unsaturated double bond, and the other two are independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1~C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or Any one of an unsubstituted phenyl group, a substituted or unsubstituted C=C-containing group.

A typical but non-limiting example of the aforementioned three-dimensional random network structure MQ vinyl organic tantalum resin is the trade name of DY-VMQ102 of Shandong Dayi Chemical Co., Ltd., and R ₅ , R ₆ and R ₇ are respectively methyl and methyl groups. , vinyl. The detection was carried out by a GPC apparatus using toluene as a mobile phase, and the molecular weight of the resin was Mn = 2632.

The aforementioned three-dimensional network structure has a plurality of nodes, and a structure in which a plurality of holes are formed, for example, the following structure (this structure is only exemplified, not exhaustive):

Desirably, the aforementioned vinyl modified polyphenylene ether resin has the following structure:

Among them, 1 e 100 (for example, e is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.), 1 f 100 (for example, f is 1, 3, 5, 7, 9, 15, 22, 32, 38, 48, 50, 61, 72, 81, 90, 92 or 100, etc.), 2 e+f 100 (for example 2 e+f 10, 10 e+f 20, 15 e+f 30, 25 e+f 40, 30 e+f 55,60 e+f 85, 65 e+f 75, 80 e+f 98 or 85 e+f 100, etc.); in addition M is selected from: or,

Wherein N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO ₂ -, -C(CH ₃ ) ₂ - or a combination of at least two; R ₈ , R ₁₀ , R ₁₂ , R ₁₄ , R ₁₇ , R ₁₉ , R ₂₁ and R ₂₃ are each independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) Any one or at least one of a linear alkyl group, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, substituted or unsubstituted phenyl group; a combination of two; R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are each independently selected from a hydrogen atom, a substituted or unsubstituted C1 to C8 (eg, C1, C2). a C3, C4, C5, C6, C7 or C8, etc.) linear alkyl group, a substituted or unsubstituted C1 to C8 (e.g., C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, Any one or a combination of at least two of substituted or unsubstituted phenyl groups; R _{16 is} selected from: or, Wherein B is a subaromatic group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10); R ₂₅ And R ₂₆ and R ₂₇ are each independently selected from a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10). .

Desirably, the vinyl-modified polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol, for example, 500 g/mol, 800 g/mol, 1000 g/mol, 1100 g/mol, 1500 g/mol, 4000 g/mol, 5600 g/ Mol, 8000 g/mol or 10000 g/mol, etc., preferably 800 to 8000 g/mol, further preferably 1000 to 4000 g/mol.

Desirably, the aforementioned free radical initiator is a peroxide free radical initiator.

Further desirably, the aforementioned radical initiator is selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate or n-butyl 4,4-di(tert-butylperoxy)pentanoate Any one or a mixture of at least two, wherein a typical but non-limiting mixture is: a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and t-butyl peroxybenzoate, a mixture of benzamidine oxide and dicumyl peroxide, a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and benzammonium peroxide, tert-butyl peroxybenzoate and A mixture of dicumyl peroxide, a mixture of n-butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxybenzoate, and benzammonium peroxide.

In the resin composition of the present invention, the radical initiators may be used singly or in combination, and a mixed effect may be used to achieve a better synergistic effect.

Desirably, the weight of the radical initiator is from 1 to 3 parts by weight of the vinyl organic oxime resin and the vinyl modified polyphenylene ether resin, for example, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts or 3 parts, and the like.

Desirably, the resin composition of the present invention may further comprise a powder filler.

Desirably, the aforementioned powder filler is selected from the group consisting of crystalline cerium oxide, amorphous cerium oxide, spherical cerium oxide, molten cerium oxide, titanium dioxide, cerium carbide, glass fiber, oxygen. Any one or a mixture of at least two of aluminum, aluminum nitride, boron nitride, barium titanate or barium titanate, wherein a typical but non-limiting mixture is: crystalline cerium oxide and amorphous cerium oxide Mixture, a mixture of spherical cerium oxide and titanium dioxide, a mixture of cerium carbide and glass fiber, a mixture of aluminum oxide and aluminum nitride, a mixture of boron nitride and barium titanate, a mixture of barium titanate and strontium carbide, spherical a mixture of cerium oxide, crystalline cerium oxide and amorphous cerium oxide.

In the resin composition of the present invention, the powder filler functions to improve dimensional stability, lower thermal expansion coefficient, lower system cost, and the like. The shape and particle diameter of the powder filler are not particularly limited, and the particle diameter generally used is 0.2 to 10 μm, for example, 0.2 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 5 μm, 8 μm, 9 μm or 10 μm, etc., for example, A spherical cerium oxide having a particle diameter of 0.2 to 10 μm can be selected.

Desirably, the weight of the powdered filler is 100 to 300 parts, for example, 100 parts, 110 parts, 120 parts, 130 parts by weight of 100 parts by weight of the vinyl organic oxime resin and the vinyl modified polyphenylene ether resin. , 140 parts, 150 parts, 160 parts, 180 parts, 180 parts, 190 parts, 200 parts, 210, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280, 290 or 300 parts, and the like.

The term "comprising" as used in the present invention means that it may contain, in addition to the foregoing components, other components which impart different characteristics to the aforementioned resin composition. In addition, the "include" described in the present invention may be replaced by a closed "yes" or "consisting of".

For example, the thermosetting vinyl phthalocyanine resin composition of the present invention may be added with a thermosetting resin, and specific examples thereof include an epoxy resin, a cyanate resin, a phenol resin, a polyurethane resin, a melamine resin, and the like. Add these curing agents for thermosetting resins or Curing accelerator.

Further, the resin composition may further contain various additives, and specific examples thereof include a decane coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, and a coloring. Agents, lubricants, etc. These additives may be used singly or in combination of two or more.

As a preparation method of one of the resin compositions of the present invention, the aforementioned vinyl organic oxime resin, vinyl-modified polyphenylene ether resin, radical initiator, powder filler, and various various kinds can be blended, stirred, and mixed by a conventional method. It is prepared by using a thermosetting resin and various additives.

Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the resin composition as described above in a solvent.

The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl. Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used singly or in combination of two or more. It is preferably an aromatic hydrocarbon solvent such as toluene, xylene or mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone or methyl A ketone flux such as butyl ketone or cyclohexanone is used in combination. The amount of the aforementioned solvent used can be selected according to one's own experience in the field, so that the obtained resin glue can reach a viscosity suitable for use.

In the process of dissolving or dispersing the resin composition as described above in the solvent, To add an emulsifier. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.

A third object of the present invention is to provide a prepreg obtained by dipping a glass fiber cloth in a resin glue as described above and drying it.

In the present invention, the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material. Depending on the thickness of the sheet, etc., different types of fiberglass cloth can be used. Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.

The weight of the glass fiber cloth is 40 to 150 parts, for example, 40 parts, 50 parts, 60 parts, 70, based on 100 parts by weight of the sum of the weights of the vinyl organic oxime resin, the vinyl modified polyphenylene ether resin, and the powder filler. Parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, and the like.

The drying temperature is 80-220 ° C, such as 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C, etc.; the aforementioned drying time is 1 ~ 30 min, such as 1 min, 5 min, 8 min, 13min, 17min, 21min, 24min, 28min or 30min.

A fourth object of the present invention is to provide a high-frequency circuit substrate which is made of the prepreg as described above, and in particular, the above-mentioned high-frequency circuit substrate is obtained by overlapping at least one of the above The prepreg is prepared by placing a copper foil on the upper and lower sides of the overlapping prepreg and performing lamination molding.

The aforementioned overlap is ideal for automatic stacking operations, which makes the process operation easier.

The aforementioned lamination molding is desirably a vacuum lamination molding, and the vacuum lamination molding can be realized by a vacuum laminator. The lamination time is 70-120 min, such as 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min, etc.; the lamination temperature is 180-220 ° C, for example 180 ° C, 185 °C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C; the pressure of the aforementioned lamination is 40 ~ 60 kg / cm ² , for example 40 kg / cm ² , 45 kg / cm ² , 50 kg / cm ^{2, 55kg / cm 2, 58kg} / cm 2 or 60kg / cm ² and the like.

A typical but non-limiting method for preparing a high-frequency circuit substrate of the present invention is as follows: (1) According to the above-mentioned resin composition formulation, each component is weighed: the weight of the vinyl organic oxime resin is 100 parts, and the vinyl is changed. The weight of the polyphenylene ether resin is 10 to 30 parts; and the weight of the vinyl organic oxime resin and the vinyl modified polyphenylene ether resin is 100 parts by weight, and the weight of the radical initiator is 1 to 3 parts; The weight of the vinyl filler resin and the vinyl modified polyphenylene ether resin is 100 parts by weight, and the weight of the powder filler is 100 to 300 parts; (2) the vinyl organic resin and vinyl modification are used. Polyphenylene ether resin, free radical initiator and powder filler are mixed, and an appropriate amount of solvent is added, and the mixture is uniformly dispersed, so that the powder filler and the flame retardant are uniformly dispersed in the resin glue; the glass fiber cloth is infiltrated with the prepared glue liquid, Drying, removing the solvent to obtain a prepreg; (3) overlapping at least one prepreg, placing copper foil on both sides of the prepreg, and laminating and solidifying in a vacuum laminator to obtain a high-frequency circuit substrate.

A fifth object of the present invention is to provide an application of the above-described resin composition for preparing a resin glue, a prepreg, and a high-frequency circuit substrate.

The resin composition of the present invention can be prepared to have a low medium The high-frequency circuit substrate with constant, low dielectric loss, low water absorption, and the interlayer adhesion between the substrates can meet the requirements of the adhesion between the layers of the copper-clad laminate.

The aforementioned "high frequency" in the present invention means that the frequency is greater than 100 MHz.

Compared with the prior art, the present invention has the following effects: (1) The present invention ensures that the prepared substrate has a chemical structure because it does not contain a polar group by applying a vinyl organic oxime resin to the field of copper clad laminates. Low dielectric constant and low dielectric loss performance; (2) The present invention uses a vinyl organic oxime resin as a host resin, and a vinyl-modified polyphenylene ether as a substrate interlayer adhesion modifier relative to a pure vinyl organic ruthenium The system has a greatly improved adhesion between the substrates, and can meet the requirements of the adhesion between the copper-clad laminates, and the dielectric constant and dielectric loss performance of the prepared substrates are consistent with the pure vinyl organic ruthenium system. The modified polyphenylene ether as the interlaminar adhesion modifier does not impair the dielectric constant and dielectric loss performance of the substrate; (3) The present invention uses a vinyl organic oxime resin as a host resin and a vinyl modified polyphenylene ether as a substrate. The interlayer adhesion modifier can realize halogen-free and phosphorus-free V-0 flame retardant without using a flame retardant; the invention adopts vinyl organic germanium resin as The resin and vinyl modified polyphenylene ether are used as the interlaminar adhesion modifier. The prepared substrate has low dielectric constant and low dielectric loss, and good adhesion between the substrates can meet the needs of the copper clad laminate. It realizes halogen-free and phosphorus-free V-0 flame retardant, and is very suitable for the circuit board for preparing high-frequency electronic equipment.

To facilitate an understanding of the invention, the invention is set forth below. It is to be understood by those skilled in the art that the foregoing embodiments are merely to be construed as an understanding of the present invention and are not to be construed as limiting the invention. In the following embodiments and comparative examples, four sheets of 2116 may be replaced by one sheet of 2116. 6 sheets of 2116, 2 sheets of 1080, etc.

Table 1 below shows the materials used in the respective examples and comparative examples.

Example 1

80.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 20.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Example 2

80.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 20.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Example 3

80.0 parts by weight of the cyclic vinyl organic fluorene resin WD-V4, 20.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 1

100 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity . The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 2

100 parts by weight of a linear vinyl organic oxime resin DMS-V05, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of cerium fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 3

100 parts by weight of the cyclic vinyl organic hydrazine resin WD-V4, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of cerium fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative example 4

20.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 80.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative Example 5

20.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 80.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

Comparative Example 6

20.0 parts by weight of the cyclic vinyl organic fluorene resin WD-V4, 80.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 2.

As can be seen from Table 2, in Examples 1 to 3, compared with Comparative Examples 1 to 3, the adhesion between the substrates prepared in Examples 1 to 3 was 0.4 to 0.6, and the substrates prepared in Comparative Examples 1 to 3 were used. The bonding force between the layers is only 0.1~0.2, which indicates that the invention adopts vinyl organic oxime resin as the main resin and vinyl modified polyphenylene ether as the interlaminar adhesion modifier, compared with the pure vinyl organic ruthenium system. The prepared interlaminar adhesion between the substrates was greatly improved; in addition, the dielectric constants and dielectric loss properties of the substrates prepared in Examples 1 to 3 were basically the same as those in Comparative Examples 1 to 3, indicating that the present invention uses vinyl modified polyphenylene ether. As the interlayer adhesion modifier, the dielectric constant and dielectric loss performance of the substrate were not impaired. Comparing Examples 1 to 3 with Comparative Examples 4 to 6, respectively, the substrates prepared in Examples 1 to 3 were able to achieve halogen-free and phosphorus-free V-0 flame retardant without using a flame retardant. In Comparative Examples 4 to 6, the V-0 grade flame retardant could not be achieved; in addition, the substrates prepared in Examples 1 to 3 had lower dielectric constants and dielectric loss than Comparative Examples 4 to 6, indicating that the present invention is Vinyl organic fluorene resin is used as the main resin, vinyl modified polyphenylene ether is used as the interlaminar adhesion modifier, and vinyl organic fluorene resin is used as the main resin and vinyl organic hydrazine resin as the crosslinking. The substrate prepared by the invention has better dielectric constant and dielectric loss performance, and can realize halogen-free and phosphorus-free V-0 flame retardant.

Example 4

90.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 10.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to impregnate the resin glue, and the clamp shaft was controlled to be suitable for single weight, and dried in an oven to remove the toluene solvent, 2116 prepreg. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Example 5

90.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 10.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Example 6

90.0 parts by weight of the cyclic vinyl organic fluorene resin WD-V4, 10.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Comparative Example 7

10.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Comparative Example 8

10.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

Comparative Example 9

10.0 parts by weight of a cyclic vinyl organic fluorene resin WD-V4, 90.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, and 233.0 parts by weight of a cerium fine powder 525 were dissolved in In toluene solvent, and adjusted to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 3.

As can be seen from Table 3, the substrates prepared in Examples 4 to 6 were able to achieve halogen-free and phosphorus-free V without using a flame retardant, as compared with Comparative Examples 7 to 9, respectively. -0 grade flame retardant, while Comparative Examples 7-9 can not achieve V-0 flame retardant; in addition, relative to the ratio Compared with Examples 7-9, the substrates prepared in Examples 4-6 have lower dielectric constant and dielectric loss, indicating that the present invention uses vinyl-based phthalocyanine resin as the host resin and vinyl-modified polyphenylene ether as the substrate layer. The adhesive modifier has a superior dielectric constant and dielectric loss performance compared with a vinyl-modified polyphenylene ether resin as a host resin and a vinyl organic oxime resin as a crosslinking agent. It can realize halogen-free and phosphorus-free V-0 flame retardant.

Example 7

85.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 15.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

Example 8

85.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 15.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

Example 9

85.0 parts by weight of the cyclic vinyl organic fluorene resin WD-V4, 15.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 233.0 parts by weight of the cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

Comparative Example 10

15.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 85.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of ruthenium The fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

Comparative Example 11

15.0 parts by weight of a linear vinyl organic oxime resin DMS-V05, 85.0 parts by weight of a vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight of cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

Comparative Example 12

15.0 parts by weight of the cyclic vinyl organic fluorene resin WD-V4, 85.0 parts by weight of the vinyl modified polyphenylene ether resin SA9000, 3.0 parts by weight of the radical initiator DCP, 2330 parts by weight of the cerium fine powder 525, dissolved in toluene In the solvent, and adjust to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 4.

As can be seen from Table 4, Examples 7-9 are respectively compared with Comparative Examples 10-12. In comparison, the substrates prepared in Examples 7 to 9 can achieve halogen-free and phosphorus-free V-0 flame retardant without using a flame retardant, while the comparative examples 10-12 cannot achieve V-0 flame retardant. Further, with respect to Comparative Examples 10 to 12, the substrates prepared in Examples 7 to 9 had lower dielectric constants and dielectric loss, indicating that the present invention uses a vinyl organic oxime resin as a host resin, vinyl modified poly As a binder for interlaminar adhesion between substrates, phenyl ether has a more excellent dielectric constant than a vinyl-modified polyphenylene ether resin as a host resin and a vinyl organic oxime resin as a crosslinking agent. Dielectric loss performance, and can achieve halogen-free and phosphorus-free V-0 flame retardant.

Example 10

90.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 10.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The fine powder 525 is dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 11

80.0 parts by weight of linear vinyl organic oxime resin DMS-V05, 20.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of free radical initiator DCP, 185.0 parts by weight of bismuth micropowder 525, dissolved In toluene solvent, and adjusted to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 12

70.0 parts by weight of a cyclic vinyl organic fluorene resin WD-V4, 30.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, 155.0 parts by weight of bismuth fine powder 525, Dissolve in toluene solvent and adjust to suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 13

85.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 15.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The fine powder 525 is dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 14

85.0 parts by weight of linear vinyl organic oxime resin DMS-V05, 15.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of free radical initiator DCP, 185.0 parts by weight of bismuth micropowder 525, dissolved In toluene solvent, and adjusted to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 15

85.0 parts by weight of a cyclic vinyl organic fluorene resin WD-V4, 15.0 parts by weight of a vinyl-modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of bismuth fine powder 525, Dissolve in toluene solvent and adjust to suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 16

80.0 parts by weight of a three-dimensional random network structure MQ vinyl organic resin DY-VMQ102, 20.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 3.0 parts by weight of a radical initiator DCP, 233.0 parts by weight The bismuth micropowder SC-2300SVJ is dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 17

80.0 parts by weight of linear vinyl organic oxime resin DMS-V05, 20.0 parts by weight of vinyl modified polyphenylene ether resin OPE-2ST, 2.0 parts by weight of free radical initiator DCP, 185.0 parts by weight of bismuth micropowder SC-2300SVJ , dissolved in toluene solvent and adjusted to the appropriate viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

Example 18

80.0 parts by weight of a cyclic vinyl organic fluorene resin WD-V4, 20.0 parts by weight of a vinyl modified polyphenylene ether resin OPE-2ST, 1.0 part by weight of a radical initiator DCP, and 155.0 parts by weight of a bismuth micropowder SC- 2300SVJ, dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent. Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 90 minutes in a press, the curing pressure was 50 kg/cm ² , and the curing temperature was 200 ° C to obtain a high-frequency circuit substrate. The overall performance of the substrate is shown in Table 5.

It can be seen from Table 5 that the present invention adopts a vinyl organic fluorene resin as a host resin and a vinyl modified polyphenylene ether as a substrate interlayer adhesion modifier, and the prepared substrate has a good adhesion between the substrates. It can meet the requirements of adhesion between layers of CCL, has low dielectric constant and low dielectric loss, and can realize halogen-free and phosphorus-free V-0 flame retardant. It is very suitable for the circuit board of high-frequency electronic equipment.

The Applicant declares that the present invention is described by the above-described embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must be implemented by the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, the equal replacement of the raw materials of the products of the present invention, the addition of auxiliary components, the selection of specific means, etc., are all within the scope of the present invention and the scope of the disclosure.

Claims (15)

A thermosetting vinyl organic oxime resin composition, comprising: (1) a vinyl organic oxime resin; the vinyl phthalocyanine resin is a linear vinyl organic oxime resin, a cyclic vinyl organic ruthenium resin, a three-dimensional random network Any one or a mixture of at least two of the MQ vinyl organic oxime resin; (2) a vinyl modified polyphenylene ether resin; (3) a radical initiator; and a weight of the vinyl organic oxime resin of 100 parts The weight of the vinyl modified polyphenylene ether resin is 10 to 30 parts; the structure of the linear vinyl organic oxime resin is: Wherein at least one of R ₁ , R ₂ and R ₃ is a substituted or unsubstituted C 2 -C 10 group containing C=C; the other two are independently selected from substituted or unsubstituted C1 to C8 linear chains. An alkyl group, a substituted or unsubstituted C1 to C8 branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C2 to C10 group containing a C=C group, and 5 m 100, m is a natural number; the structure of the aforementioned cyclic vinyl organic bismuth resin is: Wherein R _{4 is} selected from a substituted or unsubstituted C 1 -C 12 linear alkyl group or a substituted or unsubstituted C 1 -C 12 branched alkyl group; n 10, n is a natural number; the structure of the aforementioned three-dimensional random network structure MQ vinyl organic bismuth resin is: (R ₅ R ₆ R ₇ SiO _1/2 ) _x (SiO _4/2 ) _y wherein 3 x 100,6 y 100,9 x+y 200, and 0.1 x/y 4; at least one of R ₅ , R ₆ , and R ₇ is a group containing an unsaturated double bond, and the other two are independently selected from a substituted or unsubstituted C 1 -C 8 linear alkyl group, substituted or unsubstituted Any one of a C1 to C8 branched alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C=C-containing group; the aforementioned vinyl modified polyphenylene ether resin has the following structure: Among them, 1 e 100,1 f 100, 2 e+f 100; in addition M is selected from: Wherein N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO ₂ -, -C(CH ₃ ) ₂ - or a combination of at least two; R ₈ , R ₁₀ , R ₁₂ , R ₁₄ , R ₁₇ , R ₁₉ , R ₂₁ and R ₂₃ are each independently selected from substituted or unsubstituted C 1 -C 8 linear alkyl, substituted or unsubstituted C 1 -C 8 branched alkyl, substituted Or a combination of any one or at least two of the unsubstituted phenyl groups; R ₉ , R ₁₁ , R ₁₃ , R ₁₅ , R ₁₈ , R ₂₀ , R ₂₂ and R ₂₄ are each independently selected from a hydrogen atom, a substitution or Any one or a combination of at least two of an unsubstituted C1 to C8 linear alkyl group, a substituted or unsubstituted C1 to C8 branched alkyl group, a substituted or unsubstituted phenyl group; and R _{16 is} selected from the group consisting of: Wherein B is any one of a subaromatic group, a carbonyl group or an alkylene group having 1 to 10 carbon atoms; and R ₂₅ , R ₂₆ and R ₂₇ are each independently selected from a hydrogen atom or a carbon number of 1 to 10; Any of the alkyl groups. The resin composition according to claim 1, wherein the vinyl-modified polyphenylene ether resin has a number average molecular weight of 500 to 10,000 g/mol. The resin composition according to claim 1, wherein the radical initiator is a peroxide radical initiator. The resin composition according to claim 1, wherein the radical initiator is selected from the group consisting of dicumyl peroxide, dibenzoyl peroxide, benzammonium peroxide, and t-butyl peroxybenzoate. Or a mixture of any one or a mixture of at least two of 4,4-di(tert-butylperoxy)-n-butyl valerate. The resin composition according to claim 1, wherein the weight of the radical initiator is 1 part by weight based on 100 parts by weight of the vinyl organic oxime resin and the vinyl modified polyphenylene ether resin. 3 copies. The resin composition according to the first aspect of the invention, wherein the resin composition further comprises a powder filler. The resin composition according to claim 6, wherein the powder filler is selected from the group consisting of crystalline cerium oxide, amorphous cerium oxide, spherical cerium oxide, molten cerium oxide, titanium oxide, cerium carbide, and glass fiber. Any one or a mixture of at least two of alumina, aluminum nitride, boron nitride, barium titanate or barium titanate. The resin composition according to claim 6, wherein the powder filler has a particle diameter of 0.2 to 10 μm. The resin composition according to claim 6, wherein the weight of the powder filler is 100 to 300 parts by weight of 100 parts by weight of the vinyl organic oxime resin and the vinyl modified polyphenylene ether resin. . A resin glue obtained by dissolving or dispersing a resin composition as described in any one of claims 1 to 9 in a solvent. A prepreg characterized in that a glass fiber cloth is impregnated with a resin glue as described in claim 10 of the patent application, and dried. The prepreg according to claim 11, wherein the weight of the glass fiber cloth is 100 parts by weight based on 100 parts by weight of the weight of the vinyl organic oxime resin, the vinyl modified polyphenylene ether resin and the powder filler. 40~150 copies. A high-frequency circuit substrate characterized in that the high-frequency circuit substrate is as claimed in the patent scope Made of prepreg as described in item 11 or 12. The high-frequency circuit board according to claim 13, wherein the high-frequency circuit board is obtained by laminating at least one of the prepregs described above, and placing copper foil on both sides of the prepreg. , obtained by lamination molding. The use of the resin composition according to any one of claims 1 to 9 for the preparation of a resin glue, a prepreg, and a high-frequency circuit substrate.