TWI658929B - Prepregs, laminates and printed circuit boards - Google Patents

Abstract

The present invention provides a prepreg and a laminate and a printed circuit board including the same. The prepreg includes a reinforcing material and a thermosetting resin composition adhered thereto after being dried by dipping. The reinforcing material is coated with a VIB compound. The Group VIB compound may be selected from a molybdenum compound, a tungsten compound, or a mixture thereof. By covering the VIB compound in the reinforcing material, it can effectively solve the problem of dispersion and settlement of the VIB compound, so that it can be evenly distributed in the prepreg, and at the same time greatly increase the contact area between the drill and the VIB compound , Effectively reduce the wear of the drill and significantly improve the quality of drilling.

Description

Prepregs, laminates and printed circuit boards

The invention relates to a prepreg. Specifically, the present invention relates to a prepreg and a laminate and a printed circuit board including the same.

With the rapid development of electronic products toward miniaturization, multifunction, high performance, and high reliability, printed circuit boards have begun to move rapidly in the direction of high precision, high density, high performance, microporosity, thinning, and multilayering. Development, its application scope is becoming more and more extensive, and it has rapidly entered civilian electrical appliances and related products from large-scale industrial computers, communication instruments, electrical measurement, national defense and aviation, aerospace and other departments. The base material largely determines the performance of the printed circuit board, so it is urgent to develop a new generation of base material. As a new generation of base material in the future, it must have high heat resistance, low thermal expansion coefficient, and excellent chemical stability and mechanical properties.

In order to reduce the thermal expansion coefficient of the laminate, a resin with a low thermal expansion coefficient or an increased content of an inorganic filler is usually selected. However, the resin with a low thermal expansion coefficient has a special structure and higher cost; and the method of increasing the content of the inorganic filler can not only effectively reduce the thermal expansion coefficient of the composite, but also greatly reduce the cost. However, highly filled resins significantly reduce the drillability and interlayer adhesion of laminates. Therefore, some people use block fillers such as talc as a lubricant in the thermosetting resin composition to improve the processability, but the effect is not obvious, and the addition of these block fillers further deteriorates the interlayer adhesion. In addition, in order to improve the drilling processability, a metal molybdenum compound is added, as mentioned in CN102656234A. Metal molybdenum such as zinc molybdate is added to the thermosetting resin composition. Compounds improve processability, and the patent recommends the use of molybdenum compound particles supported by talc, which has the problem that the interlayer adhesion of the laminate is significantly reduced, and the dispersibility of the molybdenum compound in the resin is poor, and the density It is also large and easy to settle, and satisfactory results cannot be obtained. CN103554844A mentions that the inclusion of a tungsten compound in a thermosetting resin composition can reduce the thermal expansion coefficient of a laminate, and can effectively block UV light and reduce light transmittance. However, the tungsten compound in the thermosetting resin composition has problems of dispersion and sedimentation, insufficient distribution uniformity on the reinforcing material, and insufficient thickness uniformity of the obtained reinforcing material, and further needs to reduce the drill bit of the laminate prepared thereby. Wear rate.

One of the objectives of the present invention is to provide a prepreg and a laminate and a printed circuit board including the prepreg, which effectively solve the problem of dispersion and sedimentation of the VIB group compound, and the uniformity of distribution on the reinforcing material and obtain The problem is that the thickness uniformity of the reinforcing material is insufficient, and the drill wear rate of the laminate prepared thereby is further reduced.

In one aspect, the present invention provides a prepreg comprising a reinforcing material and a thermosetting resin composition attached thereto after drying by dipping, wherein the reinforcing material is coated with a group VIB compound.

Optionally, the VIB compound is selected from a molybdenum compound, a tungsten compound, or a mixture thereof.

Preferably, the VIB compound is liquid or solid.

Optionally, the molybdenum compound is selected from the group consisting of molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithio molybdenum phosphate, molybdenum dialkyl dithioaminoformate, molybdenum amine complex, and naphthene Any one or a mixture of any two or more of molybdate acid, molybdenum alkyl salicylate, molybdenum thiocene, molybdenum dithiol, molybdenum alkylamine, organic molybdate, or molybdenum octoate.

Optionally, the molybdenum compound is selected from the group consisting of molybdic acid, molybdate, molybdenum oxide, heteropoly acid of molybdenum and its sodium salt, potassium salt, and ammonium salt, polyacid salt of molybdenum, molybdenum blue, and molybdenum sulfide Any one or a mixture of any two or more of selenium, molybdenum selenide, molybdenum telluride, molybdenum halide, molybdenum alloy, or molybdenum disilicide.

Optionally, the molybdenum compound is selected from: any one of ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate, molybdenum oxide, or molybdenum sulfide or a mixture of any two or more .

Optionally, the tungsten compound is selected from the group consisting of: tungsten disulfide, amine tetrathiotungstate, tungsten tetrabromide, tungsten tetrachloride, tungsten tetrabromide, zinc tungstate, calcium tungstate, magnesium tungstate, tungsten Ammonium acid, tungsten selenide, tungsten oxide, tungsten dioctyl dithiocarbamate, tungsten dithiophenol, 3,4-dimercaptotolyl tungsten, tungsten diisopropyl dithiophosphate, organic Any one or a mixture of at least two of tungsten-molybdenum complex, tungsten dithiocarbamate compound, aromatic tungsten compound, or tungsten alkyl (aryl) amino thiophosphate.

Optionally, the tungsten compound is selected from any one of tungsten disulfide, amine tetrathiotungstate, tungsten tetrabromide, tungsten tetrachloride, tungsten tetrabromide, or tungsten alk (aryl) amino thiophosphate. One or a mixture of at least two.

Optionally, the group VIB compound is selected from a mixture of a molybdenum compound and a tungsten compound, wherein in the mixture of the molybdenum compound and the tungsten compound, the mixing ratio of the molybdenum compound and the tungsten compound is from about 1: 100 to about 100: Within the range of 1.

Optionally, the VIB compound is in a solid state, and its average particle diameter is 0.01 to 1 μm.

Optionally, the content of the group VIB compound in the reinforcing material subjected to the coating treatment of the group VIB compound is 0.01 to 5% by weight.

The reinforcing material may be an inorganic or organic material. Examples of the inorganic reinforcing material may include woven fabric or non-woven fabric or paper of glass fiber, carbon fiber, boron fiber, metal, and the like. Examples of the glass fiber cloth or the non-woven cloth may include E-glass, Q-type cloth, NE cloth, D-type cloth, S-type cloth, high silica cloth, and the like. Examples of the reinforcing material may include woven or non-woven fabric or paper made of organic fibers such as polyester, polyamine, polyacrylic acid, polyimide, aramid, polytetrafluoroethylene, syndiotactic polystyrene, and the like. However, the reinforcing material is not limited to this, and other reinforcing materials that can be used for resin reinforcement can also be used in the present invention. Preferably, the reinforcing material is glass fiber cloth.

In another aspect, the invention provides a laminate, wherein the laminate contains at least one prepreg as described above.

In yet another aspect, the present invention provides a printed circuit board, wherein the printed circuit board contains at least one prepreg as described above.

According to the present invention, by covering the VIB group compound in the reinforcing material, the problem of dispersion and settlement of the VIB group compound can be effectively solved, so that it can be evenly distributed in the prepreg, and at the same time, the drill cutter and the VIB group are greatly increased. The contact area of the compound effectively reduces the wear of the drill and significantly improves the drilling quality.

In the following, the technical solutions in the examples of the present invention will be clearly and completely described in combination with the specific embodiments of the present invention. Obviously, the described embodiments and / or examples are only a part of the embodiments and / or examples of the present invention. Not all implementations and / or examples. Based on the embodiments and / or examples in the present invention, all other embodiments and / or all other examples obtained by a person of ordinary skill in the art without creative labor shall fall within the protection scope of the present invention.

In the present invention, all numerical characteristics are within the measurement error range, for example, within ± 10% of the limited value, or within ± 5%, or within ± 1%.

The “comprising”, “including” or “containing” in the present invention means that it may have other components besides the components, and these other components impart different characteristics to the prepreg. In addition, the terms "comprising", "including" or "containing" in the present invention may also include "consisting essentially of" and may be replaced by "is" or "consisting of".

In the present invention, the amounts, ratios, etc. are by weight unless specifically stated.

As described above, the present invention can provide a prepreg. The prepreg may include a reinforcing material and a thermosetting resin composition attached thereto after being dried by dipping. The reinforcement is treated with a VIB compound.

Examples of the reinforcing material may include glass fiber cloth. In the following description, glass fiber cloth reinforcement material and glass fiber cloth may be used interchangeably.

According to one embodiment of the present invention, the group VIB compound is selected from a molybdenum compound, a tungsten compound, or a mixture thereof. According to another embodiment of the present invention, the molybdenum compound may include an inorganic molybdenum compound and an organic molybdenum compound.

According to another embodiment of the present invention, the molybdenum compound is selected from the group consisting of: molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithioaminoformate, molybdenum amine Any one of the compound, molybdenum naphthenate, molybdenum alkyl salicylate, molybdenum thiocene, dimercaptothiazole, molybdenum alkylamine, molybdate, molybdenum octoate, or a mixture of any two or more.

In the present invention, the alkyl group may represent an alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. Alkyl may also include cycloalkyl, such as cycloalkyl containing 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Aromatics may represent benzene, toluene, xylene and naphthalene.

Examples of the molybdenum dialkyl dithiophosphate may include: molybdenum dimethyl dithiophosphate, molybdenum diethyl dithiophosphate, molybdenum dipropyl dithiophosphate, molybdenum dibutyl dithiophosphate, Molybdenum dithiophosphate, molybdenum dihexyl dithiophosphate, molybdenum diheptyl dithiophosphate, etc.

Examples of the nitrogen-containing dialkyl molybdenum dithiophosphate may include: nitrogen-containing dimethyl dithiophosphate, nitrogen-containing diethyl dithiophosphate, nitrogen-containing dipropyl dithiophosphate, nitrogen-containing Molybdenum dibutyl dithiophosphate, molybdenum containing dipentyl dithiophosphate, molybdenum containing dihexyl dithiophosphate, molybdenum containing diheptyl dithiophosphate and the like.

Examples of the molybdenum dialkyldithiocarbamate may include: molybdenum dimethyldithiocarbamate, molybdenum diethyldithiocarbamate, molybdenum dipropyldithiocarbamate, dibutyl Molybdenum dithiocarbamate, molybdenum dipentyl dithiocarbamate, molybdenum dihexyl dithiocarbamate, molybdenum diheptyl dithiocarbamate, and the like.

Examples of the molybdenum salicylate may include: molybdenum methyl salicylate, molybdenum ethyl salicylate, molybdenum salicylate, molybdenum butylsalicylate, molybdenum salicylate, hexylsalicylic acid Molybdenum, molybdenum salicylate, etc.

Examples of the alkylamine molybdenum may include: methylamine molybdenum, ethylamine molybdenum, propylamine molybdenum, butylamine molybdenum, pentylamine molybdenum, hexylamine molybdenum, heptylamine molybdenum, and the like.

Examples of the organic molybdate may include: organic methyl molybdate, organic ethyl molybdate, propyl organic molybdate, and the like.

According to another embodiment of the present invention, the molybdenum compound may be selected from the group consisting of molybdic acid, molybdate, molybdenum oxide, heteropolyacids and polyacids of molybdenum, molybdenum blue, molybdenum sulfide, molybdenum selenide, Any one of molybdenum telluride, molybdenum halide, molybdenum alloy, or molybdenum disilicide, or a mixture of any two or more.

Examples of the molybdate may include: ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate, and the like.

Examples of heteropoly acids of molybdenum may include: H ₃ [P (Mo ₃ O ₁₀ ) ₄ )]. nH ₂ O, H ₄₅ Si (Mo ₃ O ₁₀ ) ₄ . nH ₂ O and its sodium, potassium or ammonium salts.

Examples of molybdenum polyacids may include: dimolybdate (M ₂ O. ₂ MoO ₃ ), paramolybdate (3M ₂ O. 7 MoO), pentamolybdate (M ₂ O. 5MoO ₃ ), octamolybdenum Acid salts (3M ₂ O.8MoO ₃ .3H ₂ O) and tetramolybdate (M ₂ O.4MoO).

Examples of the molybdenum alloy may include: Mo-Au alloy, Mo-Ag alloy, Mo-Cu alloy, Mo-Al alloy, Mo-Ti alloy, and the like.

According to another embodiment of the present invention, the molybdenum compound may be selected from any one or any two of ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate, molybdenum oxide, or molybdenum sulfide Or a mixture of more.

According to another embodiment of the present invention, the tungsten compound is selected from the group consisting of: tungsten disulfide, amine tetrathiotungstate, tungsten bromide oxide, tungsten tetrachloride, tungsten tetrabromide, zinc tungstate, calcium tungstate, Magnesium Tungstate, Ammonium Tungstate, Tungsten Selenide, Tungsten Oxide, Tungsten Dioctyl Dithiocarbamate, Tungsten Dithiophenol, 3,4-Dimercaptotolyl Tungsten, Amino Diisopropyl Disulfide Any one or a mixture of at least two kinds of tungsten phosphorophosphate, tungsten dithioaminoformate, and alkyl (aryl) aminothiothiophosphate.

Examples of the alkyl (aryl) amino thiophosphate may include: methylamino thiophosphate, tolylamino thiophosphate, and the like.

According to another embodiment of the present invention, the tungsten compound may be selected from tungsten disulfide, amine tetrathiotungstate, tungsten tetrabromooxide, tungsten tetrachloride, tungsten tetrabromide, or methylamino tungsten thiophosphate. Any one or a mixture of at least two of them.

According to another embodiment of the present invention, a mixture of a molybdenum compound and a tungsten compound may be used. In a mixture of a molybdenum compound and a tungsten compound, a mixing ratio by weight may be in a range of about 1: 100 to about 100: 1, preferably in a range of about 1:50 to about 50: 1, and more preferably in a range of about 1:50 to about 50: 1. approximately In the range of 1:20 to about 20: 1, still more preferably in the range of about 1:10 to about 10: 1, even more preferably in the range of about 1: 5 to about 5: 1, and most preferably in the range of In the range of about 1: 2 to about 2: 1.

According to another embodiment of the present invention, the average particle diameter of the inorganic VIB compound is 0.01 to 1 μm, preferably 0.01 to 0.5 μm. The mass of the inorganic VIB compound is 0.01 to 5%, preferably 0.05 to 2%, of the mass of the reinforcing material subjected to the VIB group coating treatment. If the amount is greater than or equal to 0.01% of the mass of the reinforcing material coated with the VIB compound, the effect is more obvious. If it is less than or equal to 5% of the reinforcing material coated with the VIB compound, the original overall performance of the glass fiber cloth can be further improved. When the amount of the inorganic VIB compound used is 0.05 to 2% of the mass of the reinforcing material coated with the VIB group compound, the performance of the VIB group compound exhibits the best performance, and the dispersion of the inorganic VIB compound is uniform. Also best.

According to another embodiment of the present invention, the group VIB compound has an average particle diameter of about 0.01 μm to about 1 μm, preferably about 0.01 μm to about 0.5 μm. By setting the average particle diameter of the inorganic VIB compound within the above range, the fluidity and the uniformity of dispersion of the inorganic VIB compound can be further well maintained, and the mixing probability of coarse particles can be further reduced and the occurrence of coarse particle defects can be suppressed. Here, the average particle diameter refers to the particle diameter of a point corresponding to 50% of the volume when the cumulative degree distribution curve based on the particle diameter is obtained by taking the total volume of the particles as 100%, and a laser diffraction scattering method can be used. Determination of the fineness distribution.

According to another embodiment of the present invention, the content of the group VIB compound is about 0.01% to about 5%, preferably about 0.05% to about 5% of the total mass of the reinforcing material subjected to the coating treatment of the group VIB compound. 2%. By setting the content of the VIB group compound within the range, the effect of the present invention can be further embodied, and the original overall performance of the glass fiber cloth is further improved, so that the VIB group compound has better dispersion uniformity.

The thermosetting resin composition may include a thermosetting resin, a curing agent, an accelerator, and a solvent.

The thermosetting resin according to the present invention is any one or a combination of at least two polymers that can be cross-linked to form a network structure, and is preferably an epoxy resin, a phenol resin, a cyanate resin, a polyamide resin, and a polyamide. Any one or a combination of at least two of an amine resin, a polyether resin, a polyester resin, a hydrocarbon resin, or a silicone resin; and an epoxy resin or a phenol resin is further preferred.

Specific examples of the combination of the thermosetting resin may be a combination of an epoxy resin and a polyamide resin, a combination of a polyimide resin and a hydrocarbon resin, a combination of a cyanate resin, a polyamide resin, and a polyether resin, and a cyanide resin. Acid ester resin, polyimide resin, combination of polyimide resin and epoxy resin, etc.

For epoxy resin and its combination with other resins, the curing agent may be a phenolic resin, an acid anhydride compound, an active ester compound, dicyandiamide, diaminodiphenylmethane, diaminodiphenylhydrazone, and diamine group. One or two or more of diphenyl ether and maleimide; the curing accelerator is 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-methyl-4 -One or a mixture of two or more of phenylimidazoles.

For the phenolic resin and its combination with other resins, the curing agent may be an organic acid anhydride, an organic amine, a Lewis acid, an organic amidine, an imidazole compound, an organic phosphine compound, and a mixture thereof mixed at any ratio.

For olefin resins, reactive polyphenylene ether resins, polyamine resins containing two or more unsaturated double bonds, and combinations thereof with other resins, the curing agent is selected from organic peroxide crosslinking agents, Preferably, it is one of dicumyl peroxide, benzoylperoxide, di-t-butyl peroxide, diethylammonium peroxide, tert-butyl pivalate, and diphenyl oxide peroxydicarbonate. Multiple. The accelerator is an allyl organic compound, preferably triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, and trimethylolpropane triacetate. One or more of acrylates.

For silicone resins, the accelerator is selected from organic platinum compounds.

The thermosetting resin composition may further include a silane coupling agent or / and a wetting and dispersing agent. The silane coupling agent is not particularly limited as long as it is a silane coupling agent generally used in the surface treatment of inorganic fillers. Specific examples include amine silane based on γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and γ-glycidyl ether oxypropyl. Silane-based epoxy silanes such as trimethoxysilane, vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzoylaminoethyl) -γ- An anionic silane type such as aminopropyltrimethoxysilane hydrochloride, a phenylsilane type, or the like may be selected from one or at least two in an appropriate combination. The wet dispersant is not particularly limited as long as it is a wet dispersant used in the solid resin composition. Examples include wetting and dispersing agents such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 manufactured by BYKChemie Japan.

The thermosetting resin composition may further contain various additives. Specific examples include flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, and lubricants. These various additives may be used alone or in combination of two or more.

As a method for preparing the resin composition of the present invention, it can be prepared by a known method such as compounding, stirring, and mixing the thermosetting resin, inorganic filler, porous molybdenum compound, curing agent and accelerator, and various additives.

The solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl alcohol. Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, aromatic hydrocarbons such as toluene, xylene, mesitylene, and ethoxy Ethyl acetate, acetic acid Ester such as ethyl ester, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing solvents. The above solvents may be used singly, or two or more kinds may be used in combination, preferably aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl methyl Ketones such as ketones and cyclohexanone are mixed for use. The use amount of the solvent can be selected by those skilled in the art according to their own experience, so that the obtained resin glue solution can reach a suitable viscosity.

According to the invention, the reinforcing material is coated with a Group VIB compound. Examples of the method of the coating treatment may include a spraying method and a dipping method. When solid VIB compounds are used, spraying can be used. When a liquid Group VIB compound is used, a dipping method may be used.

The spraying method may include: firstly, dispersing an appropriate amount of a group VIB compound in a solvent; and then spraying uniformly on the surface of the reinforcing material by spraying at room temperature; and after spraying the solution of the group VIB compound, warming to 120-160 ° C and drying Within 4-6 hours, a reinforcing material coated with a VIB compound is obtained. Dispersion can be performed using a sand mill. Preferably, spraying is performed using a nozzle so that the sprayed droplets are smaller than 0.2 μm.

The impregnation method may include: first, diluting the VIB compound with a solvent, and then uniformly impregnating the reinforcing material at 60-100 ° C, heating to 120-160 ° C and drying for 2-4 hours to obtain a VIB-encapsulated reinforcing material .

The thermosetting resin composition is formulated into a glue solution by mechanical stirring, emulsification or ball milling dispersion, and then the glue solution is used to soak the glass fiber cloth covered with the inorganic filler and dried to obtain a prepreg. The prepreg and a metal foil such as a copper foil are hot-pressed in a vacuum press to prepare a laminate.

Specifically, the method for preparing a laminate from a reinforcing material coated with a VIB compound can include the following steps:

(1) Glue making: Add the solvent to the ingredients container, and add the epoxy resin, curing agent solution, and accelerator solution separately under stirring; after stirring, add the inorganic filler and continue stirring to obtain the glue solution.

(2) Impregnation: The VIB compound-coated reinforcing material is immersed in the glue solution.

(3) Impregnation: The reinforcing material impregnated with the glue solution is passed through a vertical or horizontal impregnation machine, and the prepreg is obtained by controlling the conditions of the extrusion wheel speed, line speed, wind temperature, and furnace temperature.

Specific examples of vertical impregnation machines are: extrusion wheel speed: -1.3 to -2.5 ± 0.1M / min; main line speed: 4 to 18m / min; wind temperature: 120 to 170 ° C; furnace temperature: 130 to 220 ° C .

(4) Pressing: Combine the cut prepreg with metal foil such as copper foil, put it into a vacuum hot press, and finally make a metal-clad laminate such as a copper-clad layer at a certain temperature, time and pressure Pressure plate, the specific example is: temperature program: 130 ℃ / 30min + 155 ℃ / 30min + 190 ℃ / 90min + 220 ℃ / 60min; pressure program: 25kgf. cm ^-2 / 30min + 50kgf. cm ^-2 / 30min + 90kgf. cm ^-2 / 120min + 30kgf. cm ^-2 / 90min; vacuum program: 30mmHg / 130min + 800mmHg / 130min.

Through the above procedure, a prepreg is laminated between a metal foil such as a copper foil, and a laminate (ie, a copper clad laminate) can be obtained after hot pressing.

The present invention can also provide a laminated board and a printed circuit board.

The laminate may contain at least one sheet of fiberglass cloth-based prepreg as described in any of the above.

The printed circuit board may contain at least one glass fiber cloth-based prepreg as described in any of the above.

According to the present invention, by covering the VIB group compound in the reinforcing material, the problem of dispersion and settlement of the VIB group compound can be effectively solved, so that it can be evenly distributed in the prepreg, and at the same time, the drill cutter and the VIB group are greatly increased. The contact area of the compound effectively reduces the wear of the drill and significantly improves the drilling quality.

Examples

The technical solutions of the present invention will be further described below through specific embodiments.

The codes and their components used in the examples and comparative examples are as follows: Epoxy resin A: A phenolic epoxy resin produced by Hexion Chemicals (formerly American Bolton Chemical Company and German Beklett Company) under the trade name EPR627- MEK80 has an epoxy equivalent weight between 160 and 250 g / eq.

Epoxy Resin B: The epoxy resin produced by Dow Chemical Company of the United States, trade name is DER-592A80, and its epoxy equivalent is between 300 and 460 g / eq.

Epoxy Resin C: A high bromine epoxy resin produced by Japan Ink Chemical Company under the trade name EPICLON153. Its epoxy equivalent is between 350 and 450 g / eq.

Curing agent: Phenolic resin curing agent produced by Hexion Chemical Company, USA, trade name is PHL6635M65.

Accelerator: 2MI (dimethylimidazole) produced by Shikoku Chemical Co., Ltd.

Inorganic filler E: fused silica, with an average particle diameter of 0.5 microns.

Auxiliary: W903, BYK Chemical.

Molybdenum dialkyl dithiophosphate, Pacific Union (Beijing) Petrochemical, trade name POUPC 1001B.

Zinc molybdate, Kemgard.

Molybdenum disulfide, Changsha Huajing Powder Material Technology Co., Ltd.

Tungsten disulfide, Changsha Huajing Powder Material Technology Co., Ltd.

Dioctyl dithiocarbamate tungsten, Guangdong Shengyi Technology Co., Ltd.

Ammonium octamolybdate, Guangzhou Xijia Chemical Co., Ltd.

Examples 1-17

The reinforcing materials of Examples 1 and 12 were coated with a Group VIB compound using a dipping method; and the reinforcing materials of Examples 2-11 and 13-17 were coated with a Group VIB compound using a spraying method. The VIB compounds used in Examples 1-17 and their content in the coated glass fiber cloth, and the particle size of the VIB compounds used in Examples 2-11 and 13-17 are listed in Table 1.

Spray method: First, the VIB compound is dispersed in water using a sand mill to obtain a dispersion solution, so that the VIB compound accounts for 20% of the weight of the dispersion solution; then, the nozzle is sprayed uniformly on the surface of the reinforcing material at room temperature in a spraying manner. The droplets are less than 0.2 μm; and after spraying the VIB compound solution, the temperature is raised to 140 ° C. and dried for 5 hours to obtain a VIB-coated reinforcing material.

Impregnation method: First, dilute the VIB group compound with acetone so that the weight ratio of the VIB group compound to acetone is 25%; then uniformly impregnate the reinforcing material at 80 ° C and dry it for 3 hours at 140 ° C to obtain a VIB group compound Wrapped reinforcement.

See Tables 1 and 2 for the solid composition formula of the thermosetting resin composition used to prepare the laminate from the VIB compound-coated reinforcing material. Using methyl ethyl ketone to prepare a thermosetting epoxy resin varnish used for manufacturing laminates, the solid content of which is 67%.

The copper-clad laminates of Examples 1-17 were prepared according to the following preparation process:

(1) Glue making: Add the solvent to the ingredients container, and add the epoxy resin, curing agent solution, and accelerator solution separately under stirring; after stirring for 2 hours, add the inorganic filler and continue stirring for 6 hours to obtain the glue solution.

(2) Impregnation: The VIB compound-coated reinforcing material is immersed in the glue solution.

(3) Impregnation: The reinforced material impregnated with the glue solution is passed through a vertical impregnation machine, and the prepreg is prepared by controlling the conditions of the extrusion wheel speed, line speed, wind temperature, and furnace temperature. The conditions of the vertical impregnation machine are: extrusion wheel speed: -1.8 ± 0.1M / min; main line speed: 10m / min; wind temperature: 150 ° C; furnace temperature: 180 ° C.

(3) Pressing: After combining the cut prepreg and copper foil, put it into a vacuum hot press, and finally obtain a copper-clad laminate at a certain temperature, time and pressure. The specific conditions are: temperature program : 130 ℃ / 30min + 155 ℃ / 30min + 190 ℃ / 90min + 220 ℃ / 60min; pressure program: 25kgf. cm ^-2 / 30min + 50kgf. cm ^-2 / 30min + 90kgf. cm ^-2 / 120min + 30kgf. cm ^-2 / 90min; vacuum program: 30mmHg / 130min + 800mmHg / 130min.

Through the above procedure, eight prepregs with a thickness of 0.2 mm were laminated between 35 μm-thick copper foils, and a 1.6 mm thick laminate was obtained after hot pressing. After obtaining the copper-clad laminate, the properties of the plates were tested. Table 2 shows the comparison of the properties of the plates.

Comparative Example 1

The reinforcing material of Comparative Example 1 was not coated with a VIB compound. Comparative Example 1 is shown in Table 1 in detail for the composition of the solid content formula, and was prepared by using methyl ethyl ketone to produce a thermosetting epoxy resin glue solution for manufacturing a laminate, in which the solid content accounts for 67%. Except for the above differences, the preparation method of Comparative Example 1 is as in Examples 1-17.

Comparative Example 2

The reinforcing material of Comparative Example 2 was not coated with a VIB compound. Zinc molybdate was directly added to the thermosetting resin composition of Comparative Example 2. The solid composition formulation is shown in Table 2. The thermosetting epoxy resin glue used for the manufacture of laminates was prepared by methyl ethyl ketone, in which the solid content was 67%. . Except for the above differences, the preparation method of Comparative Example 2 is as in Examples 1-17.

Comparative Example 3

The reinforcing material of Comparative Example 3 was not coated with a VIB compound. Tungsten disulfide was directly added to the thermosetting resin composition of Comparative Example 3, and its solid composition formula is shown in Table 2. The thermosetting epoxy resin glue used for manufacturing the laminate was prepared by methyl ethyl ketone, in which the solid content was 67%. Except for the above differences, the preparation method of Comparative Example 3 is as in Examples 1-17.

Performance Testing:

1. Evaluation of drilling processability: The produced copper-clad laminates were stacked in two pieces, and a new drill of 0.3 mm was used to drill holes at a speed of 155 krmp at a drilling machine (HITACHI NDR-1V 212E). Each plate was drilled with 6 New knives, each with 6000 holes. Use a drill with a different number of holes to observe the bit of the drill bit using a microscope hole inspection machine (Taiwan Mude PM-2824), determine the amount of wear retreat of the blade tip to measure the distance between the intersection of the vertical line and the central axis and the upper edge of the wear. To evaluate the drilling effect, the following formula is used to calculate the wear rate of the drill.

Wear rate% = distance between the edge after drilling and the center axis / distance between the edge before drilling and the center axis × 100%

2. Evaluation of the distribution uniformity of Group VIB compounds: The treated reinforcing material was cut to a size of 5 mm square, injection molded with injection molding resin, placed on a conductive adhesive, and sprayed with gold to make an observation test piece. Observe with a scanning electron microscope, observe the dispersion of the compound in the glass fiber cloth, and evaluate it.

Table 1

From Tables 1 to 2, it can be seen that the use of glass fiber cloth coated with Group VIB compounds as a reinforcing material can significantly improve the drilling processability of laminates, and the treatment of glass fiber cloth with a small amount of Group VIB compounds, that is, The abrasion rate of the laminate to the drill can be reduced from 95% to 40-82%, the effect is quite obvious, and its comprehensive performance is excellent. In addition, as can be seen from Tables 1 to 2, it can be seen from Examples 8-9 and 14-15 that the particle size of the VIB group compound is in the range of 0.01 μm to 1 μm, which can further improve the uniform distribution of the VIB group compound. Properties, and will further improve the drilling workability of the laminate. It can be seen from Examples 2-6 and Examples 16-17 that the content of the VIB group compound in the coated glass fiber cloth is in the range of 0.01 to 5% by weight, which can further improve the uniformity of the glass fiber cloth and the laminate. Drillability. In addition, it can be seen from Examples 4, 5, 9, and 13 that the molybdenum compound and the tungsten compound are more effective when used in combination. The same particle size and the same amount of use, the drilling effect achieved by the combination of the two is equivalent to that of the separate. Using 2 times the amount of one of the compounds with the same particle size (that is, 1 part by weight of a 1: 1 mixture of molybdenum compound and tungsten compound is equivalent to 2 parts by weight of molybdenum compound or tungsten compound), and the effect is significant With. From Example 2-6 and Example 11 compared with Comparative Example 2-3, it can be seen that by processing and coating the VIB group compound on the glass fiber cloth, the drilling processability is significantly improved, and the same compound is used The direct addition amount is 5 times the coating treatment amount, but the drilling effect after the coating treatment is better than the direct addition, indicating that the present invention can significantly reduce the amount of VIB group compounds, and can effectively improve the plate. Drilling performance.

Obviously, those skilled in the art can make various modifications and changes to the embodiments of the present invention without departing from the spirit and scope of the present invention. In this way, if these modifications and changes of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these changes and changes.

Claims (14)

A prepreg comprising a reinforcing material and a thermosetting resin composition attached to the prepreg after being dried by dipping, wherein the reinforcing material is coated with a VIB group compound; wherein the VIB group compound is subjected to A content of the reinforcing material coated with the VIB compound is 0.01 to 5% by weight. The prepreg according to claim 1, wherein the group VIB compound is selected from a molybdenum compound, a tungsten compound, or a mixture thereof. The prepreg according to claim 2, wherein the molybdenum compound is selected from the group consisting of: molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithiophosphate, molybdenum dialkyl dithioaminoformate, Any one or any two or more of molybdenum amine complex, molybdenum naphthenate, molybdenum alkyl salicylate, molybdenum molybdenum, dimercaptothiazole molybdenum, molybdenum alkylamine, organic molybdate, or molybdenum octoate A mixture of species. The prepreg according to claim 1, wherein the group VIB compound is liquid or solid. The prepreg according to claim 2, wherein the molybdenum compound is selected from the group consisting of molybdic acid, molybdate, molybdenum oxide, heteropolyacids of molybdenum and their sodium, potassium, and ammonium salts, and polyacids of molybdenum Any one of Molybdenum Blue, Molybdenum Sulfide, Molybdenum Selenide, Molybdenum Telluride, Molybdenum Halide, Molybdenum Alloy, or Molybdenum Disilide or a mixture of any two or more of them. The prepreg according to claim 2, wherein the molybdenum compound is selected from any one or any of ammonium molybdate, sodium molybdate, zinc molybdate, calcium molybdate, magnesium molybdate, molybdenum oxide, or molybdenum sulfide A mixture of two or more. The prepreg according to claim 2, wherein the tungsten compound is selected from the group consisting of: tungsten disulfide, amine tetrathiotungstate, tungsten tetrabromide, tungsten tetrachloride, tungsten tetrabromide, zinc tungstate, tungsten Calcium Acid, Magnesium Tungstate, Ammonium Tungstate, Tungsten Selenide, Tungsten Oxide, Dioctyl Dithiocarbamate, Dithiophenol Tungsten, 3,4-Dimercaptotolyl Tungsten, Amino Diisopropyl Any one or a mixture of at least two kinds of tungsten dithiophosphate, organic tungsten molybdenum complex, tungsten dithiocarbamate compound, aromatic tungsten compound or alk (aryl) amino tungsten thiophosphate. The prepreg according to claim 2, wherein the tungsten compound is selected from the group consisting of tungsten disulfide, amine tetrathiotungstate, tungsten tetrabromooxide, tungsten tetrachloride, tungsten tetrabromide, or alk (aryl) amine Any one of tungsten thiophosphate or a mixture of at least two of them. The prepreg according to claim 1, wherein the group VIB compound is selected from a mixture of a molybdenum compound and a tungsten compound, and in the mixture of the molybdenum compound and the tungsten compound, the mixing ratio of the molybdenum compound and the tungsten compound is by weight in In the range of about 1: 100 to about 100: 1. The prepreg according to claim 1 or 2, wherein the group VIB compound is in a solid state and has an average particle diameter of 0.01 to 1 μm. The prepreg according to claim 1, wherein the content of the group VIB compound in the reinforcing material subjected to the coating treatment of the group VIB compound is 0.05 to 2% by weight. The prepreg according to claim 1, wherein the reinforcing material comprises glass fiber cloth. A laminate comprising at least one prepreg according to claim 1. A printed circuit board containing at least one prepreg according to claim 1.