WO2019126928A1

WO2019126928A1 - Thermosetting resin composition, prepreg, laminate, and printed circuit board

Info

Publication number: WO2019126928A1
Application number: PCT/CN2017/118262
Authority: WO
Inventors: 杜翠鸣
Original assignee: 广东生益科技股份有限公司
Priority date: 2017-12-25
Filing date: 2017-12-25
Publication date: 2019-07-04

Abstract

The present invention provides a thermosetting resin composition, a prepreg, a laminate, and a printed circuit board. The thermosetting resin composition comprises: a thermosetting resin, an inorganic filler, and a porous molybdenum compound. By using the porous molybdenum compound as a solid lubricant, the problems of dispersion and sedimentation of a molybdenum compound can be effectively solved, so that the molybdenum compound can be evenly distributed in a prepreg; the porous molybdenum compound has better thermal conductivity, and can better conduct heat during drilling, and the melted resin can be prevented from adhering to a drilling tool; in addition, hole cracks can also be reduced, and the quality of the wall of a drilled hole can be obviously improved.

Description

Thermosetting resin composition, prepreg, laminate, and printed circuit board

Technical field

The present invention relates to a thermosetting resin composition and a prepreg. In particular, the present invention relates to a thermosetting resin composition, a prepreg, a laminate, and a printed circuit board.

Background technique

With the rapid development of electronic products in terms of miniaturization, multi-function, high performance, and high reliability, printed circuit boards are beginning to be high-precision, high-density, high-performance, micro-porous, thin, and multi-layered. The direction has developed rapidly, and its application range has become more and more extensive. It has rapidly entered civilian electrical appliances and related products from large-scale industrial electronic computers, communication instruments, electrical measurement, defense and aviation, and aerospace. While the matrix material largely determines the performance of printed circuit boards, there is an urgent need to develop a new generation of matrix materials. As a new generation of matrix materials in the future, it must have high heat resistance, low coefficient of thermal expansion, and excellent chemical stability and mechanical properties.

In order to reduce the coefficient of thermal expansion of the laminate, a resin having a low coefficient of thermal expansion or an increase in the content of the inorganic filler is usually used. However, the low thermal expansion coefficient resin structure is special and the cost is high; and the method of increasing the inorganic filler content can not only effectively reduce the thermal expansion coefficient of the composite, but also the cost can be greatly reduced. However, highly filled resins can significantly reduce the drilling processability and interlayer adhesion of the laminate. Therefore, a block filler such as talc is added as a lubricant to improve workability, but the effect is not remarkable, and the addition of these block fillers further deteriorates interlayer adhesion. In addition, in order to improve the drilling processability, a metal molybdenum compound is added, and a metal molybdenum compound such as zinc molybdate added to the thermosetting resin composition is mentioned in CN102656234A to improve workability, and the patent is recommended to be loaded on talc or the like. The molybdenum compound particles are formed, which has a problem that the interlayer adhesion of the laminate is remarkably lowered, and the molybdenum compound has poor dispersibility in the resin, a large density, and is liable to cause sedimentation, and satisfactory results cannot be obtained.

Summary of the invention

One of the objects of the present invention is to provide a thermosetting resin composition, a prepreg, a laminate, and a printed circuit board in which a porous molybdenum compound is used as a solid lubricant, which effectively solves the problem of dispersion and sedimentation of a molybdenum compound, thereby making it possible to solve the problem of dispersion and sedimentation of a molybdenum compound. Evenly distributed in the prepreg, the porous molybdenum compound has better thermal conductivity, better conducts heat when drilling, prevents the resin from sticking to the drill after melting, and also reduces cracking of the hole, etc., and significantly improves the drilling. The quality of the hole wall afterwards.

In one aspect, the present disclosure provides a thermosetting resin composition comprising: a thermosetting resin, an inorganic filler, and a porous molybdenum compound.

Optionally, the porous molybdenum compound content is from 0.01 to 10% by weight based on the total mass of the thermosetting resin composition.

Optionally, the porous molybdenum compound is selected from the group consisting of: molybdenum disulfide, molybdenum dioxide, molybdenum trioxide, molybdate or molybdenum alloy, or a mixture of at least two.

Alternatively, the porous molybdenum compound has an average particle diameter of 0.1 to 50 μm.

Optionally, the porous molybdenum compound has a porosity of from 5 to 80%.

Alternatively, the porous molybdenum compound has a pore diameter of 50 nm to 10 μm; preferably 50 nm to 1 μm.

Optionally, the thermosetting resin accounts for 20 to 70% by weight of the total mass of the thermosetting resin composition.

Optionally, the inorganic filler is contained in an amount of 10 to 80% by weight based on the total mass of the thermosetting resin composition.

Optionally, the inorganic filler is selected from the group consisting of silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, nitrogen. Any one or at least two of boron, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow fine powder or boehmite Kind of mixture.

Alternatively, the inorganic filler has an average particle diameter of 0.1 to 100 μm.

Optionally, the thermosetting resin composition further includes a curing agent, wherein the curing agent accounts for 1 to 30% by weight based on the total mass of the thermosetting resin composition.

Optionally, the thermosetting resin composition further includes an accelerator, wherein the content of the accelerator in the thermosetting resin composition is in a range of more than 0 and less than or equal to 10% by weight.

In another aspect, the present disclosure provides a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered thereto by dipping and drying.

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

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

According to the present disclosure, by using a porous molybdenum compound as a solid lubricant, the problem of dispersion and sedimentation of the molybdenum compound can be effectively solved, so that it can be uniformly distributed in the prepreg, and the porous molybdenum compound has better thermal conductivity. It can better conduct heat, can prevent the resin from sticking to the drill after melting, and can also reduce the cracking of the hole, etc., and can significantly improve the quality of the hole wall after drilling.

Detailed ways

The technical solutions in the embodiments of the present disclosure will be clearly and completely described in the following, and the embodiments and/or embodiments described are only a part of the embodiments and/or embodiments of the present disclosure. Rather than all embodiments and/or embodiments. All other embodiments and/or all other embodiments obtained by a person of ordinary skill in the art based on the embodiments and/or embodiments of the present disclosure without departing from the inventive scope are the scope of the disclosure.

In the present disclosure, all numerical features are within the measurement error range, for example within ±10% of the defined value, or within ±5%, or within ±1%.

The term "comprising", "including" or "containing" as used in the present invention means that in addition to the components, it may have other components which impart different characteristics to the prepreg. In addition, "including", "including" or "containing" as used in the present invention may also include "consisting essentially of" and may be replaced by "for" or "consisting of."

In the present disclosure, the amounts, ratios, and the like are by weight unless otherwise specified.

As described above, the present disclosure can provide a thermosetting resin composition including: a thermosetting resin, an inorganic filler, and a porous molybdenum compound.

The present disclosure, by including a porous molybdenum compound in a thermosetting resin composition, can not only improve the thermal conductivity of the prepared laminate, but also significantly improve the drilling processability of the laminate, and can significantly improve the quality of the pore walls. Further, since the porous molybdenum compound has a small density and is porous, it has good compatibility with the resin system, and it is possible to obtain a resin composition which is uniformly dispersed and stable without using a complicated dispersing device.

According to another embodiment of the present disclosure, the porous molybdenum compound content may be from about 0.01% by weight to about 10% by weight, preferably from about 0.5% by weight to about 5% by weight, based on the total mass of the thermosetting resin composition. By setting the content within the range, the drilling processability can be further improved without affecting the original overall performance of the thermosetting resin composition.

According to another embodiment of the present disclosure, the porous molybdenum compound may be selected from any one of molybdenum disulfide, molybdenum dioxide, molybdenum trioxide, molybdate or molybdenum alloy, or a mixture of at least two.

Examples of the molybdenum alloy may include: a Mo-Au alloy, a Mo-Ag alloy, a Mo-Cu alloy, a Mo-Al alloy, a Mo-Ti alloy, a molybdenum silicon-boron three-phase alloy, and the like.

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

The porous zinc molybdate can be prepared by the method described in the examples of CN 101660078A. Porous zinc molybdate having different porosities, pore sizes and particle sizes can be prepared by adjusting the process conditions.

According to another embodiment of the present disclosure, the porous molybdenum compound may have an average particle diameter of from about 0.1 μm to about 50 μm, preferably from about 0.5 μm to about 20 μm.

By setting the average particle diameter of the porous molybdenum compound within the above range, the desired effect can be achieved, and at the same time, the probability of incorporation of coarse particles can be reduced and the occurrence of coarse particle defects can be suppressed.

According to another embodiment of the present disclosure, the porous molybdenum compound may have a porosity of from about 5% to about 80%, preferably from about 20% to about 70%. When the porosity is less than 5%, it is almost a solid solid, and the special effect of the porous compound cannot be achieved; when the porosity is more than 80%, the thermal conductivity is deteriorated, and the resin is easily adhered to the surface of the drill, resulting in poor processability. . The porous molybdenum compound may have a pore diameter of more than 50 nm to 10 μm, preferably 50-1 μm. When the pore diameter is less than 50 nm, the resin compound is difficult to enter into the pore due to capillary action, and the specific effect of the porous compound cannot be achieved; when the pore diameter is larger than 10 μm, The thermal conductivity also drops sharply, failing to achieve the special effects of the porous compound, and the overall effect is also deteriorated. . By setting the porosity and the pore diameter of the porous molybdenum compound within the above range, the problem of dispersion and sedimentation of the molybdenum compound can be further effectively solved, so that it can be uniformly distributed in the prepreg.

According to another embodiment of the present disclosure, the thermosetting resin may comprise from about 20% by weight to about 70% by weight, preferably from about 25% by weight to about 65% by weight, and more preferably about 30% by weight to the total mass of the thermosetting resin composition. About 60% by weight. The mass percentage of the thermosetting resin to the total mass of the thermosetting resin composition may be, for example, about 23% by weight, about 26% by weight, about 31% by weight, about 35% by weight, about 39% by weight, about 43% by weight, about 47% by weight. %, about 51% by weight, about 55% by weight, about 59% by weight, about 63% by weight or about 67% by weight and any range therebetween, for example about 23% by weight, about 26% by weight, about 31% by weight About 35 wt% or about 39 wt% to about 43 wt%, about 47 wt%, about 51 wt%, about 55 wt% about, about 59 wt%, about 63 wt%, or about 67 wt%.

According to another embodiment of the present disclosure, the inorganic filler may be included in an amount of from about 10% by weight to about 80% by weight, based on the total mass of the thermosetting resin composition, preferably from about 20% by weight to about 60% by weight, for example, about 23% % by weight, about 28% by weight, about 32% by weight, about 37% by weight, about 42% by weight, about 47% by weight, about 52% by weight, about 57% by weight, about 62% by weight, about 67% by weight, about 72% % by weight, about 76% by weight or about 78% by weight and any range therebetween, such as about 23% by weight, about 28% by weight, about 32% by weight, about 37% by weight or about 42% by weight to about 47% by weight, About 52% by weight, about 57% by weight, about 62% by weight, about 67% by weight, about 72% by weight, about 76% by weight, or about 78% by weight.

By setting the content of the inorganic filler in the range, the formability and low thermal expansion of the thermosetting resin composition can be favorably maintained, and in the case where a highly filled inorganic filler is realized and a porous molybdenum compound is used, the drilling can be suppressed. The processability and the deterioration of the interlayer adhesion force give the resulting laminate a low coefficient of thermal expansion, excellent drilling processability and heat resistance, and high interlayer adhesion.

According to another embodiment of the present disclosure, the inorganic filler may be selected from the group consisting of silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc stannate, oxidation Zinc, titanium oxide, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow fine powder or boehmite Any one or a mixture of at least two.

Examples of the hollow fine powder may include hollow silica, hollow boron nitride, hollow glass powder, hollow alumina, and the like.

According to another embodiment of the present disclosure, the inorganic filler may have an average particle diameter of from about 0.1 μm to about 100 μm, preferably from about 0.5 μm to about 20 μm. By setting the average particle diameter of the inorganic filler within the above range, the fluidity at the time of high filling in the thermosetting resin composition can be favorably maintained, and at the same time, the probability of incorporation of coarse particles can be reduced and the occurrence of coarse particle defects can be suppressed. Here, the average particle diameter refers to a particle diameter at a point corresponding to a volume of 50% when the cumulative volume distribution curve based on the particle diameter is obtained by taking the total volume of the particles as 100%, and the laser diffraction scattering method can be used. Particle size distribution determination.

According to another embodiment of the present disclosure, the thermosetting resin composition may further include a curing agent. The curing agent may comprise from about 1% to about 30% by weight, preferably from about 4% to about 25% by weight, further preferably from about 10% to about 20% by weight, such as about 2% by weight, based on the total mass of the thermosetting resin composition. , about 5% by weight, about 8% by weight, about 11% by weight, about 14% by weight, about 17% by weight, about 19% by weight, about 22% by weight, about 26% by weight or about 28% by weight, and between Any range, such as about 2% by weight, about 5% by weight, about 8% by weight, about 11% by weight, or about 14% to about 17% by weight, about 19% by weight, about 22% by weight, about 26% by weight, or about 28% weight%.

According to another embodiment of the present disclosure, the thermosetting resin composition may further include an accelerator. The content of the accelerator in the thermosetting resin composition may be in a range of more than 0 and less than or equal to about 10% by weight, preferably in a range of from about 1% by weight to about 10% by weight, further preferably at about 2% by weight. To a range of about 8% by weight, such as about 0.5% by weight, about 1.5% by weight, about 2.5% by weight, about 3.5% by weight, about 4.5% by weight, about 5.5% by weight, about 6.5% by weight, about 7.5% by weight, About 8.5 wt% or about 9.5% by weight and any range therebetween, such as about 0.5 wt%, about 1.5 wt%, about 2.5 wt%, about 3.5 wt% or about 4.5 wt% to about 5.5 wt%, about 6.5 wt% %, about 7.5% by weight, about 8.5% by weight or about 9.5% by weight.

According to another embodiment of the present disclosure, the thermosetting resin composition further includes a solvent.

The present disclosure may also provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described in any of the above, adhered thereto by dipping and drying.

Examples of the reinforcing material may include a fiberglass cloth. In the following description, the fiberglass cloth reinforcing material and the fiberglass cloth are used interchangeably.

The thermosetting resin composition may include a thermosetting resin, a curing agent, a promoter, and a solvent. The thermosetting resin according to the present invention is any one or a combination of at least two of the polymers which can be crosslinked to form a network structure, and preferably an epoxy resin, a phenol resin, a cyanate resin, a polyamide resin, or 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; more preferably an epoxy resin or a phenol resin.

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 cyanate ester. A combination of a resin, a polyamide resin, a polyimide resin, and an epoxy resin.

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, diaminodiphenyl sulfone, diaminodiphenyl ether. And one or a mixture of two or more of maleimide; the curing accelerator is 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-methyl-4-benzene One or a mixture of two or more of the imidazoles;

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 amide, an imidazole compound, an organic phosphine compound, and a mixture thereof in any ratio.

For an olefin resin, a reactive polyphenylene ether resin containing two or more unsaturated double bonds, a polyamide resin, and a combination thereof with other resins, the curing agent is selected from an organic peroxide crosslinking agent, preferably Is one or more of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, diacetyl peroxide, tetrabutyl peroxypivalate and diphenyl oxide dicarbonate Kind. The promoter is an allyl organic compound, preferably triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate and trimethylolpropane One or more of acrylates.

For silicone resins, the promoter is selected from the group consisting of organoplatinum 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 which is usually used in the surface treatment of inorganic barium. Specific examples include aminosilane such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-glycidyloxy propyl acrylate. Ethylene silane such as trimethoxysilane or vinyl silane such as γ-methacryloxypropyltrimethoxysilane, N-β-(N-vinylphenylacylaminoethyl)-γ-ammonia An anionic silane type such as propyltrimethoxysilane hydrochloride or a phenylsilane type may be used, and one type or at least two types may be used in combination as appropriate. Further, the wetting dispersing agent is not particularly limited as long as it is a wetting dispersing agent used in the thermosetting resin composition. For example, a wet dispersing agent such as Disperbyk-110, 111, 180, 161, BYK-W996, W9010, W903 manufactured by BYK Chemie Japan can be cited.

The thermosetting resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.

The preparation method of the resin composition of the present invention can be produced by a known method such as compounding, stirring, mixing the above-mentioned 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 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 alone or in combination of two or more. Preferred are aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group. A ketone flux such as butyl ketone or cyclohexanone is used in combination. The amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.

Specifically, the thermosetting resin composition is formulated into a glue by mechanical stirring, emulsification or ball mill dispersion, and then the glass cloth is impregnated with the glue, and dried to obtain a prepreg. A laminate can be prepared by hot pressing the prepreg and a metal foil such as a copper foil in a vacuum press.

Specifically, the method of preparing a laminate from a reinforcing material may include the following steps:

(1) Glue: The solvent is added to the ingredient container, and a solution of the epoxy resin, the curing agent solution, and the accelerator is separately added under stirring. After stirring, the inorganic filler is added and stirring is continued to obtain a glue.

(2) Impregnation: The reinforcing material is immersed in the glue.

(3) Impregnation: The prepreg is prepared by passing the reinforced material immersed in the glue through a vertical or horizontal impregnation machine by controlling the conditions of the extrusion wheel speed, the line speed, the air temperature and the furnace temperature.

The specific example of the vertical impregnation machine is: extrusion wheel speed: -1.3 to -2.5 ± 0.1 M / min. Main line speed: 4 to 18 m/min. Air temperature: 120 to 170 °C. Furnace temperature: 130 to 220 °C.

(4) Pressing: After the cut prepreg is combined with metal foil such as copper foil, it is placed in a vacuum hot press, and a metal-clad laminate such as a copper-clad layer is finally obtained according to a certain temperature, time and pressure. The pressure plate, the specific example is:

Temperature program:

130 ° C / 30 min + 155 ° C / 30 min + 190 ° C / 90 min + 220 ° C / 60 min.

Pressure program:

25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/90min.

Vacuum program:

30 mmHg / 130min + 800mmHg / 130min.

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

The present disclosure can also provide a laminate and a printed circuit board.

The laminate may contain at least one prepreg as described in any of the above.

The printed circuit board may contain at least one prepreg as described in any of the above.

Further, by including the porous molybdenum compound in the thermosetting resin composition, not only the thermal conductivity of the prepared laminate can be improved, but also the drilling processability of the laminate can be remarkably improved, and the quality of the pore walls can be remarkably improved. Further, since the porous molybdenum compound has a small density and is porous, it has good compatibility with the resin system, and it is possible to obtain a resin composition which is uniformly dispersed and stable without using a complicated dispersing device.

Example

The technical solution of the present invention will be further described below by way of specific embodiments.

The porosity in the examples was measured by volumetric weighing and the pore size was measured using a mercury porosimeter.

Example 1-22

Brominated bisphenol A type epoxy resin (Dow Chemical, epoxy equivalent 435, bromine content 19%, product name DER530) (epoxy resin), dicyandiamide (curing agent), 2-methylimidazole (promoted) , porous zinc molybdate (porous molybdenum compound) and fused silica (Silver, Singapore, 525, average particle size 2 μm) were added to methyl ethyl ketone (solvent) and mechanically stirred to prepare a 65 wt% gum solution. Then, impregnated glass fiber cloth (7628, Zhuhai Zhubo Electronic Materials Co., Ltd.) (reinforcing material), dried to form a prepreg after heating, copper foil placed on both sides, and heated to form a copper-clad laminate.

The copper clad laminates of the examples and comparative examples were prepared in accordance with the following preparation procedures:

(1) Glue: The solvent was added to the ingredient container, and the epoxy resin, the curing agent and the accelerator were respectively added under stirring; after stirring for 2 hours, the porous molybdenum compound and the inorganic filler were added, and stirring was continued for 6 hours to obtain a glue liquid.

(2) Impregnation: The reinforcing material is immersed in the glue.

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

(3) Pressing: After the cut prepreg is combined with the copper foil, it is placed in a vacuum hot press, and a copper clad laminate is finally obtained according to a certain temperature, time and pressure, and the specific conditions are as follows:

Temperature program:

130 ° C / 30 min + 155 ° C / 30 min + 190 ° C / 90 min + 220 ° C / 60 min;

Pressure program:

25kgf·cm-2/30min+50kgf·cm-2/30min+90kgf·cm-2/120min+30kgf·cm-2/90min;

Vacuum program:

30 mmHg / 130min + 800mmHg / 130min.

Through the above procedure, eight sheets of prepreg having a thickness of 0.2 mm were laminated between 35 μm thick copper foils, and a 1.6 mm thick laminate was obtained by hot pressing. A copper clad laminate is obtained. Using the obtained copper-clad laminate, the drilling processability, the pore wall whiteness, and the stability were evaluated by the method shown below, and the results are shown in Table 1.

Example 23

Brominated bisphenol A type epoxy resin (Dow Chemical, epoxy equivalent 435, bromine content 19%, product name DER530) (epoxy resin), dicyandiamide (curing agent), 2-methylimidazole (promoted) Agent), porous molybdenum dioxide (prepared according to CN 105977479 A) (porous molybdenum compound) and boehmite (Anhui Shishitong Material Technology Co., Ltd., BG601, average particle size 0.5 μm) added to methyl ethyl ketone (solvent) , mechanically stirred to prepare a 65% by weight glue, and then impregnated with glass fiber cloth (7628, Zhuhai Zhubo Electronic Materials Co., Ltd.) (reinforcing material), dried to form a prepreg after heating, copper foil placed on both sides Pressurized heating to form a copper clad laminate.

A copper clad laminate using a resin composition was obtained in the same manner as in Example 1. The measurement and evaluation results are shown in Table 2.

Example 24

100g of brominated bisphenol A type epoxy resin (Dow Chemical, epoxy equivalent 435, bromine content 19%, product name DER530), 24g novolac resin (Japan Qunrong, hydroxyl equivalent 105, product name TD2090), 0.05g 2-methylimidazole, porous molybdenum dioxide (prepared according to CN 105977479 A) (porous molybdenum compound) and 50g boehmite (Anhui Shishitong Material Technology Co., Ltd., BG601, average particle size 0.5μm) were added to Butanone (solvent), mechanically stirred to prepare a 65% by weight glue, then impregnated with glass fiber cloth (7628, Zhuhai Zhubo Electronic Materials Co., Ltd.) (reinforcing material), dried by heating to form a prepreg (prepreg) ), copper foil is placed on both sides, and pressure-heated to form a copper clad laminate.

Example 25

20 g of phenol novolac type cyanate PT30, 40 g of o-methyl phenol novolac type epoxy resin N695, 20 g of brominated styrene and an appropriate amount of catalyst zinc octoate, 0.05 g of 2-phenylimidazole, porous molybdenum dioxide (according to CN 105977479 A preparation) (porous molybdenum compound) and 50g boehmite (Anhui 通石通材料科技股份有限公司, BG601, average particle size 0.5μm) were added to methyl ethyl ketone (solvent), mechanically stirred to prepare 65% by weight The glue is then impregnated with glass fiber cloth (7628, Zhuhai Zhubo Electronic Materials Co., Ltd.) (reinforcing material), dried to form a prepreg after heating, copper foil is placed on both sides, and heated to form a copper-clad laminate. .

Example 26

30 g of dicyclopentadiene epoxy HP-7200H, 60 g of benzoxazine resin D125, 5 g of novolac resin EPONOL 6635M65, 5 g of dicyandiamide, porous molybdenum dioxide (prepared according to CN 105977479 A) (porous molybdenum compound) and 50 g Bom Stone (Anhui Yushitong Material Technology Co., Ltd., BG601, average particle size 0.5μm) was added to methyl ethyl ketone (solvent), mechanically stirred to prepare 65% by weight of glue, and then impregnated with glass fiber cloth (7628) , Zhuhai Zhubo Electronic Materials Co., Ltd.) (reinforcing material), after heating and drying to form a prepreg, placed on both sides of copper foil, pressurized heating to form a copper clad laminate.

In Examples 24-26, a copper clad laminate using a resin composition was obtained in the same manner as in Example 1. The measurement and evaluation results are shown in Table 3.

Comparative example 1

A copper-clad laminate using a resin composition was obtained in the same manner as in Example 1 except that zinc molybdate (Kemgard, 911B) was used instead of the porous molybdenum compound. The results of the measurement and evaluation are shown in Table 4.

Comparative example 2

A copper-clad laminate using a resin composition was obtained in the same manner as in Example 1 except that the porous molybdenum compound was not blended. The results of the measurement and evaluation are shown in Table 4.

1. Evaluation of drilling processability

The copper clad laminates to be produced, two stacks, were drilled at 155 krmp on a drilling rig (HITACHI NDR-1V 212E) with a new 0.3 mm knife. Each new plate was drilled with 6 new knives, each with 6,000 holes drilled. . The drills with different number of drill holes were observed with a microscope hole inspection machine (Taiwan Mude PM-2824) to measure the blade edge portion, and the blade tip wear back amount was measured to measure the distance between the intersection of the vertical line and the central axis and the upper edge of the wear. The drilling effect is evaluated by calculating the wear rate of the drill by the following formula. Wear rate%=distance between the trailing edge of the borehole and the central axis/distance between the front edge of the borehole and the central axis×100%

2, hole wall white line test

The plate with a number of holes of 5000 was removed from the slag, and then copper was plated to make a slice. The length of the white line of the hole wall was observed and measured using a microscope. The longer the length, the worse the quality of the hole wall.

3. Stability evaluation of resin composition

100 ml of the resin composition was placed in a 100 ml stopper cylinder, and allowed to stand in an environment of 25 ° C, and the time during which the precipitate was retained to the bottom of the settling tube was measured, and the stability was evaluated.

Overview:

A sample having a wear rate of less than or equal to 80%, a white wall of the pores of less than or equal to 80 μm, and a stability of greater than or equal to 7 days was rated as excellent;

A sample having a wear rate of less than or equal to 95% and greater than 80%, a pore wall whiteness of less than or equal to 105 μm and greater than 85 μm and a stability of greater than or equal to 3 days and less than 7 days is rated as acceptable;

Samples with a wear rate greater than 95%, a white wall 105 μm, and a stability of less than 3 days were evaluated as unacceptable.

table 3

Table 4

As can be seen from Tables 1-4, in the case of Example 1-22 and Comparative Example 1-2, the stability of the addition of the porous molybdenum compound was significantly enhanced as compared with the non-porous compound, and the drilling property was also significantly higher than that of the non-porous molybdenum. The compound is good and the wall quality is also significantly improved. With respect to Examples 1-4 and Examples 16-17, in the case where the amount of the porous molybdenum compound added is 0.01 to 10% by weight based on the total mass of the thermosetting resin composition, the drilling property and the pore wall can be further improved. Quality while increasing the stability of the composition. From the viewpoints of Examples 5-9 and Comparative Examples 20-21, the smaller the particle diameter of the porous molybdenum compound, the better the compatibility with the resin, the better the stability, the better the workability and the greater the workability thereof. When it is equal to 0.01 μm, since its dispersing ability becomes better, it is not easy to agglomerate; similarly, when the particle diameter is less than or equal to 50 μm, the sedimentation stability becomes remarkably better, and the drilling performance is also enhanced. Further, in the case of Examples 11 to 12 and Comparative Examples 20 to 21, the porosity was 5 to 80%, especially when the porosity was 20 to 60%, the sedimentation stability was the best, and the drilling processability was also the most. good.

It will be apparent to those skilled in the art that various modifications and changes can be made in the embodiments of the present disclosure without departing from the spirit and scope of the disclosure. Thus, it is intended that the present invention cover the modifications and the modifications

Claims

A thermosetting resin composition comprising: a thermosetting resin, an inorganic filler, and a porous molybdenum compound.
The thermosetting resin composition according to claim 1, wherein the porous molybdenum compound content is from 0.01 to 10% by weight based on the total mass of the thermosetting resin composition.
The thermosetting resin composition according to claim 1 or 2, wherein the porous molybdenum compound is selected from the group consisting of: molybdenum disulfide, molybdenum dioxide, molybdenum trioxide, molybdate or molybdenum alloy or at least two mixture.
The thermosetting resin composition according to claim 1, wherein the porous molybdenum compound has an average particle diameter of 0.1 to 50 μm.
The thermosetting resin composition according to claim 1, wherein the porous molybdenum compound has a porosity of from 5 to 80%.
The thermosetting resin composition according to claim 1, wherein the porous molybdenum compound has a pore diameter of 50 nm to 10 μm; preferably, the porous molybdenum compound has a pore diameter of 50 nm to 1 μm.
The thermosetting resin composition according to claim 1, wherein the thermosetting resin accounts for 20 to 70% by weight based on the total mass of the thermosetting resin composition.
The thermosetting resin composition according to claim 1, wherein the inorganic filler is contained in an amount of from 10 to 80% by weight based on the total mass of the thermosetting resin composition.
The thermosetting resin composition according to claim 1, wherein the inorganic filler is selected from the group consisting of silica, boehmite, alumina, talc, mica, kaolin, aluminum hydroxide, magnesium hydroxide, zinc borate, and stannic acid. Zinc, zinc oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, barium titanate, aluminum borate, potassium titanate, E glass powder, S glass powder, D glass powder, NE glass powder, hollow micro powder or boomer Any one of the stones or a mixture of at least two.
The thermosetting resin composition according to claim 1, wherein the inorganic filler has an average particle diameter of from 0.1 to 100 μm.
A prepreg comprising a reinforcing material and the thermosetting resin composition according to claim 1 adhered thereto by dipping and drying.
A laminate comprising at least one prepreg according to claim 11.
A printed circuit board comprising at least one prepreg as claimed in claim 11.