JP5055956B2 - Manufacturing method of substrate with resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin-coated base material having high performance equivalent to or higher than those of conventional organic solvent varnish-impregnated products, through reducing affecting safety and workplace environment and needing no special equipment for organic solvent treatment. <P>SOLUTION: The method for producing the resin-coated base material comprises the step of preparing a coating liquid comprising a cyanate resin, an epoxy resin, 16-30 pts.wt., based on 100 pts.wt. of the epoxy resin, of an emulsifier, an inorganic filler, a curing agent and water, the step of impregnating a fiber base material with the coating liquid, and the step of drying the fiber base material impregnated with the coating liquid. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a base material with a resin obtained by adhering and drying a coating solution on a base material.

Generally, as a base material with resin used for a printed circuit board, prepreg, resin-coated copper foil (RCC: Resin Coated Copper foil), etc. are mentioned.
The prepreg is obtained by impregnating a fiber base material such as glass cloth with a coating solution obtained by dissolving a resin component such as a thermosetting resin in an organic solvent, and drying by heating. Moreover, the copper foil with resin is obtained by applying the coating solution on the surface of the copper foil and drying by heating. Conventionally, a large amount of organic solvent has been used for such a coating solution. This is because preparation of the coating liquid and subsequent handling are easy, and there is an advantage that coating and impregnation on the substrate can be performed uniformly.

  However, the organic solvent is evaporated in the drying process when manufacturing the substrate with resin, and most of the organic solvent is processed by a combustion device or the like, or is released into the atmosphere as it is. For this reason, it has been pointed out that the impact on safety and work environment becomes a problem, and further contributes to global warming and air pollution. In addition, a combustion apparatus for treating the organic solvent is required separately. For this reason, in recent years, various attempts have been made to reduce the amount of organic solvent used in the production of a substrate with resin by using a water-dispersed coating solution or the like.

Patent Document 1 includes a glass substrate, an epoxy resin, a curing agent, a curing accelerator, 0 to 30 parts by weight of an organic solvent with respect to 100 parts by weight of the epoxy resin, and 100 parts by weight of the epoxy resin. On the other hand, a method for producing a prepreg containing 1.0 to 15 parts by weight of an emulsifier and water and containing a dried product of an aqueous coating solution is described.
Japanese Patent Laid-Open No. 9-316219

  However, the water-based coating liquid described in the above document may contain an organic solvent, and the impact on the safety and working environment associated with the use of the organic solvent has not been solved yet, and equipment such as a combustion device is required. There was also a problem. Moreover, in the aqueous coating liquid described in the above document, the dispersibility of the emulsified particles may become unstable. Therefore, there are cases where the resin composition cannot be adhered to the substrate with a uniform composition, and the substrate with resin obtained from this coating solution has to be solved in terms of electrical characteristics.

[1] A step of emulsifying a cyanate resin and an epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin;
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Attaching the coating solution to a substrate;
Method for producing a resin-base material, characterized in that it and a step of drying the substrate that the coating liquid is attached.
In the present invention, “attaching the coating liquid to the base material” includes both an aspect in which the coating liquid is attached to the surface of the base material and an aspect in which the base material is impregnated with the coating liquid.

[ 2 ] The step of preparing the emulsion includes a step of melt-mixing a cyanate resin, an epoxy resin, and an emulsifier, phase-inversion emulsification by adding water to the molten mixture obtained by the step, and further adding water. Adding the step of preparing the emulsion, and the method for producing a resin-coated substrate according to [ 1 ].

[ 3 ] The method for producing a resin-coated substrate according to any one of [1] or [ 2 ], wherein the curing agent is sparingly water-soluble.

[ 4 ] In any one of [1] to [ 3 ], the emulsifier is contained in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the cyanate resin and the epoxy resin. Manufacturing method of substrate with resin.

[ 5 ] The resin-coated substrate according to any one of [1] to [ 4 ], wherein the epoxy resin is contained in an amount of 20 to 200 parts by weight with respect to 100 parts by weight of the cyanate resin. Production method.

[ 6 ] A step of emulsifying the cyanate resin and the epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin;
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Impregnating the fiber base material with the coating solution;
Drying the fiber substrate impregnated with the coating solution;
The manufacturing method of the prepreg characterized by including.

[ 7 ] A step of emulsifying the cyanate resin and the epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin;
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Attaching the coating solution to the surface of the metal foil;
Drying the metal foil to which the coating solution is attached;
The manufacturing method of the metal foil with resin characterized by including.

  According to the present invention, the safety and the influence on the work environment are reduced, no special equipment for treating the organic solvent is required, and more than equivalent to the substrate with resin using the conventional organic solvent varnish. Provided is a production method capable of obtaining a resin-coated substrate having excellent performance.

Embodiments of the present invention will be described below.
The manufacturing method of the base material with a resin of this embodiment includes the following processes.
(A) A step of preparing a coating solution containing at least 16 parts by weight of an emulsifier, an inorganic filler, a curing agent and water with respect to 100 parts by weight of a cyanate resin, an epoxy resin, and (b) a coating solution on a substrate The process of making it adhere (c) The process of drying the base material which the coating liquid adhered

  In such a manufacturing method, the organic solvent is not substantially contained in the coating solution. Therefore, the safety and the influence on the working environment are reduced, and special equipment for treating the organic solvent is unnecessary. In this embodiment, only water is included as a solvent, but a small amount of an organic solvent, preferably a hydrophilic organic solvent, may be added.

As a base material with resin of this embodiment, a prepreg, metal foil with resin, a film with resin, etc. can be mentioned. Examples of the resin-coated metal foil include a resin-coated copper foil (RCC: Resin Coated Copper foil). In addition, a resin-attached film (RCF: Resin Coated Film) using a film instead of the metal foil may be used.
As the cyanate resin, a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethylbisphenol F type cyanate resin, or a prepolymer thereof can be used.

  The cyanate resin or the prepolymer thereof may have a weight average molecular weight of 150 to 4,500, preferably 300 to 3,000.

  When the weight average molecular weight is less than 150, the substrate with resin is tacky, and when the substrates with resin come into contact with each other, they may adhere to each other or transfer of the resin may occur. Moreover, when it exceeds 4,500, reaction will become quick too much, and when it is set as a laminated board, a shaping | molding defect may arise or interlayer peel strength may fall. Therefore, if it is the said numerical range, the base material with a resin and laminated board which were excellent in all of the said characteristic can be obtained.

  As the epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, arylalkylene type epoxy resin, or a prepolymer thereof may be used. it can.

  The epoxy resin may have a weight average molecular weight of 300 to 15,000, preferably 500 to 10,000.

  When the weight average molecular weight is less than the lower limit, problems such as tackiness may occur in the substrate with resin, and when the upper limit is exceeded, the impregnation property to the substrate is reduced when preparing the substrate with resin. However, there may be a problem that a uniform product cannot be obtained. Therefore, if it is the said numerical range, the base material with a resin and laminated board which were excellent in all of the said characteristic can be obtained.

  By using such a cyanate resin and an epoxy resin, imparting flame resistance, low linear expansion, heat resistance, mechanical properties, and electrical properties, which are basically required as a substrate with a resin and a laminate, are provided. Can do. In this embodiment, the cyanate resin and the epoxy resin are included, and by melting and mixing them, the melt viscosity of the resin is lowered and the subsequent emulsification becomes easy.

  The cyanate resin and epoxy resin preferably have a softening point of 100 ° C. or lower. Thus, after the resin is melted, an operation for emulsification can be easily performed by a usual method, and the obtained emulsion is stable, and in the impregnation drying step, the resin is placed in the fiber base material. It can be easily penetrated. Further, it is preferable that at least one of the cyanate resin and the epoxy resin has a softening point of 40 ° C. or lower. This facilitates heat melting and mixing and emulsification of the resin, and in addition, the resin can sufficiently penetrate between the monofilaments of the fiber base material. Therefore, it is more preferable that at least one of the cyanate resin and the epoxy resin used in the present invention has a softening point of 40 ° C. or lower.

  As an emulsifier in this embodiment, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, and a water-soluble polymer can be used.

  Examples of the anionic emulsifier include fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkane sulfonate sodium salts, and alkyl diphenyl ether sulfonate sodium salts. Can be mentioned.

  Examples of the cationic emulsifier include laurylamine acetate, stearyltrimethylammonium chloride, stearylbenzyldimethylammonium chloride, dodecylpyridium bromide and the like.

  Nonionic emulsifiers include polyoxyalkylene alkyl ether types such as polyoxyethylene alkyl ether, polyoxyalkylene aryl ether types, and polyoxyethylene fatty acid ester types.

  Examples of the water-soluble polymer include polyvinyl alcohol, carboxymethyl cellulose, and methyl cellulose.

  In the present embodiment, a nonionic emulsifier can be used from the viewpoint of dispersion stability of the emulsified particles.

  Hereinafter, it demonstrates in order along each process.

(A) Process of preparing coating liquid The process (a) of preparing the coating liquid in the present embodiment can include the following processes.
(A1) Step of melt-mixing cyanate resin, epoxy resin and emulsifier (a2) Water is added to the molten mixture obtained by step (a1) for phase inversion emulsification, and further water is added to prepare an emulsion. Step (a3) Step of preparing a dispersion by mixing and stirring the inorganic filler and curing agent (a4) Step of preparing a coating solution by mixing and stirring the emulsion and the dispersion

  Hereinafter, each process of a process (a1)-(a4) is demonstrated.

(A1) Step of melting and mixing cyanate resin, epoxy resin, and emulsifier In this step, the cyanate resin, the epoxy resin, and the emulsifier are heated, melted, and mixed.

  In this embodiment, the temperature at which the cyanate resin, the epoxy resin, and the emulsifier are melt-mixed is usually a temperature at which the melt viscosity is such that the resin and the emulsifier can be easily mixed. Moreover, it does not specifically limit about the method of heat-melt-mixing, It can carry out by a well-known method.

  In the conventional method, it is difficult to emulsify with a resin whose softening point is considerably higher than room temperature, and it has been pulverized into fine particles and dispersed in water to form a slurry. In addition, in the prescription using a plurality of resins, there are cases where emulsification and slurrying are required, both the equipment for emulsification and the equipment for slurrying are required, and the burden of equipment investment increases. The process of preparing the water-dispersed resin liquid is also complicated. In the present embodiment, since the cyanate resin and the epoxy resin are heated, melted and mixed together with an emulsifier to be emulsified, the above problems are solved.

  In this step, the epoxy resin can be used in an amount of 20 to 200 parts by weight, preferably 30 to 150 parts by weight with respect to 100 parts by weight of the cyanate resin. If it is less than the said lower limit, the reactivity of cyanate resin may fall, or the moisture resistance of the product obtained may fall. On the other hand, if the upper limit is exceeded, the heat resistance may decrease. Therefore, it is preferable that it is the said numerical range from the viewpoint of the reactivity of cyanate resin, the moisture resistance of the product obtained, and heat resistance.

  The emulsifier can be used in an amount of 16 to 30 parts by weight, preferably 16 to 25 parts by weight, based on 100 parts by weight of the epoxy resin. If it is less than the lower limit, the emulsified particles in the coating solution are unstable, and there is a problem in dispersion stability such that the resin once emulsified is re-agglomerated. Therefore, since the glass substrate cannot be impregnated with a uniform composition or attached to the surface of the metal foil with a uniform composition, the resin-coated substrate obtained from this emulsion has a problem in electrical characteristics. On the other hand, when the above upper limit is exceeded, the amount of emulsifier is excessive, which may adversely affect the heat resistance and peeling properties of the laminate. Therefore, if it is in these numerical ranges, the base material with a resin excellent in the dispersion stability of an emulsion and excellent in the electrical property, and the laminated board excellent in heat resistance and peeling property can be obtained.

  The emulsifier can be used in an amount of 1 part by weight or more and 10 parts by weight or less, preferably 3 parts by weight or more and 8 parts by weight or less based on 100 parts by weight of the total amount of cyanate resin and epoxy resin.

  Within the above numerical range, it is possible to obtain a substrate with a resin that is particularly excellent in dispersion stability of the emulsion and that is excellent in electrical characteristics, and further that it is possible to obtain a laminated board that is excellent in heat resistance and peeling characteristics.

(A2) Step of adding water to the molten mixture obtained in step (a1) to perform phase inversion emulsification, and further adding water to prepare an emulsion In this step, cyanate as in step (a1) above After melt-mixing the resin, the epoxy resin, and the emulsifier, a predetermined amount of water is gradually added to and mixed with the molten mixture to perform phase inversion emulsification from W / O type to O / W. In addition, it is preferable that the added water is heated to the same extent as the molten resin.

  The method of phase inversion emulsification is not particularly limited. For example, known stirring and mixing such as a homogenizer, a disperser, and a CLEARMIX are performed while sequentially adding water (preferably, heated water) to a molten mixture that has been previously heated and melted and mixed. A method of dispersing using an apparatus is adopted.

  When transfer emulsification is confirmed, the remaining amount of water is added to prepare an emulsion. In addition, it is preferable that the water added when preparing the emulsion is also heated to the same extent as the molten resin.

  The average particle size of the emulsion particles is preferably 0.1 μm or more and 30 μm or less, more preferably 0.1 μm or more and 10 μm or less. Due to being in this range, the emulsified resin liquid can be made to have a high concentration and low viscosity, and the resin particles can easily enter between the fibers of the base material, and have excellent coating impregnation properties. Can do. Furthermore, the resin particles can be uniformly attached to the surface of the metal foil, and the coating property can be improved. Since the resin concentration of the aqueous emulsion resin liquid is high, energy consumed for drying can be reduced. Therefore, the prescription with little environmental impact can be provided with the advantage by not using an organic solvent substantially. When the average particle diameter of the emulsion particles is larger than the above upper limit value, the dispersed emulsion particles may be re-aggregated and separated and precipitated.

  As mentioned above, by heating and melt mixing cyanate resin, epoxy resin and emulsifier into aqueous emulsion resin liquid, there is no need for large capital investment, excellent handling of resin liquid, and impregnation into fiber base material Since it has excellent properties, it is extremely useful as a formulation that does not substantially use an organic solvent.

(A3) Step of preparing a dispersion by mixing and stirring the inorganic filler and the curing agent In this step, separately from the emulsion prepared in the step (a2), mixing and stirring the inorganic filler and the curing agent, the dispersion is prepared. Prepare.

  Inorganic fillers include aluminum hydroxide, kaolin clay, hydrotalcite, attapulgite, sepiolite, mica, zinc stannate, silica, colemanite, brucite, talc, synthetic magnesium hydroxide, calcium carbonate, etc. Silica and talc are preferred because they maintain the same. The average particle size is preferably 0.1 to 5 μm in order to improve water dispersibility and impregnation. Accordingly, silica and talc having an average particle size of 0.1 to 5 μm are particularly preferable. Such an inorganic filler is preferably treated with a coupling agent, but a coupling agent may be added in advance to the aqueous emulsion resin liquid.

  By blending inorganic fillers, without lowering the characteristics of the substrate with resin and the laminate, the thermal expansion coefficient of the laminate is reduced and the heat resistance is improved. be able to. Although it does not specifically limit as a compounding quantity, It is preferable that it is 30-80 weight% with respect to 100 weight% (solid content) of the whole composition containing resin and a filler, More preferably, it is 40-75 weight%.

  When the amount is less than the lower limit, the effect of reducing the flame resistance and the coefficient of thermal expansion may be insufficient. In particular, if the difference between the thermal expansion of components mounted on the laminated board is large, a problem may occur in reliability of a thermal cycle test or the like. On the other hand, if the upper limit is exceeded, the thixotropy of the resin liquid also increases, and the impregnation property and the appearance of the substrate with the resin or the laminated plate may be lowered, and the workability such as drilling of the laminated plate is lowered. Tend to. Moreover, a heat resistance fall may be seen from the relative shortage of resin. Therefore, it is preferable to be within the above numerical range from the viewpoints of improvement in flame resistance and thermal expansion rate, improvement in impregnation property, appearance of a substrate with resin or laminate, and workability of the laminate.

  As the curing agent that can be contained in the dispersion, a curing agent that is hardly soluble in water can be used. By using such a curing agent, curing of the resin can be suppressed until the heat drying step, and the storage stability of the coating liquid can be improved.

Moreover, when the hardener which is hardly soluble in water was used, the heat resistance and electrical characteristics of the prepreg tended to be further improved as compared with a hardener readily soluble in water. This is considered to be due to the following reason.
When an easily soluble curing agent is used in water, only the curing agent dissolved in the coating solution may pass through the gap between the glass cloths and the emulsified particles, the inorganic filler, or the like may not pass through when preparing the prepreg. That is, in the glass cloth, a region where only the curing agent is distributed and a region where the curing agent and the emulsified particles or the inorganic filler coexist coexist, and in this coexisting region, the amount of the curing agent with respect to the resin decreases. Sometimes. Therefore, the prepreg obtained from such a glass cloth has a region in which the amount of the curing agent relative to the resin is reduced, so that the curability of the resin composition is not sufficient, and the heat resistance and electrical characteristics are improved. There was a point. For example, such a phenomenon was observed when dicyandiamide (the solubility in water 100 g of water at 15 ° C. was 2.56 g (14906 chemical product, Chemical Industry Daily)) was used.

  On the other hand, when a curing agent having a solubility in 100 g of water at a water temperature of 15 ° C. is 2 g or less as the above-described curing agent that is hardly soluble in water, the curing agent is hardly dissolved in the coating solution. In addition, only the curing agent does not pass through the gap of the glass cloth. That is, in the glass cloth, since the curing agent and the resin or the like are present in a predetermined amount ratio, sufficient curability is obtained, and the heat resistance and electrical characteristics of the prepreg are further improved. Examples of such a water-insoluble curing agent include acid anhydride compounds, amine compounds, imidazole compounds, and novolak type phenol resins.

  Moreover, a hardening accelerator can also be used and an imidazole compound, a tertiary amine compound, etc. can be mentioned as such. A finely pulverized curing agent and curing accelerator may be added to water together with an inorganic filler and mixed with stirring, or may be added to an aqueous dispersion such as a slurry containing an inorganic filler and mixed with stirring.

(A4) Step of preparing a coating solution by mixing and stirring the emulsion and the dispersion liquid In this step, the emulsion prepared in the step (a2) and the dispersion liquid prepared in the step (a3) are mixed and stirred. Prepare the coating solution.
Thus, in this embodiment, since the emulsion and the dispersion are separately prepared, the degree of freedom of the preparation conditions such as temperature and preparation time is improved as compared with the case of preparing the coating liquid in a lump, The preparation conditions can be optimized. Thereby, dispersion stability of cyanate resin, an epoxy resin, an inorganic filler, a hardening | curing agent, etc. in a coating liquid can be improved, and a coating liquid can be made to adhere to a base material with a uniform composition. Therefore, the substrate with resin obtained from the coating solution is excellent in electrical characteristics.

  In the present embodiment, additives such as an antifoaming agent, a leveling agent, an antioxidant, a surfactant, a coloring agent, and a coupling agent can be blended in the coating solution as necessary. As described above, the coating liquid used for obtaining the substrate with resin of the present embodiment can be obtained.

(B) The process of making a coating liquid adhere to a base material Hereinafter, a process (b) is demonstrated in the case of preparing metal foil with resin, when preparing a prepreg.
In this step, when preparing a prepreg, the fiber base material is impregnated with the above coating solution. As the method, for example, the coating liquid is sprayed onto the base material using a spraying device such as a spray nozzle, the base material is immersed in the resin liquid, the knife coater, the comma coater and the like. Examples thereof include a method of coating the resin liquid on the substrate with a coater or a method of transferring the resin liquid to the substrate with a transfer roll.

  Among these, in the method in which the resin liquid is applied to the base material by the spraying device, the resin liquid sprayed from the spraying device collides with the base material with energy, so that the impregnation into the base material is improved. It is preferable.

  In addition, when applying a method of spraying a resin liquid onto a base material using a spraying device or a method of immersing a base material in a resin liquid, it may be performed only by that method or carrying A comma coater, knife coater, squeeze roll, or the like may be used in combination to adjust the amount of the resin composition to be adjusted and to improve the smoothness of the prepreg surface.

The fiber substrate used in the prepreg manufacturing method of the present invention is not particularly limited, and examples thereof include woven fabrics or nonwoven fabrics such as glass fibers, fluororesin fibers, and aramid fibers, paper, glass fiber nonwoven fabrics, and the like. A mat made of chops can also be used.
On the other hand, in this step, when preparing a resin-coated metal foil, for example, a method of spraying the coating liquid onto the metal foil using a spray device such as a spray nozzle, various coaters such as a knife coater and a comma coater The method of applying the resin solution to the substrate by the method, the method of transferring the resin solution to the substrate by a transfer roll, and the like.

(C) The process of drying the base material which the coating liquid adhered In this process, after making a coating liquid adhere to a base material as mentioned above, this is heat-dried. Thereby, substantially all of the water evaporates, and the resin component or the like melts to lower the viscosity, and can be uniformly attached to the substrate. In addition, you may add heat until a resin component will be in a semi-hardened state as needed. Although it does not specifically limit as conditions to heat-dry, Usually, 100-220 degreeC, Preferably it carries out at 120-190 degreeC for 2 to 10 minutes.

  In addition, the amount (solid content) of the resin composition supported on the substrate with resin is not particularly limited, but is usually about 40 to 60% by weight with respect to the entire substrate with substrate (substrate + resin composition). is there.

A laminated board can be manufactured by heat-pressing the base material with resin obtained by such a manufacturing method. The heat and pressure molding can be performed under the same conditions as in the case of molding a prepreg from a resin varnish using a conventional organic solvent, for example, at a temperature of 170 to 200 ° C. and a pressure of 20 to 40 kg / cm ² . Heat and press for ~ 200 minutes. In this way, it is possible to obtain a laminated plate having excellent heat resistance and no voids, equivalent to the conventional one.

  In the manufacturing method of this embodiment, since an organic solvent is not substantially used, resource saving, energy saving, and cost reduction are achieved, and further, it contributes to improvement of the working environment and reduction of air pollution. It is something that can be done.

[Example]
Hereinafter, the present invention will be described in detail with reference to examples. “Parts” and “%” described herein represent “parts by weight” and “% by weight”, respectively.

[Example 1]
Biphenyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C.) is used as the epoxy resin, and novolak type cyanate resin (Primaset, PT-30, manufactured by Lonza Japan Co., Ltd., softening point) is used as the cyanate resin. 30 ° C.) was used. Furthermore, a polyoxyethylene aryl ether type surfactant (Emulgen A-500, manufactured by Kao Corporation) was used as an emulsifier.

  56.5 g of epoxy resin and 100 g of cyanate resin were heated and mixed at 90 ° C. together with 10 g of emulsifier. Using a disperser, 20 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes while stirring the heated and melted resin with a 40 mm stirring blade at 6000 rpm, followed by further stirring and mixing for 40 minutes. Emulsified. Furthermore, 40 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes to prepare an aqueous emulsion resin solution having an average particle size of 0.7 μm.

  In addition, a silica slurry treated with a coupling agent as an inorganic filler (Admafine SC2050-WND, manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, filler content 70%) 241.6 g, phenol resin (GPH-103, A dispersion was prepared by stirring and mixing 17.5 g of a finely pulverized product in a jet mill and 0.06 g of a curing accelerator (P-200K, manufactured by Japan Epoxy Resin Co., Ltd.).

The dispersion liquid was mixed with the aqueous emulsion resin liquid obtained as described above to obtain a coating liquid for impregnation. This impregnating resin solution was impregnated and applied to a glass cloth (Nitto Boseki Co., Ltd., WE116E-S136, thickness 100 μm) and dried by heating at 170 ° C. for 5 minutes to obtain a prepreg. The resin liquid solid content in the prepreg was 50% by weight.
Further, the obtained aqueous emulsion resin liquid was stored at 10 ° C. for 1 month and then taken out, and the presence or absence of the occurrence of aggregates was visually confirmed according to the following criteria. The results are shown in Table 1.
○: No aggregate ×: There is aggregate

[Example 2]
Biphenyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C.) is used as the epoxy resin, and novolak type cyanate resin (Primaset, PT-30, manufactured by Lonza Japan Co., Ltd., softening point) is used as the cyanate resin. 30 ° C), a polyoxyethylene aryl ether type surfactant (Emulgen A-500, manufactured by Kao Corporation) as an emulsifier, and imidazole (1B2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. used.

  After 56.5 g of epoxy resin and 100 g of cyanate resin were heated and mixed at 90 ° C. with 10 g of emulsifier, 0.03 g of a curing accelerator was added, and the above heat-melted resin was added with a 40 mm stirring blade using a disperser. While stirring at 6000 rpm, 20 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes, and further stirred and mixed for 40 minutes for phase inversion emulsification. Furthermore, 40 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes to prepare an aqueous emulsion resin solution having an average particle size of 0.7 μm.

  In addition, a silica slurry treated with a coupling agent as an inorganic filler (Admafine SC2050-WND, manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, filler content 70%) 241.6 g, phenol resin (GPH-103, Nippon Kayaku Co., Ltd.) 17.5 g of finely pulverized product in a jet mill was stirred and mixed to prepare a dispersion.

The dispersion liquid was mixed with the aqueous emulsion resin liquid obtained as described above to obtain a coating liquid for impregnation. This impregnating resin solution was applied to a glass cloth (Nitto Boseki Co., Ltd., WE116E-S136, thickness 100 μm) by a spray method and dried by heating at 170 ° C. for 5 minutes to obtain a prepreg. The resin liquid solid content in the prepreg was 50% by weight.
Further, the obtained aqueous emulsion resin solution was stored at 10 ° C. for 1 month and then taken out, and in the same manner as in Example 1, the presence or absence of aggregates was confirmed. The results are shown in Table 1.

[Example 3]
Biphenyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd., softening point 70 ° C.) is used as the epoxy resin, and novolak type cyanate resin (Primaset, PT-30, manufactured by Lonza Japan Co., Ltd., softening point) is used as the cyanate resin. 30 ° C), a polyoxyethylene aryl ether type surfactant (Emulgen A-500, manufactured by Kao Corporation) as an emulsifier, and imidazole (1B2PZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) as a curing accelerator. used. Further, a silica slurry treated with a coupling agent as an inorganic filler (Admafine SC2050-WND, manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, filler content 70%) and phenol resin (GPH-103, Nippon Kayaku) A dispersion obtained by mixing and stirring a finely pulverized product in a jet mill and adjusting the concentration with ion-exchanged water was used.

  After 56.5 g of epoxy resin and 100 g of cyanate resin were heated and mixed at 90 ° C. with 10 g of emulsifier, 0.03 g of a curing accelerator was added, and the above heat-melted resin was added with a 40 mm stirring blade using a disperser. While stirring at 6000 rpm, 20 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes, and further stirred and mixed for 40 minutes for phase inversion emulsification. Further, a dispersion obtained by previously dispersing and mixing 241.6 g of silica slurry, 17.5 g of phenol resin and 40 g of ion-exchanged water was heated to 75 ° C. and added in small portions over 10 minutes, and an impregnation solution having an average particle size of 0.9 μm Was prepared.

  The impregnating resin solution obtained as described above was impregnated and applied to glass cloth (manufactured by Nitto Boseki Co., Ltd., WE116E-S136, thickness 100 μm), and dried by heating at 170 ° C. for 5 minutes to obtain a prepreg. The resin liquid solid content in the prepreg was 50% by weight.

[Comparative Example 1]
As in Example 1, biphenyl type epoxy resin (NC-3000H, Nippon Kayaku Co., Ltd., softening point 70 ° C.) was used as the epoxy resin, and novolak type cyanate resin (Primaset, PT-30, Lonza) as the cyanate resin. Japan Co., Ltd., softening point 30 ° C.) was used. Furthermore, a polyoxyethylene aryl ether type surfactant (Emulgen A-500, manufactured by Kao Corporation) was used as an emulsifier.

  56.5 g of epoxy resin and 100 g of cyanate resin were heated and mixed at 90 ° C. together with 7 g of emulsifier. Using a disperser, 20 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes while stirring the heated and melted resin with a 40 mm stirring blade at 6000 rpm, followed by further stirring and mixing for 40 minutes. Emulsified. Furthermore, 40 g of ion-exchanged water heated to 90 ° C. was added in small portions over 10 minutes to prepare an aqueous emulsion resin solution having an average particle size of 0.7 μm.

  In addition, a silica slurry treated with a coupling agent as an inorganic filler (Admafine SC2050-WND, manufactured by Admatechs Co., Ltd., average particle size 0.5 μm, filler content 70%) 241.6 g, phenol resin (GPH-103, A dispersion was prepared by stirring and mixing 17.5 g of a finely pulverized product in a jet mill and 0.06 g of a curing accelerator (P-200K, manufactured by Japan Epoxy Resin Co., Ltd.).

  The dispersion liquid was mixed with the aqueous emulsion resin solution obtained as described above to prepare an impregnation coating solution. However, aggregation occurred during mixing and stirring, and the solution could not be used as the impregnation resin solution.

  From this result, it can be seen that the prepreg and resin-coated metal foil having excellent electrical characteristics can be obtained by the coating solution of the present invention.

Claims (7)

A step of emulsifying a cyanate resin and an epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin; and
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Attaching the coating solution to a substrate;
And drying the substrate to the coating liquid is attached,
The manufacturing method of the base material with resin characterized by including. The step of preparing the emulsion comprises:
Melting and mixing a cyanate resin, an epoxy resin and an emulsifier;
Adding water to the molten mixture obtained by the above step to phase inversion emulsification, and further adding water to prepare the emulsion;
Method for producing a resin-base material according to claim 1, characterized in that it comprises a. The method for producing a resin-coated substrate according to claim 1 or 2 , wherein the curing agent is sparingly water-soluble. The resin-coated substrate according to any one of claims 1 to 3 , wherein the emulsifier is contained in an amount of 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the total amount of the cyanate resin and the epoxy resin. Manufacturing method. The relative cyanate resin 100 parts by weight, the epoxy resin 20 parts by weight or more, the production method of the resin-based material according to any one of claims 1 to 4, characterized in that it comprises 200 parts by weight or less. A step of emulsifying a cyanate resin and an epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin; and
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Impregnating the fiber base material with the coating solution;
Drying the fiber substrate impregnated with the coating solution;
The manufacturing method of the prepreg characterized by including. A step of emulsifying a cyanate resin and an epoxy resin in water with an emulsifier of 16 parts by weight or more and 30 parts by weight or less based on 100 parts by weight of the epoxy resin; and
A step of mixing and stirring a slurry containing an inorganic filler and a curing agent to prepare a dispersion;
A step of mixing and stirring the emulsion and the dispersion to prepare a coating solution;
Attaching the coating solution to the surface of the metal foil;
Drying the metal foil to which the coating solution is attached;
The manufacturing method of the metal foil with resin characterized by including.