JP2012151118A - Dielectric constant conditioner and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dielectric constant conditioner capable of achieving a desired dielectric constant and less in change of resin characteristics and reactivity, and to provide a resin composition including the dielectric constant conditioner.SOLUTION: In a dielectric constant conditioner, an organic material is first filled in a pore of a porous material at 1-99 vol.% of total pore capacity, then a resin for fixing the organic material is filled at 30-100 vol.% of the remaining capacity of the pore capacity. In the dielectric constant conditioner, a mixture in which an organic material and a resin for fixing the organic material are mixed is filled at 5-100 vol.% of the total pore capacity of the porous material. The resin composition includes 1-700 pts. mass of the dielectric constant conditioner dispersed in 100 pts. mass of a resin.

Description

  The present invention relates to a dielectric constant adjusting agent and a resin composition in which a dielectric constant adjusting agent is dispersed in a resin.

  Conventionally, the relative dielectric constant of a resin is adjusted by mixing the resin and a material (dielectric constant adjusting agent) having a different relative dielectric constant from that of the resin. Examples of the contact mixing method include a method of uniformly dissolving the dielectric constant adjusting agent in the resin, a method of dispersing and mixing the dielectric constant adjusting agent in the resin, and a method of providing voids in the resin. However, with these methods, it is possible to adjust the required dielectric constant of the resin, but the original strength of the resin, glass transition temperature, etc. cannot be maintained, and these physical properties are relative to those of the resin. It is known that it is intermediate or lower than that of materials with different rates. In addition, depending on the types of materials having different relative dielectric constants to be mixed, when the materials having different relative dielectric constants are uniformly dissolved (compatibilized) in the resin, the reaction rate (for example, the curing rate) of the resin may decrease or increase. In addition, there are problems in terms of chemical properties such as difficulty in reaction control, in addition to physical properties such as heat resistance (including glass transition temperature, dimensional stability against heat, etc.), dielectric loss tangent, adhesion, mechanical strength, etc. There was also a problem in terms of characteristics. As described above, when the dielectric constant adjusting agent is contact-mixed with the resin, there is a problem that the performance of the characteristic originally expected from the resin is lowered and not all the desired performance can be obtained.

  Another possible method is to immobilize an organic substance having a dielectric constant different from that of the resin in the porous material and use the porous material thus obtained. However. According to this method, there is an advantage that the relative permittivity can be reduced while suppressing the influence of the organic matter on the reactivity and physical properties. However, when the porous material is stored in a solvent for a long time, the impregnated organic matter is dissolved. It turned out that the bad influence of organic matter comes out.

  An object of the present invention is to provide a dielectric constant adjusting agent that can achieve a resin having a desired relative dielectric constant and has little change in properties and reactivity of the resin, and a resin composition using the same. is there.

  In order to solve the above-described problems, the present inventors have filled the organic material in the pores of the porous material, fixed the organic material filled in the pores with a resin, and the organic material filled in the pores. A dielectric constant adjusting agent capable of achieving the above-mentioned object by preventing the resin from contacting or elution from the resin outside the pores of the porous material, and a resin composition using the same, have been found. It came to complete.

Thus, according to the present invention, the following inventions 1 to 11 are provided.
1. First, the pores of the porous material were filled with organic matter in an amount of 1 to 99% by volume of the whole pore volume, and then the organic matter fixing resin was filled with 30 to 100% by volume of the unfilled volume of the pore volume. Characteristic dielectric constant modifier.
2. A dielectric constant adjuster characterized by filling a mixture of an organic substance and an organic substance fixing resin in an amount of 5 to 100% by volume of the entire pore volume of the porous material.
3. Item 3. The dielectric constant adjusting agent according to Item 2, wherein the ratio of the organic substance in the mixture obtained by mixing the organic substance and the organic substance fixing resin is 10 to 90% by volume.
4). Item 4. The dielectric constant adjusting agent according to any one of Items 1 to 3, wherein the organic material filled in the pores of the porous material is solid at 20 ° C.
5. Item 5. The dielectric constant adjuster according to any one of Items 1 to 4, wherein the pore volume of the porous material is 10 to 700 ml / 100 g in terms of oil absorption.
6). Item 6. The dielectric constant modifier according to any one of Items 1 to 5, wherein the porous material has an average particle diameter of 0.1 to 100 µm.
7). Item 7. The dielectric constant modifier according to any one of Items 1 to 6, wherein the porous material has an average pore diameter of 0.5 to 1000 nm.
8). Item 8. The dielectric constant modifier according to any one of Items 1 to 7, wherein the porous material is porous silica.
9. Item 9. The dielectric constant adjusting agent according to any one of Items 1 to 8, wherein the organic substance or the organic substance fixing resin filled in the pores has thermosetting properties.
10. Item 11. A resin composition, wherein 1 to 700 parts by mass of the dielectric constant adjusting agent according to any one of Items 1 to 9 are dispersed in 100 parts by mass of a resin.
11. Item 11. The resin composition according to Item 10, which has thermosetting properties.

  The dielectric constant adjusting agent of the present invention and the resin composition using the same can change the relative dielectric constant of the resin to a desired relative dielectric constant, and are less affected by changes in properties and reactivity applied to the resin.

  The porous material used in the present invention may be any material as long as it has pores, and the material is not particularly limited. Examples of the porous material include spherical porous silica powder, porous silica powder, porous silica gel, zeolite, calcium silicate, activated carbon and the like, and porous silica powder is particularly preferable. In addition, the shape of the porous material is not particularly limited, and examples thereof include a spherical shape, a scale shape, and an indeterminate shape, and a spherical material is particularly preferable since the inhibition on the fluidity of the resin is small. Moreover, the average particle diameter of a porous material is 0.1-100 micrometers, Preferably it is 0.2-20 micrometers, More preferably, it is 0.3-10 micrometers.

  The pore volume of the porous material is 10 to 700 ml / 100 g, preferably 50 to 500 ml / 100 g, more preferably 100 to 400 ml / 100 g in terms of the oil absorption amount of JIS K 510.01 oil method. If the amount of oil absorption is 10 ml / 100 g or more, the effect of expressing flame retardancy is good, and if it is 700 ml / 100 g or less, the strength of the porous material is sufficient. The average pore diameter is 0.5 to 1000 nm, preferably 3 to 100 nm, more preferably 5 to 50 nm. When the average pore diameter is 0.5 nm or more, the organic material can be easily filled. On the other hand, when the average pore size is 1000 nm or less, the contact area with the resin is not large and the outflow amount of the organic material does not increase. The material, shape, average pore diameter, oil absorption, and average particle diameter of the porous material may be the same, or two or more types may be different.

  When the organic material is filled in the pores of the porous material and the organic material fixing resin is filled in the upper portion of the organic material, the filling ratio of the organic material into the pores of the porous material is 1 to 1 of the entire pore volume. It is 99 volume%, Preferably it is 1-90 volume%, More preferably, it is 20-80 volume%. When the filling ratio of the organic substance into the pores is 1% by volume or more of the whole pore volume, the porous material is sufficiently isolated from inside and outside the pores. This means that, for example, when an organic substance is filled in the pores under normal pressure, air remains in the pores after the organic substance is filled. The periphery of the portion where the air remains is surrounded by an organic substance and an organic substance fixing resin and blocked from the outside, so that the air can be fixed inside the pores. Since the dielectric constant of air is the lowest among the materials and is almost 1, this air dielectric constant can be reduced. Further, this air amount can be changed under reduced pressure conditions. It means that the air remaining inside the pores can be isolated inside the pores so as not to leak out to the outside of the pores and can withstand the pressure applied from the outside due to the strength of the porous material.

  The filling rate of the organic substance fixing resin is 30 to 100% by volume, preferably 40 to 95% by volume, more preferably 50 to 90% by volume of the unfilled volume of the pore volume filled with the organic substance. When the filling rate of the organic matter fixing resin is 30% by volume or more of the unfilled volume, the organic matter sequestration effect is sufficient. That is, the organic substance does not come into contact with the solvent or the surrounding resin by the organic substance fixing resin.

  In the case of obtaining a dielectric constant adjusting agent by filling a mixture of an organic substance and an organic substance fixing resin into the pores of the porous material to obtain a dielectric constant adjusting agent, first, an organic substance fixing resin is prepared, dissolved, and the organic substance is put therein. Dissolve and mix thoroughly to make a mixture. Then, 5-100 volume% of the mixture of organic substance and organic substance fixing resin is filled with respect to the whole pore volume of the porous material. Moreover, the ratio of the organic substance in a mixture is 10-90 volume%, Preferably it is 30-80 volume%, More preferably, it is 30-70 volume%. When the organic substance is 10% by volume or more, the effect of reducing the dielectric constant is exhibited. On the other hand, when the organic substance is 90% by volume or less, the effect of fixing the organic substance by the organic substance fixing resin is exhibited.

  In the present invention, in order to fill an organic substance or an organic substance fixing resin, it is necessary to make these materials liquid. If the material is in a liquid state, the pore diameter of the porous material is small, so that the liquid material is filled inside the pores by capillary action. Therefore, when the volume of the liquid material is smaller than the pore volume of the porous material, the liquid material is all sucked into the pore space of the porous material. For this reason, the filling amount of the liquid material into the pores depends on the blending amount of the organic substance and the organic substance fixing resin, and the filling amount is adjusted by adjusting the blending amount. However, in order to completely fill the liquid material into the pores, it is necessary to reduce the pressure before extracting the air from the pores before filling the material. This is because if there is air inside the pores, it becomes difficult to finally completely fill the pores with the material. However, when filling is performed at normal pressure and air is trapped inside, the dielectric constant becomes lower than that of complete filling. At normal pressure, filling is possible only up to a spatial volume of about 70 to 80% of the pore volume of the porous material. Conversely, when it is desired to increase the amount of air, filling under pressure is effective.

  In the present invention, the organic material filled in the pores of the porous material may be any material as long as the dielectric constant is different from that of the resin containing the dielectric constant adjusting agent, and is 20 ° C. in order to suppress dissolution of the organic material in the resin. From the point of flowing into the pores, the fluid viscosity is 1000 Pa · s or less (10000 poise or less), preferably 10 Pa · s or less (100 poise or less), more preferably 5 Pa. -It is the thing which is s or less (50 poise or less). Organic materials include polyethylene, polypropylene, polyester, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyether ether ketone, polyethylene oxide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene Thermosetting of thermoplastic resins such as polyvinyl ether, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, malein resin, melamine resin, urea resin Pressure of organic resin, wax, etc. that have fluidity by heating with photosensitive resin, epoxy resin, photosensitive resin, melting point, softening point Organic matter having fluidity can include a liquid organic substances at room temperature such as a solvent. However, the organic substance used in the present invention is not particularly limited. Moreover, the organic substance to be filled may be one type or two or more types.

  In the present invention, the organic substance fixing resin filled in the pores of the porous material may be any material as long as it can be mixed with a dielectric constant adjusting agent and does not dissolve in the solvent. However, the organic fixing resin is preferably a solid at 20 ° C. in order to suppress dissolution in the resin, and the viscosity during flow is 1000 Pa · s or less (10,000 poises) from the point of flowing into the pores. The following is more preferable, and it is more preferable that it is curable.

  Examples of organic fixing resins include polyethylene, polypropylene, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyetheretherketone, polyethylene oxide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, Thermoplastic resins such as polybutadiene and polyvinyl ether, monomer or semi-cured epoxy resin, xylene resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, malein resin, melamine resin, urea resin And a photosensitive resin such as a monomer or a semi-cured epoxy acrylate. However, the organic substance fixing resin used in the present invention is not particularly limited. Moreover, the organic substance fixing resin to be filled may be one type or two or more types.

  In the present invention, the method of filling the organic material into the pores of the porous material is not particularly limited. For example, a method of stirring a liquid organic substance and a porous material and filling the pores, a method of stirring a liquid organic substance and a porous material under pressure and filling the pores, a liquid state after reducing the pressure A method of charging a porous material into the organic material and stirring to fill the pores, a method of mixing the porous material and the organic material in advance and dissolving the organic material by heating to fill the pores, A method of mixing the material and the organic material, reducing the pressure and then dissolving the organic material by heating to fill the pores, mixing the porous material and the organic material in advance and dissolving the organic material by applying pressure and heating A method of filling in the pores, a method of dissolving the organic substance with a solvent and stirring it with the porous material and filling the pores, a solvent dissolving the organic substance with a solvent and stirring the porous material and filling the pores After that, the method of removing the solvent by heating, the organic substance is dissolved with a solvent etc. Stirring the material was filled into the pores, and a method for removing the solvent by heating under reduced pressure.

  The porous material that has been filled with the organic substance may be washed with a solvent or the like in order to remove the organic substance remaining outside the porous material before being used as a dielectric constant adjusting agent. Moreover, in order to improve the filling property of organic matter before filling with organic matter, the pore surface of the porous material may be treated with a coupling agent or the like. The dielectric constant modifier filled with an organic substance may be surface-treated with a coupling agent or the like in order to enhance dispersibility, or may be subjected to a treatment such as pulverization to reduce the particle size.

  The organic material fixing resin is then filled into the unfilled pores of the porous material that has been filled with the organic material. The method of filling the organic substance fixing resin is essentially the same as the method of filling the organic substance. The porous material impregnated with organic matter is taken out of the container and heated to cure the organic substance fixing resin, and a dielectric constant adjusting agent is prepared. The filled dielectric constant adjusting agent may be surface-treated with a coupling agent or the like in order to enhance dispersibility.

  The method of filling the mixture of organic substance and organic substance fixing resin into the pores of the porous material is essentially organic substance, then organic substance fixation, except that the mixture of organic substance and organic substance fixing resin is used in advance. There is no difference from the method of filling the resin. The filled dielectric constant adjusting agent may be surface-treated with a coupling agent or the like in order to improve dispersibility, or may be pulverized to reduce the particle size.

  When mix | blending the dielectric constant modifier of this invention in resin, 1-700 mass parts of a dielectric constant regulator is used with respect to 100 mass parts of resin, Preferably it is 30-600 mass parts, More preferably, 50-500 mass parts is used. Is preferred. When the blending amount of the dielectric constant adjusting agent is 1 part by mass or more, the effect of adjusting the dielectric constant is exhibited, and when it is 700 parts by mass or less, the resin composition is easily handled. Further, in order to improve the dispersibility of the dielectric constant adjusting agent, it may be dispersed by using a kneading method such as kneader, ball mill, bead mill, three rolls, nanomizer, etc., and the dielectric constant adjusting agent is in the state of the resin composition. May be pulverized and dispersed with a reduced particle size.

  In the present invention, the resin in which the dielectric constant adjusting agent is dispersed may be arbitrary. Such resins include polyethylene, polypropylene, polyamide, polyamideimide, polyarylate, thermoplastic polyimide, polyether ether ketone, polyethylene oxide, polyethylene terephthalate, polyvinylidene chloride, polyvinyl chloride, polycarbonate, polyvinyl acetate, polystyrene, polybutadiene. Thermosetting of thermoplastic resins such as polyvinyl ether, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin, polyimide, polyurethane, malein resin, melamine resin, urea resin And photosensitive resins such as epoxy resins and epoxy acrylates. However, the resin used in the present invention is not particularly limited. Moreover, the dielectric constant adjusting agent to be dispersed may be one type or two or more types.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited thereto.
In this example and comparative example, TG-DTA was used as a method for confirming the volume% after the organic substance and the organic substance fixing resin were filled in the pores. That is, the organic substance and the organic substance fixing resin were heated to 1000 ° C. and burned, and the decomposition residue was calculated from the specific gravity using the mass of the porous material and the decomposition component as the organic substance. Further, in the two-stage filling, it was confirmed by burning twice in the intermediate stage and the final stage and measuring the decomposition residue.
The dielectric constant was measured at 1 GHz using an RF impedance / material analyzer (manufactured by Agilent Technologies, HP 4291B).

Example 1
(1) Liquid epoxy resin (Japan Epoxy Resin Epicoat 815), liquid phenol (Maywa Kasei, MEH-8000H), and imidazole as a curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd.) 2E4MZ) was used. 50 parts by mass of a liquid epoxy resin (Epicoat 815), 37.9 parts by mass of liquid phenol (MEH-8000H) and 0.5 parts by mass of imidazole (2E4MZ) were placed in a beaker and stirred and mixed at 25 ° C. for 1 hour.
(2) As a porous material, porous silica (oil absorption 150 ml / 100 g, average particle size 1.1 μm, Suzuki Oil & Fat Industries, Inc., God Ball E-2C (trade name))) is used as an organic substance to be filled. Acid ester (melting point 95 ° C., PX-200 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Take 200 parts by weight of porous silica (E-2C) and 207 parts by weight of condensed phosphate ester (PX-200) in a four-necked separable flask equipped with a thermometer, a condenser, a decompressor, and a stirrer and stir. The pressure in the four-neck separable flask was reduced. After confirming that the pressure in the four-neck separable flask has dropped to 10 mmHg or less, heat the four-neck separable flask so that the internal temperature becomes 120 ° C., and heat and stir for 1 hour while maintaining the temperature. The condensed phosphate ester was filled in the pores of the porous silica at 60% by volume with respect to the pore volume.
(3) After filling, the four-neck separable flask is cooled to 50 ° C., 72 parts by mass of the organic substance fixing resin prepared in (1) is taken into the four-neck separable flask, and the four-neck separable flask is stirred. The inside of the flask was depressurized. After confirming that the pressure in the four-neck separable flask has dropped to 10 mmHg or less, heat the four-neck separable flask so that the internal temperature becomes 120 ° C., and stir for 1 hour while maintaining the temperature. Then, the organic substance fixing resin was filled into the pores of the porous silica at 50% by volume of the unfilled volume of the pore volume.
(4) After filling, the four-necked separable flask is cooled to 50 ° C., the porous silica impregnated with the organic matter is taken out, heated at 180 ° C. for 2 hours to cure the organic substance fixing resin, and the dielectric constant adjuster Was made.
(5) Take 10 parts by mass of methanol, 40 parts by mass of diphenyldimethoxysilane, and 20 parts by mass of dimethyldimethoxysilane in a four-necked separable flask equipped with a thermometer, a condenser, a decompressor, and a stirrer, and add distilled water while stirring. 6 parts by mass and 0.5 part by mass of acetic acid were added to the solution and heated at 50 ° C. for 4 hours to conduct hydrolysis and polycondensation reactions. Once cooled to 0 ° C., 8 parts by mass of trimethoxymethylsilane was added dropwise and stirred at room temperature for 2 hours to obtain a silicone polymer.
(6) 100 parts by mass of the dielectric constant adjusting agent prepared in (4), 100 parts by mass of methyl ethyl ketone, and 0.6 parts by mass of the silicone polymer prepared in (5) were placed in a beaker and mixed with stirring for 1 hour. Thereafter, the following materials were added and stirred for 2 hours to prepare an evaluation varnish. The varnish was stored at room temperature for 2 days, then coated on an 18 μm copper foil and dried at 100 ° C. for 15 minutes to prepare a resin film having a film thickness of 100 ± 3 μm.
Dielectric constant adjusting agent solution: 120 parts by mass Biphenyl type epoxy resin: NC3000-H (Nippon Kayaku Co., Ltd., trade name): 78 parts by mass Thermosetting agent: Dicyandiamide (Nippon Carbide, trade name) ): 3.1 parts by mass / thermosetting agent novolak phenol resin: HP-850 (manufactured by Hitachi Chemical Co., Ltd., trade name): 14.1 parts by mass / imidazole: 2-phenylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd.) (Product name 2PZ): 0.6 parts by mass. Solvent: methyl ethyl ketone: 100 parts by mass. (7) Next, the resin film was cured under curing conditions of 180 ° C.-120 minutes. Thereafter, the copper foil was removed by etching to produce a film for evaluation.

(Example 2)
The same procedure as in Example 1 was carried out except that the blending amount of the dielectric constant adjusting agent was 150 parts by mass, 150 parts by mass of methyl ethyl ketone, 1.0 part by mass of the silicone polymer, and 240 parts by mass of the dielectric constant adjusting agent solution.

(Example 3)
The porous silica was made by Fuji Silysia Chemical Co., Ltd. porous silica (oil absorption 330 ml / 100 g, average particle size 2.6 μm, SYLYSIA310P (trade name)), and the blending amount was 100 parts by mass. The compounding amount of the condensed phosphate ester is 230 parts by mass (filling 60% by volume of the pore volume), the organic substance fixing resin is 80 parts by mass (filling 51% of the remaining volume of the pore volume), The same procedure as in Example 1 was carried out except that the content was 100 parts by mass and the silicone polymer was 1.0 part by mass.

Example 4
(1) 41 parts by mass of liquid epoxy resin (Epicoat 815) used in Example 1, 31 parts by mass of liquid phenol (MEH-8000H), 207 parts by mass of condensed phosphate ester (PX-200), thermometer, condenser, It took in the 4-neck separable flask provided with the pressure reduction apparatus and the stirring apparatus, and it stirred and stirred for 1 hour at 120 degreeC, and mixed. Thereafter, the mixture was cooled to 50 ° C., 0.4 parts by mass of imidazole (2E4MZ) was blended, and stirred and mixed for 30 minutes to mix the organic substance and the organic substance fixing resin.
(2) 200 parts by mass of porous silica (E-2C) used in Example 1 was added, and the pressure in the four-necked separable flask was reduced while stirring. After confirming that the pressure in the four-neck separable flask has dropped to 10 mmHg or less, heat the four-neck separable flask so that the internal temperature becomes 120 ° C., and stir for 1 hour while maintaining the temperature. Then, 83 volume% of the pore volume of the porous silica was filled with a resin obtained by mixing the organic substance and the organic substance fixing resin.
(3) After filling, the four-necked separable flask is cooled to 50 ° C., the porous silica impregnated with the organic matter is taken out, heated at 180 ° C. for 2 hours to cure the resin for fixing the organic matter, and a dielectric constant adjuster Was made.
(4) Take 10 parts by weight of methanol, 40 parts by weight of diphenyldimethoxysilane, and 20 parts by weight of dimethyldimethoxysilane in a four-necked separable flask equipped with a thermometer, a condenser, a decompression device, and a stirrer. 6 parts by mass and 0.5 part by mass of acetic acid were added to the solution, followed by hydrolysis by heating at 50 ° C. for 4 hours to carry out a polycondensation reaction. Once cooled to 0 ° C., 8 parts by mass of trimethoxymethylsilane was added dropwise and stirred at room temperature for 2 hours to obtain a silicone polymer.
(5) 50 parts by mass of the dielectric constant adjuster prepared in (3), 50 parts by mass of methyl ethyl ketone, and 0.3 part by mass of the silicone polymer prepared in (4) were placed in a beaker and mixed with stirring for 1 hour. Thereafter, the following materials were added and stirred for 2 hours to prepare an evaluation varnish. The varnish was stored at room temperature for 2 days, then coated on an 18 μm copper foil and dried at 100 ° C. for 15 minutes to prepare a resin film having a film thickness of 100 ± 3 μm.
Dielectric constant adjusting agent solution: 120 parts by mass Biphenyl type epoxy resin: NC3000-H (Nippon Kayaku Co., Ltd., trade name): 78 parts by mass Thermosetting agent: Dicyandiamide (Nippon Carbide, trade name) ): 3.1 parts by mass / thermosetting agent: novolak phenol resin, HP-850 (manufactured by Hitachi Chemical Co., Ltd., trade name): 14.1 parts by mass / imidazole: 2-phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) (Trade name 2PZ): 0.6 parts by mass. Solvent: methyl ethyl ketone: 100 parts by mass. (6) Next, the resin film was cured under curing conditions of 180 ° C. for 120 minutes. Thereafter, the copper foil was removed by etching to produce a film for evaluation.

(Comparative Example 1)
(1) An evaluation varnish is prepared by blending non-porous silica, phosphate ester, liquid epoxy resin, liquid phenol and curing accelerator having the same mass as the dielectric constant adjusting agent of Example 1 in the following composition. did. The varnish was stored at room temperature for 2 days, then coated on an 18 μm copper foil and dried at 100 ° C. for 10 minutes to prepare a resin film having a film thickness of 100 ± 3 μm.
・ Condensed phosphate ester: PX-200 (trade name, manufactured by Daihachi Chemical Industry Co., Ltd.): 26 parts by mass ): 25 parts by mass Liquid epoxy resin: Epicoat 815 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.): 5.2 parts by mass Liquid phenol: MEH-8000H (trade name, manufactured by Meiwa Kasei Co., Ltd.): 3.8 Part by mass / imidazole: 2E4MZ (Shikoku Chemicals Co., Ltd., trade name): 0.5 part by mass / biphenyl epoxy resin: NC3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd.): 78 parts by mass / thermosetting Agent: Dicyandiamide (trade name, manufactured by Nippon Carbide Co., Ltd.): 3.1 parts by mass / thermosetting agent novolak phenol resin: HP-850 (manufactured by Hitachi Chemical Co., Ltd., product) ): 14.1 parts by mass-Imidazole: 2-phenylimidazole (trade name 2PZ, manufactured by Shikoku Chemicals Co., Ltd.): 0.6 parts by mass-Solvent: methyl ethyl ketone: 100 parts by mass (2) Next, 180 ° C.-120 The resin film was cured under the curing conditions of minutes. Thereafter, the copper foil was removed by etching to produce a film for evaluation.

(Comparative Example 2)
In Comparative Example 1, the procedure was the same as Comparative Example 1 except for the condensed phosphate ester.

(Comparative Example 3)
(1) Porous silica (oil absorption 150 ml / 100 g, average particle size 1.1 μm, God Ball E-2C (trade name) manufactured by Suzuki Oil & Fat Co., Ltd.) as a porous material, condensed phosphate ester ( A melting point of 95 ° C., PX-200 (trade name) manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Take 200 parts by weight of porous silica (E-2C) and 207 parts by weight of condensed phosphate ester (PX-200) in a four-necked separable flask equipped with a thermometer, a condenser, a decompressor, and a stirrer and stir. The pressure in the four-neck separable flask was reduced. After confirming that the pressure in the four-neck separable flask has dropped to 10 mmHg or less, heat the four-neck separable flask so that the internal temperature becomes 120 ° C., and stir for 1 hour while maintaining the temperature. Then, 60% by volume of the condensed phosphate ester was filled in the pores in the porous silica with respect to the pore volume.
(2) After filling, the four-necked separable flask was cooled to 50 ° C., the porous silica impregnated with the organic matter was taken out, and heated at 180 ° C. for 2 hours to prepare a dielectric constant adjusting agent.
(3) Take 10 parts by weight of methanol, 40 parts by weight of diphenyldimethoxysilane, and 20 parts by weight of dimethyldimethoxysilane in a four-necked separable flask equipped with a thermometer, a condenser, a decompressor, and a stirrer, and add distilled water while stirring. Add 6 parts by weight, 0.5 parts by weight of acetic acid to the solution,
The polycondensation reaction was performed by heating at 4 ° C. for 4 hours for hydrolysis. Once cooled to 0 ° C., 8 parts by mass of trimethoxymethylsilane was added dropwise and stirred at room temperature for 2 hours to obtain a silicone polymer.
(4) 75 parts by mass of the dielectric constant adjuster prepared in (2), 75 parts by mass of methyl ethyl ketone, and 0.6 parts by mass of the silicone polymer prepared in (3) were placed in a beaker and mixed with stirring for 1 hour. Thereafter, the following materials were added and stirred for 2 hours to prepare an evaluation varnish. The varnish was stored at room temperature for 2 days, then coated on an 18 μm copper foil and dried at 100 ° C. for 15 minutes to prepare a resin film having a film thickness of 100 ± 3 μm.
Dielectric constant adjusting agent solution: 102 parts by mass Biphenyl type epoxy resin: NC3000-H (Nippon Kayaku Co., Ltd., trade name): 78 parts by mass Thermosetting agent: Dicyandiamide (Nippon Carbide, trade name) ): 3.1 parts by mass / thermosetting agent: novolak phenol resin: HP-850 (manufactured by Hitachi Chemical Co., Ltd., trade name): 14.1 parts by mass / imidazole: 2-phenylimidazole (manufactured by Shikoku Chemicals Co., Ltd.) (Trade name 2PZ): 0.6 parts by mass. Solvent: methyl ethyl ketone: 100 parts by mass. (5) Next, the resin film was cured under curing conditions of 180 ° C. for 120 minutes. Thereafter, the copper foil was removed by etching to produce a film for evaluation.

  The dielectric constant at 1 GHz was measured for the produced evaluation film using an RF impedance / material analyzer (manufactured by Agilent Technologies, HP 4291B). Moreover, the test piece was cut out from the film for evaluation, and the glass transition temperature (Tg) was measured on the conditions of temperature rising; 5 degreeC / min using the thermomechanical analyzer (TMA-4000 by Mac Science Co., Ltd.). The results are shown in Table 1.

  From Table 1, in Examples 1-4, even if a dielectric constant changes, a big change is not looked at by glass transition temperature (Tg), but in Comparative Examples 1-3, with a change of a dielectric constant. It can be seen that the glass transition temperature (Tg) varies greatly.

  From this, by mix | blending the dielectric constant modifier of this invention with resin, a dielectric constant can be reduced, suppressing the influence on the physical property of a resin composition, or the reactivity of a resin composition.

  The dielectric constant adjusting agent and the resin resin composition of the present invention can change the relative dielectric constant of a resin used for an electronic component to a desired relative dielectric constant.

Claims (11)

  First, the pores of the porous material are filled with 1 to 99% by volume of the organic substance with respect to the whole pore volume, and then filled with the resin for fixing the organic substance with 30 to 100% by volume of the unfilled volume of the pore volume. Characteristic dielectric constant modifier.   A dielectric constant adjusting agent characterized by filling a mixture of an organic substance and an organic substance fixing resin in an amount of 5 to 100% by volume of the entire pore volume of the porous material.   The dielectric constant adjusting agent according to claim 2, wherein a ratio of the organic substance in the mixture obtained by mixing the organic substance and the organic substance fixing resin is 10 to 90% by volume.   The dielectric constant adjusting agent according to any one of claims 1 to 3, wherein the organic substance filling the pores of the porous material is solid at 20 ° C.   The dielectric constant modifier according to any one of claims 1 to 4, wherein the pore volume of the porous material is 10 to 700 ml / 100 g in terms of oil absorption.   The dielectric constant adjusting agent according to claim 1, wherein the porous material has an average particle diameter of 0.1 to 100 μm.   7. The dielectric constant adjusting agent according to claim 1, wherein the porous material has an average pore diameter of 0.5 to 1000 nm.   The dielectric constant adjusting agent according to any one of claims 1 to 7, wherein the porous material is porous silica.   The dielectric constant adjusting agent according to any one of claims 1 to 8, wherein the organic substance or the organic substance fixing resin filled in the pores has thermosetting properties.   A resin composition, wherein 1 to 700 parts by mass of the dielectric constant adjusting agent according to any one of claims 1 to 9 is dispersed in 100 parts by mass of a resin.   It has thermosetting property, The resin composition of Claim 10 characterized by the above-mentioned.