JP6768366B2 - Non-aqueous dispersion of fluororesin, thermosetting resin composition containing fluororesin using it, and its cured product - Google Patents

Description

The present invention relates to a non-aqueous dispersion of a fluororesin having a fine particle diameter, low viscosity, and excellent storage stability, a fluororesin-containing thermosetting resin composition using the same, and a cured product thereof.

In recent years, as electronic devices have become faster and more sophisticated, there is a demand for higher communication speeds. Under these circumstances, lower dielectric constants and lower dielectric loss tangents of various electronic device materials are required, and lower dielectric constants and lower dielectric loss tangents of thermosetting resins that can be used for insulating materials and substrate materials are also required. Has been done.

As a material having a low dielectric constant and a low dielectric loss tangent, polytetrafluoroethylene (PTFE, relative permittivity 2.1), which has the best properties among resin materials, is attracting attention, and among various resin materials, A method of melt-mixing PTFE, for example, a composition containing at least 50% by mass of PTFE and an amount of polyarylene ether ketone effective for imparting melt processability to the composition, wherein at least 20% by mass of the PTFE is used. percent composition characterized by having a melt viscosity of at least 10 8 ^Pa · s has been proposed (e.g., see Patent Document 1).

Such melt mixing is a method that is not suitable for mixing with a thermosetting resin material or the like because the resin is mixed in a softened state by heating.

As a method for solving this problem, the applicant of the present application prepares an oil-based solvent-based dispersion of PTFE and adds it to a thermosetting resin material or the like, for example, PTFE having a primary particle size of 1 μm or less. ~ 70% by mass, 0.1 to 40% by mass of a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group with respect to the mass of polytetrafluoroethylene, and the total water content by the Karl Fisher method is 20000 ppm. We have proposed an oil-based solvent-based dispersion of PTFE, which is characterized by the following, and an oil-based solvent-based dispersion of PTFE for adding an epoxy resin material. (See, for example, Patent Document 2 and Patent Document 3).

Although the above-mentioned resin material to which PTFE is added can be effective in terms of low dielectric constant and low dielectric loss tangent, the non-adhesiveness of PTFE makes it possible to bond resins or resin to metal. In such cases, there is a problem in slightly reducing the adhesive strength and the adhesive strength, and further improvement of the adhesive strength and the adhesive strength is desired.

Japanese Unexamined Patent Publication No. 2001-49068 JP-A-2015-199901 JP 2015-199903

The present invention is intended to solve the above-mentioned conventional problems, and has a fine particle size, low viscosity, excellent storage stability, is suitable for mixing with various resin materials, and achieves low dielectric constant and low dielectric loss tangent. An object of the present invention is to provide a non-aqueous dispersion of a fluororesin capable of suppressing a decrease in adhesive strength and adhesive strength, a thermosetting resin composition containing a fluororesin using the same, and a cured product thereof.

As a result of diligent studies on the above-mentioned conventional problems, the present inventors have made the above-mentioned non-aqueous dispersion of a fluororesin according to the following first to eighth inventions, and a composition of a fluororesin-containing thermosetting resin using the same. They have found that a product and a cured product thereof can be obtained, and have completed the present invention.

That is, the present invention is characterized in that it contains at least a fluororesin micropowder, a thermoplastic elastomer, a compound represented by the following formula (I), and a non-aqueous solvent. It is a non-aqueous dispersion of.

In the second invention, the micropowder of the fluororesin is polytetrafluoroethylene, fluoroethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene co-weight. The fluororesin according to the first invention, which is a micropowder of one or more fluororesins selected from the group consisting of coalesced, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene. It is a non-aqueous dispersion of.

The third invention is the non-aqueous dispersion of the fluororesin according to the first invention or the second invention, wherein the fluororesin micropowder is contained in an amount of 5 to 70% by mass.

The fourth invention is any one of the first invention to the third invention, wherein the thermoplastic elastomer is contained in an amount of 0.1 to 100% by mass based on the mass of the micropowder of the fluororesin. It is a non-aqueous dispersion of the fluororesin described in 1.

The fifth invention to the present invention is characterized in that the compound represented by the formula (I) is contained in an amount of 0.1 to 20% by mass with respect to the mass of the micropowder of the fluororesin. It is a non-aqueous dispersion of a fluororesin according to any one of the four inventions.

The sixth invention is characterized by containing at least a non-aqueous dispersion of a fluororesin according to any one of the first invention to the fifth invention and a resin composition containing a thermosetting resin. It is a thermosetting resin composition containing a fluororesin.

The seventh invention comprises at least a non-aqueous dispersion of a fluororesin according to any one of the first invention to the fifth invention and a resin composition containing a cyanate ester resin and / or an epoxy resin. It is a fluororesin-containing thermosetting resin composition characterized by containing.

The eighth invention is a cured product of a fluororesin-containing thermosetting resin, which is obtained by curing the fluororesin-containing thermosetting resin composition according to the sixth invention or the seventh invention.

The non-aqueous dispersion of the fluororesin of the present invention has a fine particle size, low viscosity, excellent storage stability, and is suitable for mixing with various resin materials. The non-aqueous dispersion of the present invention contains a fluororesin. The thermosetting resin composition and the cured product thereof can suppress a decrease in adhesion strength and adhesive strength while achieving low dielectric constant and low dielectric loss tangent.

Hereinafter, embodiments of the present invention will be described in detail.

[Non-aqueous dispersion of fluororesin]
The non-aqueous dispersion of the fluororesin of the present invention is characterized by containing at least a fluororesin micropowder, a thermoplastic elastomer, a compound represented by the following formula (I), and a non-aqueous solvent. Is to be.

Examples of the fluororesin micropowder that can be used in the present invention include polytetrafluoroethylene (PTFE), ethylene fluoride-propylene copolymer (FEP), perfluoroalkoxypolymer (PFA), and chlorotrifluoroethylene. At least selected from the group consisting of ethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE). Examples thereof include micropowder of one kind of fluororesin, and these are preferably those having a primary particle size of 1 μm or less.
Among the above-mentioned fluororesin micropowder, in particular, as a material having a low relative permittivity and a low dielectric loss tangent, polytetrafluoroethylene (PTFE, relative permittivity 2.1) having the best characteristics among resin materials. Desirable to use.

Such fluororesin micropowder is obtained by an emulsion polymerization method, and is a commonly used method such as the method described in the Fluororesin Handbook (edited by Takaomi Kurokawa, Nikkan Kogyo Shimbun). Can be obtained by Then, the fluororesin micropowder obtained by the emulsion polymerization is agglomerated and dried, and is recovered as a fine powder as secondary particles having agglomerated primary particle diameters, but is generally used. Various fine powder production methods can be used.

The particle size of the fluororesin micropowder is preferably one having a primary particle size of 1 μm or less, and preferably an average particle size of 1 μm or less even in a non-aqueous dispersion.
For stable dispersion in a non-aqueous solvent, a more uniform dispersion can be obtained by setting the primary particle size to preferably 0.5 μm or less, more preferably 0.3 μm or less.
Further, if the average particle size of the fluororesin micropowder in the non-aqueous dispersion exceeds 1 μm, it tends to settle and it becomes difficult to disperse stably, which is not preferable. It is preferably 0.5 μm or less, more preferably 0.3 μm or less.

In the present invention, as a method for measuring the primary particle size, a volume-based average particle size (50% volume size, median size) measured by a laser diffraction / scattering method, a dynamic light scattering method, an image imaging method, or the like is used. However, the fluororesin micropowder that has been dried into a powder state has a strong cohesive force between the primary particles, and the primary particle size can be easily measured by a laser diffraction / scattering method or a dynamic light scattering method. It can be difficult to do. In this case, it may indicate a value obtained by an image imaging method.

On the other hand, as a method for measuring the particle size of the fluorine-based resin in the non-aqueous dispersion, the average particle size (50%) based on the volume measured by a laser diffraction / scattering method, a dynamic light scattering method, an image imaging method, or the like. Volume diameter, median diameter) can be used.

Examples of the particle size measuring device include a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction / scattering method using Microtrack (manufactured by Nikkiso Co., Ltd.), and MacView (manufactured by Mountec Co., Ltd.) Image imaging method by (manufactured by the company) can be mentioned.

In the present invention, the fluororesin micropowder is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total amount of the non-aqueous dispersion. desirable.
When this content is less than 5% by mass, the amount of the solvent is large and the viscosity is extremely lowered, so that not only the micropowder fine particles of the fluororesin are likely to settle, but also the cyanate ester resin and the epoxy resin When mixed with such a material, a problem may occur due to a large amount of solvent, for example, an unfavorable situation may occur such that it takes time to remove the solvent. On the other hand, if it is larger than 70% by mass, the fluororesin micropowder tends to aggregate with each other, and it becomes extremely difficult to maintain the state of the fine particles in a stable and fluid state. Not preferable.

The thermoplastic elastomer used in the present invention is contained in order to eliminate the point that the adhesive strength and the adhesive strength are lowered when the resins or the resin and the metal are adhered to each other due to the non-adhesiveness of PTFE. Moreover, even if the thermoplastic elastomer is contained, the stability of the non-aqueous dispersion of the fluororesin is not impaired.
As the thermoplastic elastomer of the present invention, any elastomer that plasticizes when heated can be used. For example, a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, and a vinyl chloride-based thermoplastic elastomer can be used. At least one selected from elastomers, urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polybutadiene (1,2-BR) -based thermoplastic elastomers, acrylic-based elastomers, and silicone-based elastomers is mentioned. Therefore, it can be appropriately selected depending on the use of the non-aqueous dispersion of the fluororesin.
Specifically, a styrene-butadiene copolymer (SBS), a hydrogenated-styrene-butadiene copolymer (SEBS), a hydrogenated-styrene-isoprene copolymer (SEPS), and a polyester-polyether copolymer (SEPS). Olefin-based heat in which olefin-based rubber is finely dispersed in a matrix of olefin-based resins such as TPEE), polyurethane-polyether / polyester copolymer (TPU), nylon-polyether / polyester copolymer (TPA), and PP. Plastic elastomer (TPO) and the like can be mentioned. Commercially available products include SIS series (styrene-based thermoplastic elastomer, manufactured by JSR Corporation), TR series (styrene-butadiene thermoplastic elastomer, manufactured by JSR Corporation), RB series (polybutadiene-based thermoplastic elastomer, manufactured by JSR Corporation), JSR EXELINK (olefin-based thermoplastic elastomer, manufactured by JSR Corporation), DYNARON series (hydrated thermoplastic elastomer, manufactured by JSR Corporation), Thermolan (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), Epox TPE series (olefin) Examples thereof include based thermoplastic elastomers (manufactured by Sumitomo Chemical Co., Ltd.) and Septon series (hydrogenated styrene-based thermoplastic elastomers manufactured by Kuraray Co., Ltd.).
These exemplified thermoplastic elastomers can be used alone or in combination of two or more.

The thermoplastic elastomer used in the present invention may be soluble or insoluble in the non-aqueous solvent used.
When it is insoluble in the non-aqueous solvent used, it is preferable to use the thermoplastic elastomer in the form of fine particles.
The particle size is preferably such that the primary particle size is 10 μm or less, and the average particle size is 10 μm or less even in a non-aqueous dispersion.
For stable dispersion in a non-aqueous solvent, a more uniform dispersion can be obtained by setting the primary particle size to preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less.
Further, if the average particle size of the fine particles of the thermoplastic elastomer in the non-aqueous dispersion exceeds 10 μm, it tends to settle and it becomes difficult to disperse stably, which is not preferable. It is preferably 3 μm or less, more preferably 1 μm or less. The primary particle size of the fine particles of the thermoplastic elastomer and the average particle size of the urethane fine particles in the non-aqueous dispersion can be measured in the same manner as the above-mentioned measurement methods for the fluororesin micropowder. it can.

In the present invention, the thermoplastic elastomer is preferably contained in an amount of 0.1 to 100% by mass, more preferably 0.3 to 80% by mass, still more preferably 0, based on the mass of the fluororesin micropowder. It is desirable that the content is 5 to 50% by mass.
If this content is less than 0.1% by mass, the contribution of the addition of the thermoplastic elastomer to the adhesiveness and adhesiveness is significantly weakened, which is not preferable. On the other hand, if it exceeds 100% by mass, the electrical and physical properties of the thermoplastic elastomer and the influence of plasticization during heating will be strong, and the effect of the electrical properties due to the addition of the fluororesin will be significant. It is also not preferable because it weakens the physical characteristics.
In the present invention, the thermoplastic elastomer may be used after being dissolved in a non-aqueous solvent when the micropowder of the fluororesin is dispersed, or the thermoplastic elastomer may be used after preparing the dispersion of the micropowder of the fluororesin. It may be dissolved and used. When the thermoplastic elastomer is insoluble in a non-aqueous solvent, even if the fine particles of the thermoplastic elastomer are dispersed at the same time as the fluororesin, the fine particles of the thermoplastic elastomer and the micropowder of the fluororesin are dispersed separately. It may be mixed afterwards.

The compound represented by the above (I) used in the present invention is capable of uniformly and stably dispersing fine powder of a fluororesin micropowder in a non-aqueous solvent. Its molecular structure is a ternary polymer composed of vinyl butyral / vinyl acetate / vinyl alcohol, which is obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde (BA), and has butyral groups, acetyl groups, and hydroxyl groups. It has a structure, and by changing the ratio of these three types of structures (each ratio of l, m, and n), it is soluble in non-aqueous solvents, and the fluororesin microscopically contained in various resin materials. It is possible to control the chemical reactivity when a non-aqueous dispersion of powder is added.

As the compound represented by (I) above, commercially available products such as Sekisui Chemical's Eslek B series, K (KS) series, SV series, and Kuraray's Mobital series can be used.
Specifically, trade names manufactured by Sekisui Chemical Industry Co., Ltd .; Eslek BM-1 (hydroxyl group amount: 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 40,000), BH-3 (hydroxyl group amount). : 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 110,000), BH-6 (hydroxyl group amount: 30 mol%, butyralization degree 69 ± 3 mol%, molecular weight: 92,000), BX- 1 (hydroxyl group amount: 33 ± 3 mol%, acetalization degree 66 mol%, molecular weight: 100,000), BX-5 (hydroxyl group amount: 33 ± 3 mol%, acetalization degree 66 mol%, molecular weight: 130,000), same BM-2 (hydroxyl group amount: 31 mol%, butyralization degree 68 ± 3 mol%, molecular weight: 52,000), BM-5 (hydroxyl group amount: 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 5) .30,000), BL-1 (hydroxyl group amount: 36 mol%, butyralization degree 63 ± 3 mol%, molecular weight: 19 thousand), BL-1H (hydroxyl group amount: 30 mol%, butyralization degree 69 ± 3) Mol%, molecular weight: 20,000), BL-2 (hydroxyl group amount: 36 mol%, butyralization degree 63 ± 3 mol%, molecular weight: 2.7), BL-2H (hydroxyl group amount: 29 mol%, butyralization degree) 70 ± 3 mol%, molecular weight: 28,000), BL-10 (hydroxyl weight: 28 mol%, butyralization degree 71 ± 3 mol%, molecular weight: 15,000), KS-10 (hydroxyl weight: 25 mol%, degree of acetalization 65 ± 3 mol%, molecular weight: 17,000), etc., and trade name manufactured by Kuraray Co., Ltd .; Mobital B145 (hydroxyl group amount: 21 to 26.5 mol%, degree of acetalization 67. 5-75.2 mol%), B16H (hydroxyl group amount: 26.2 to 30.2 mol%, acetalization degree 66.9 to 73.1 mol%, molecular weight: 10,000 to 20,000) and the like.
These may be used alone or in mixture of 2 or more types.

The content of the compound represented by (I) is preferably 0.1 to 20% by mass with respect to the micropowder of the fluororesin. If the content of this compound is less than 0.1% by mass, the dispersion stability is deteriorated and the fluororesin micropowder tends to settle, and if it exceeds 20% by mass, the viscosity becomes high, which is not preferable.
Further, considering the characteristics when a non-aqueous dispersion of a fluororesin micropowder is added to a thermosetting resin or the like, 0.1 to 15% by mass is desirable, and further 0.1 to 10% by mass is desirable. In particular, 0.1 to 5% by mass is most preferable.

In the non-aqueous dispersion of the fluororesin micropowder in the present invention, other surfactants and dispersants are used in combination with the compound represented by the above (I) as long as the effects of the present invention are not impaired. It is also possible.
For example, nonionic, anionic, cationic, etc. surfactants and dispersants, nonionic, anionic, cationic, etc. polymer surfactants and polymer dispersants, regardless of whether they are fluorine-based or non-fluorinated. However, it can be used without limitation.

Examples of the non-aqueous solvent used for the non-aqueous dispersion of the present invention include γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane and ethylcyclohexane. , Methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate , Diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane , Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether , Fenetor, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, simene, mesitylene, methanol, ethanol, isopropanol, butanol, methylmonoglycidyl ether, ethylmonoglycidyl ether, butylmonoglycidyl ether, Phenyl monoglycidyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methylphenol monoglycidyl ether, ethylphenol monoglycidyl ether, butylphenol monoglycidyl ether, mineral spirit, 2-hydroxyethyl acrylate , Tetrahydrofurfuryl acrylate, 4-vinylpyridine, N-methyl-2-pyrrolidone, 2-ethylhexyl acrylate, 2-hydroxyethylmethacrylate, hydroxypropylmethacrylate Rate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methylmethacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, N, Examples thereof include one solvent selected from the group consisting of N-dimethylformamide, N, N-dimethylacetamide, dioxolane, and various silicone oils, or those containing two or more of these solvents.
Among these solvents, preferably, it varies depending on the resin type used, etc., but methyl ethyl ketone, cyclohexanone, toluene, xylene, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethyl. Examples include acetamide and dioxolane.

In the present invention, the above solvent is mainly used, but it can be used in combination with other solvents or other solvents can be used, and is suitable depending on the intended use (resin materials for various circuit boards). Is selected.
Depending on the polarity of the solvent used, it may be highly compatible with water, but if the amount of water is large, the dispersibility of the fluororesin micropowder in the solvent will be hindered, resulting in an increase in viscosity and aggregation of particles. May cause.
In the present invention, the non-aqueous solvent used is preferably one in which the water content by the Karl Fischer method is 8000 ppm or less [0 ≦ water content ≦ 8000 ppm]. In the present invention (including examples described later), the measurement of the water content by the Karl Fischer method is based on JIS K 0068: 2001, and can be measured by, for example, MCU-610 (manufactured by Kyoto Electronics Industry Co., Ltd.). it can. By reducing the amount of water in this solvent to 8000 ppm or less, a non-aqueous dispersion of fluororesin micropowder having a fine particle diameter, low viscosity, and excellent storage stability can be obtained, more preferably 5000 ppm. Below, it is more preferably 3000 ppm or less, and particularly preferably 2500 ppm or less. As the adjustment of the water content, a commonly used method of dehydrating a solvent such as an oily solvent can be used, and for example, molecular sieves or the like can be used.

The non-aqueous dispersion of the fluororesin of the present invention configured as described above includes at least a fluororesin micropowder, a thermoplastic elastomer, a compound represented by the above formula (I), and a non-aqueous solvent. By containing, it has a fine particle size, low viscosity, excellent storage stability, is suitable for mixing with various resin materials, and can suppress deterioration of adhesion strength and adhesive strength while achieving low dielectric constant and low dielectric loss tangent. A non-aqueous dispersion of a fluororesin that can be produced can be obtained.

[Fluorine-based resin-containing thermosetting resin composition]
The fluororesin-containing thermosetting resin composition of the present invention is characterized by containing at least a non-aqueous dispersion of a fluororesin and a resin composition containing a thermosetting resin.
The content of the non-aqueous dispersion of the fluororesin is the micropowder of the fluororesin such as PTFE, the thermoplastic elastomer, the compound represented by the above formula (I), and the non-aqueous solvent contained in the dispersion. It varies depending on each amount and the use of the composition such as the heat-curable resin, and the non-aqueous solvent such as the oil-based solvent in the resin composition is finally cured after the composition containing the heat-curable resin is prepared. Therefore, the content of the micropowder of the fluororesin such as PTFE is finally preferably 1 to 100 parts by mass, based on 100 parts by mass of these resins. Preferably, it is desirable to adjust the amount to 1 to 30 parts by mass and use the dispersion.
By setting the content of the micropowder of a fluororesin such as PTFE to 1 part by mass or more with respect to 100 parts by mass of the resin, it is possible to exhibit the electrical characteristics of low relative permittivity and low dielectric loss tangent, while on the other hand. By setting the amount to 100 parts by mass or less, the effect of the present invention can be exhibited without impairing the adhesiveness and heat resistance of the thermosetting resin.
Further, the content of the thermoplastic elastomer and the content of the compound represented by the above formula (I) are in the range of 0.1 to 100% by mass with respect to the micropowder of the fluororesin, respectively, as described above. , And the range is 0.1 to 20% by mass.

Examples of the resin composition used in the present invention include those containing at least a thermosetting resin. Examples of the thermosetting resin include epoxy resin, polyimide resin, polyamideimide resin, triazine resin, phenol resin, melamine resin, polyester resin, cyanate ester resin, and modified resins of these resins. May be used alone or in combination of two or more. These resins serve as the base resin of the thermosetting resin composition, and can be used without particular limitation as long as they are suitable for use such as insulation and adhesiveness in electronic devices.
Preferred resin compositions include at least cyanate ester resins and / or epoxy resins, and these resins serve as particularly suitable base resins for thermosetting resin compositions, and have insulating properties and adhesiveness in electronic devices. It is suitable for such as.
Examples of the cyanate ester resin (cyanate ester resin) that can be used in the present invention include at least bifunctional aliphatic cyanate ester, at least bifunctional aromatic cyanate ester, or a mixture thereof. , For example, 1,3,5-trisianatobenzene, 1,3-disianatonaphthalene, 1,4-disianatonaphthalene, 1,6-disianatonaphthalene, 1,8-disianatonaphthalene, 2,6-disi Polymers of at least one polyfunctional cyanate ester selected from anatonaphthalene and 2,7-disianatonaphthalene, bisphenol A type cyanate resin or bisphenol F type cyanate ester added with hydrogen. Resin or those with hydrogen added, 6F bisphenol A dicyanate resin, bisphenol E type dicyanate resin, tetramethylbisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanic acid ester At least one kind such as a resin or a novolak resin cyanate can be mentioned. Commercially available products of these cyanate ester resins can also be used.

Examples of the epoxy resin that can be used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, and naphthylene ether type epoxy resin. Glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, bird Examples thereof include a methylol type epoxy resin and a halogenated epoxy resin.
These epoxy resins can be used alone or in combination of two or more.
The epoxy resin that can be used in the present invention is not limited to the above resins as long as there is one or more epoxy groups in one molecule, but bisphenol A, hydrogenated bisphenol A, cresol novolac, and the like are preferable. is there.
In the present invention, the cyanate ester resin (cyanate ester resin) and the epoxy resin can be used alone or in combination, and in the case of combined use, they are used in a mass ratio of 1:10 to 10: 1. can do.

When the cyanate ester resin or epoxy resin is used in the present invention, an active ester compound can also be used as an additive from the viewpoints of reactivity, curability and moldability.
As the active ester compound that can be used, a compound having two or more active ester groups in one molecule is generally preferable, and examples thereof include a carboxylic acid compound, a phenol compound, and a naphthol compound. Examples of the carboxylic acid compound include acetic acid, benzoic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadienyldiphenol, and phenol novolac.
These active ester compounds can be used alone or in combination of two or more. Examples of commercially available active ester compounds include EXB-9451, EXB-9460 (manufactured by DIC Corporation), DC808, and YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.).
The amount of these active ester compounds used is determined by the type of active ester compound used and the base resin of the thermosetting resin composition used.
Further, as the active ester compound, an active ester compound curing accelerator can be used, if necessary.
As the active ester compound curing accelerator, an organometallic salt or an organometallic complex is used, and for example, an organometallic salt or an organometallic complex containing iron, copper, zinc, cobalt, nickel, manganese, tin and the like is used. .. Specifically, the cyanate ester curing accelerator includes manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octylate, copper octylate, zinc octylate, cobalt octylate and the like. Organic metal salts; examples include organic metal complexes such as acetylacetonate lead and acetylacetonate cobalt.
From the viewpoint of reactivity, curability, and moldability, these active ester compound curing accelerators are preferably 0.05 to 5 parts by mass, preferably 0 parts by mass, based on 100 parts by mass of the resin used. It can be contained in 1 to 3 parts by mass.

Further, when the epoxy resin is used in the present invention, a curing agent can be used as an additive from the viewpoints of reactivity, curability and moldability. Examples of the curing agent that can be used include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazin and isophoronediamine, metaphenylenediamine and paraphenylenediamine. Aromatic amines such as 3,3'-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether, mercaptopropionic acid Melcaptans such as esters and terminal mercapto compounds of epoxy resin, polyazelineic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3- Alicyclic acid anhydrides such as dicarboxylic acid anhydride, norbornan-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornan-2,3-dicarboxylic acid anhydride Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and salts thereof. , Amine adducts obtained by the reaction of the above aliphatic amines, aromatic amines, and / or imidazoles with an epoxy resin, hydrazines such as dihydrazide adipate, dimethylbenzylamine, 1,8-diazabicyclo [5. 4.0] Examples thereof include tertiary amines such as Undecene-7, organic phosphines such as triphenylphosphine, and at least one such as dicyandiamide.
The amount of these curing agents used is determined by the type of epoxy resin used and the curing agent used.
In the resin composition of the present invention, further, an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a colorant, a thickener, a defoaming agent, a leveling agent, a coupling agent, an adhesion imparting material, etc. Materials commonly used in thermosetting resin compositions for equipment can also be used in combination.

In the present invention, by adjusting the total resin concentration of the thermosetting resin or the like required for the final thermosetting resin composition containing a fluororesin, the micropowder of the fluororesin is uniform without agglomeration. Since the specific dielectric constant and dielectric loss tangent are low and there is no decrease in adhesion strength and adhesive strength, excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy can be exhibited. It will be like this.

[Fluorine-based resin-containing thermosetting resin cured product]
In the present invention, the fluororesin-containing thermosetting resin composition having each of the above configurations can be molded and cured by the same method as a thermosetting resin composition such as a known epoxy resin composition to obtain a cured product. The molding method and the curing method can be the same as those of a thermosetting resin composition such as a known epoxy resin composition, and the method peculiar to the fluororesin-containing thermosetting resin composition of the present invention is not required, particularly. Not limited.
The cured product obtained by curing the fluororesin-containing thermosetting resin composition of the present invention can take the form of a laminate, a molded product, an adhesive, a coating film, a film, or the like.
The fluororesin-containing thermocurable resin composition of the present invention and the cured product thereof have electrical characteristics of low specific dielectric constant and low dielectric tangent without impairing the adhesiveness and heat resistance of the thermocurable resin such as epoxy resin. It is excellent, and because it contains a thermoplastic elastomer, it is possible to suppress a decrease in adhesion strength and adhesive strength, so it is suitable for electronic substrate materials, insulating materials, adhesive materials, etc., for example, sealing used for electronic parts. It is useful as a material for materials, copper-clad laminates, insulating paints, composite materials, insulating adhesives, etc., and in particular, for forming insulating layers for multilayer printed wiring boards for electronic devices, laminated boards for circuit boards, coverlay films, and prepregs. It can be suitably used for such purposes.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples and the like.

[Preparation of non-aqueous dispersion of fluororesin: dispersions 1 to 4]
Of the blending compositions shown in Table 1 below, a predetermined amount of blending numbers [1] to [4] was blended, and then sufficiently stirred and mixed. Then, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill.
The average particle size of PTFE in the dispersions 1 to 4 consisting of the above compounding numbers [1] to [4] (the average particle size of the cumulant method analysis in the scattering intensity distribution) is measured by FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). It was measured by a dynamic light scattering method (see Table 2 below).

Further, the dispersion numbers [5] and [6] were added to the dispersions 1 and 2 consisting of the dispersion numbers [1] to [4] and sufficiently stirred and mixed to prepare the dispersions 1 to 4. ..
Moreover, when the water content of the obtained dispersions 1 to 4 was measured, each water content by the Karl Fischer method was in the range of 800 to 1800 ppm, respectively.

The obtained dispersions 1 to 4 were stored in a closed container at 40 ° C. for 1 week, and then the state of sedimentation of the particles was visually confirmed. ..

[Examples 1 and 2 and Comparative Examples 1 to 3: Preparation of a fluororesin-containing thermosetting resin composition]
Using the obtained dispersions 1 to 4, a fluororesin-containing thermosetting resin composition was prepared according to the formulation shown in Table 3 below. Further, Comparative Example 3 was prepared as a composition containing only a resin to which no PTFE dispersion was added.
After mixing at the compounding ratios shown in Examples 1 and 2 and Comparative Examples 1 to 3, the PTFE dispersion and the resins are stirred using a disper so as to be uniformly mixed to obtain a fluororesin-containing thermosetting resin composition. Obtained.
Here, all of the formulations of Examples 1 and 2 and Comparative Examples 1 and 2 showed a very uniform state, and no agglomerates of PTFE and the like were observed.

[Examples 3 and 4 and Comparative Examples 4 to 6: Preparation of a cured product containing a fluororesin-containing thermosetting resin]
The fluororesin-containing thermosetting resin composition obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was applied to the entire surface of one side of the polyimide film (thickness: 25 μm) so that the thickness after drying was about 25 μm. A sample for evaluation of relative permittivity is prepared by applying the film to a uniform thickness using a coater, drying it at about 120 ° C. for about 10 minutes, and then heating it at 180 ° C. for 60 minutes to cure it. did.

[Evaluation of relative permittivity]
The relative permittivity was measured at 1 GHz using an impedance analyzer (Impedence Analyzer) according to the test standard of JIS C6481-1996.

[Evaluation of adhesion strength]
After covering the roughened surface of the copper foil (thickness 18 μm) whose one side is roughened with a mesh having a thickness of 100 μm as a spacer, the fluororesin-based resin obtained in Examples 1 and 2 and Comparative Examples 1 to 3 is contained. A thermosetting resin composition is applied, the solvent is dried at 50 ° C. for 5 minutes, and then a copper foil (thickness 18 μm) with a roughened one side is covered with the roughened surface facing the composition side at 160 ° C. After laminating, a sample for adhesion evaluation was prepared by heating at 180 ° C. for 60 minutes to cure.

For the evaluation of the adhesion strength, a test piece cut to a width of 1 cm was prepared, and T-shaped peeling was performed with a push-pull tester.

The evaluation results of the relative permittivity and the adhesion strength are shown in Table 4 below.

As shown in Table 4 above, the fluororesin-containing thermosetting resin cured product according to Examples 3 and 4 exhibits a lower relative permittivity and is thermoplastic as compared with Comparative Example 6 which does not contain a fluororesin. As a result, the adhesion strength was higher than that of Comparative Examples 4 and 5 which did not contain the elastomer.

The non-aqueous dispersion of the fluororesin of the present invention has a fine particle size, low viscosity, excellent storage stability, and is suitable for mixing with various resin materials. The non-aqueous dispersion of the present invention contains a fluororesin. Since the thermosetting resin composition and its cured product can suppress a decrease in adhesion strength and adhesive strength while achieving low dielectric constant and low dielectric tangent, they are used for insulating layers of multilayer printed wiring boards and circuit boards. It can be suitably used for adhesives, laminated boards for circuit boards, coverlay films, prepregs, and the like.

Claims (5)

At least, the micropowder of the fluororesin is 5 to 70% by mass, and the thermoplastic elastomer is 0.1 to 100% by mass with respect to the mass of the micropowder of the fluororesin , which is represented by the following formula (I). A non-aqueous dispersion of a fluororesin , wherein the compound contains 0.1 to 20% by mass and a non-aqueous solvent with respect to the mass of the micropowder of the fluororesin.

The micropowder of the fluororesin is polytetrafluoroethylene, fluoroethylene-propylene copolymer, perfluoroalkoxypolymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotri. The non-aqueous dispersion of a fluororesin according to claim 1, wherein the micropowder is one or more fluororesins selected from the group consisting of a fluoroethylene copolymer and polychlorotrifluoroethylene. A fluororesin-containing thermosetting resin composition, which comprises at least a non-aqueous dispersion of a fluororesin according to claim 1 or 2 and a resin composition containing a thermosetting resin. A fluororesin-containing thermosetting resin composition comprising at least the non-aqueous dispersion of the fluororesin according to claim 1 or 2 and a resin composition containing a cyanate ester resin and / or an epoxy resin. object. A cured product of a fluororesin-containing thermosetting resin, which is obtained by curing the fluororesin-containing thermosetting resin composition according to claim 3 or 4 .