JP2017222762A - Fluororesin nonaqueous dispersion, fluororesin-containing thermosetting resin composition prepared therewith and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluororesin nonaqueous dispersion that has a fine particle diameter, low viscosity, and excellent storage stability, a fluororesin-containing thermosetting resin composition prepared therewith and a cured product thereof.SOLUTION: A fluororesin nonaqueous dispersion contains at least a fluororesin micro powder, a thermoplastic elastomer, a fluorine additive containing at least a fluorine-containing group and a lipophilic group, and a nonaqueous solvent.SELECTED DRAWING: None

Description

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

  In recent years, electronic devices have been increased in speed and functionality, and a communication speed has been increased. Under these circumstances, various electronic equipment materials are required to have low dielectric constants and low dielectric loss tangents, and there is also a need for low dielectric constants and low dielectric loss tangents of thermosetting resins that can be used for insulating materials and substrate materials. It has been.

As a low dielectric constant and low dielectric loss tangent material, polytetrafluoroethylene (PTFE, relative dielectric constant 2.1) having the most excellent characteristics among resin materials is attracting attention. A method of melt mixing PTFE, for example, a composition comprising at least 50% by weight of PTFE and an amount of polyarylene ether ketone effective to impart melt processability to the composition, wherein at least 20% by weight of the PTFE % Has a melt viscosity of at least 10 ⁸ Pa · s has been proposed (see, for example, Patent Document 1).

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

  As a method for solving this problem, the applicant of the present application has prepared a PTFE oil-based solvent dispersion and added it to a thermosetting resin material, for example, 5 PTFE having a primary particle size of 1 μm or less. ~ 70 mass%, containing 0.1 to 40 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 Fischer method is 20000 ppm The present invention proposes an oil-based solvent dispersion of PTFE characterized by the following, and an oil-based solvent dispersion of PTFE for adding an epoxy resin material. (For example, see Patent Document 2 and Patent Document 3)

  Although the resin material added with PTFE as described above can be effective in terms of unprecedented low dielectric constant and low dielectric loss tangent, the non-adhesive property of PTFE allows adhesion between resins or between resin and metal. In such cases, there is a problem that the adhesion strength and the adhesion strength are slightly reduced, and further improvement of the adhesion strength and the adhesion strength is desired.

JP 2001-49068 A JP 2015-199901 A JP-A-2015-199903

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

  As a result of intensive studies on the above-described conventional problems, the present inventors have found that the following non-aqueous dispersions of the above-mentioned fluororesin, and fluororesin-containing thermosetting resin compositions using the same, according to the following first to eighth inventions The present inventors have found that a product and its cured product can be obtained, and have completed the present invention.

  That is, the first invention includes at least a fluororesin micropowder, a thermoplastic elastomer, a fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous solvent. A non-aqueous dispersion of a fluororesin.

  In the second invention, the fluororesin micropowder contains polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer. The fluororesin according to the first aspect of the present invention, which is a micropowder of at least one fluororesin selected from the group consisting of a coalescence, an ethylene-chlorotrifluoroethylene copolymer, and a polychlorotrifluoroethylene This is a non-aqueous dispersion.

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

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

  The fifth invention is characterized in that the fluorine-containing additive containing at least the fluorine-containing group and the lipophilic group is contained in an amount of 0.1 to 20% by mass with respect to the mass of the micropowder of the fluorine-based resin. A non-aqueous dispersion of a fluororesin according to any one of the first to fourth inventions.

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

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

  The eighth invention is a fluorinated resin-containing thermosetting resin cured product obtained by curing the fluorinated resin-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, and contains the fluororesin using the non-aqueous dispersion of the present invention. The thermosetting resin composition and the cured product thereof can suppress a decrease in adhesion strength and adhesive strength while achieving a low dielectric constant and a 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 a fluororesin of the present invention comprises at least a micro-powder of a fluororesin, a thermoplastic elastomer, a fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous solvent. It is characterized by containing.

Examples of the micro-powder of fluororesin that can be used in the present invention include polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), and chlorotrifluoro. At least selected from the group consisting of ethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE). One type of fluororesin micropowder is exemplified, and those having a primary particle size of 1 μm or less are preferred.
Among the fluororesin micropowders, polytetrafluoroethylene (PTFE, relative dielectric constant 2.1) having the most excellent characteristics among resin materials, particularly as a material having a low relative dielectric constant and a low dielectric loss tangent. Use is desirable.

  Such a fluororesin micropowder is obtained by an emulsion polymerization method, and is a generally used method such as a method described in a fluorine resin handbook (edited by Takaomi Kurokawa, Nikkan Kogyo Shimbun). Can be obtained. The fluororesin micropowder obtained by the emulsion polymerization is agglomerated and dried, and is recovered as a fine powder as secondary particles with a primary particle size aggregated. Various fine powder production methods can be used.

The particle diameter of the fluororesin micropowder is preferably such that the primary particle diameter is 1 μm or less, and the average particle diameter is preferably 1 μm or less even in the non-aqueous dispersion.
For stable dispersion in a non-aqueous solvent, the primary particle size is preferably 0.5 μm or less, more preferably 0.3 μm or less, whereby a more uniform dispersion is obtained.
Further, if the average particle size of the fluororesin micropowder in the non-aqueous dispersion exceeds 1 μm, it tends to settle and it is difficult to stably disperse, which is not preferable. Preferably it is 0.5 micrometer or less, More preferably, it is 0.3 micrometer or less.

  In the present invention, as a method for measuring the primary particle diameter, a volume-based average particle diameter (50% volume diameter, median diameter) 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 in powder form after drying has strong cohesion between primary particles, and the primary particle diameter can be easily measured by laser diffraction / scattering method or dynamic light scattering method. It can be difficult to do. In this case, the value obtained by the image imaging method may be indicated.

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

  Examples of the particle diameter measuring apparatus 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 (Mounttech Co., Ltd.). Image imaging method by the company).

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 the content is less than 5% by mass, the amount of the solvent is large and the viscosity is extremely lowered, so that the micropowder fine particles of the fluororesin are not only easily settled, but also cyanate ester resin and epoxy resin. When mixed with a material such as the above, a problem due to a large amount of the solvent, for example, an unfavorable situation such as taking time to remove the solvent may occur. On the other hand, if it exceeds 70% by mass, the micro-powder of fluororesin tends to aggregate together, and it becomes extremely difficult to stably maintain the state of fine particles in a fluid state. It is not preferable.

The thermoplastic elastomer used in the present invention is contained in order to eliminate the point of lowering the adhesion strength and the adhesive strength in bonding between resins or between resin and metal due to the non-adhesive property 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 can be plasticized when heated can be used. For example, styrene thermoplastic elastomer, olefin thermoplastic elastomer, vinyl chloride thermoplastic At least one selected from elastomers, urethane thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, polybutadiene (1,2-BR) thermoplastic elastomers, acrylic elastomers, and silicone elastomers. And can be appropriately selected according to the use of the non-aqueous dispersion of the fluororesin.
Specifically, styrene-butadiene copolymer (SBS), hydrogenated-styrene-butadiene copolymer (SEBS), hydrogenated-styrene-isoprene copolymer (SEPS), polyester-polyether copolymer ( Olefin heat in which olefin rubber is finely dispersed in a matrix of olefin resin such as TPEE), polyurethane-polyether / polyester copolymer (TPU), nylon-polyether / polyester copolymer (TPA), PP Examples thereof include a plastic elastomer (TPO). 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 (hydrogenated thermoplastic elastomer, manufactured by JSR Corporation), Thermolane (olefin-based thermoplastic elastomer, manufactured by Mitsubishi Chemical Corporation), Epox TPE series (olefin) -Based thermoplastic elastomer, manufactured by Sumitomo Chemical Co., Ltd.), Septon series (hydrogenated styrene-based thermoplastic elastomer, manufactured by Kuraray Co., Ltd.), and the like.
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 either soluble or insoluble in the non-aqueous solvent used.
In the case of insoluble in the non-aqueous solvent to be used, it is preferable to use the thermoplastic elastomer in the form of fine particles.
As the particle size, those having a primary particle size of 10 μm or less are preferable, and it is preferable that the average particle size is 10 μm or less even in a non-aqueous dispersion.
In order to disperse stably in a non-aqueous solvent, the primary particle diameter is preferably 1 μm or less, more desirably 0.5 μm or less, and even more preferably 0.3 μm or less, whereby a more uniform dispersion is obtained.
Further, if the average particle diameter of the thermoplastic elastomer fine particles in the non-aqueous dispersion exceeds 10 μm, it tends to settle and difficult to disperse stably, which is not preferable. Preferably it is 3 micrometers or less, More preferably, it is 1 micrometer or less. The measurement of the primary particle size of the thermoplastic elastomer fine particles and the measurement of the average particle size of the urethane fine particles in the non-aqueous dispersion can be performed in the same manner as in the measurement methods for the fluororesin micropowder described above. 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, and still more preferably 0, based on the mass of the fluororesin micropowder. It is desirable to contain 5-50 mass%.
When the content is less than 0.1% by mass, the contribution to adhesion and adhesiveness due to the addition of the thermoplastic elastomer is remarkably weakened, which is not preferable. On the other hand, if the amount exceeds 100% by mass, the electrical properties and physical properties of the thermoplastic elastomer, and the influence of plasticization during heating, etc. come out strongly. It also weakens the physical properties and is not preferable.
In the present invention, the thermoplastic elastomer may be used after being dissolved in a non-aqueous solvent at the time of dispersion of the fluororesin micropowder, or after the dispersion of the fluororesin micropowder is prepared, It may be used after being dissolved. If the thermoplastic elastomer is insoluble in a non-aqueous solvent, the thermoplastic elastomer fine particles and the fluororesin micropowder are dispersed separately even if the thermoplastic elastomer fine particles are dispersed simultaneously with the fluororesin. It can be mixed afterwards.

The fluorine-based additive in the present invention is required to have at least a fluorine-containing group and a lipophilic group, and is not particularly limited as long as it has at least a fluorine-containing group and a lipophilic group. In addition, a hydrophilic group may be contained.
By using a fluorine-based additive having at least a fluorine-containing group and a lipophilic group, the surface tension of a non-aqueous solvent such as an oily solvent serving as a dispersion medium is reduced, and the wettability with respect to the polytetrafluoroethylene surface is improved. In addition to improving the dispersibility of tetrafluoroethylene, the fluorine-containing group is adsorbed on the surface of polytetrafluoroethylene, and the lipophilic group is extended into a non-aqueous solvent such as an oily solvent serving as a dispersion medium. The obstacle prevents aggregation of polytetrafluoroethylene and further improves the dispersion stability.

Examples of the fluorine-containing group include a perfluoroalkyl group and a perfluoroalkenyl group. Examples of the lipophilic group include one or more of an alkyl group, a phenyl group, and a siloxane group. Examples of the hydrophilic group include one or more of ethylene oxide, amide group, ketone group, carboxyl group, sulfone group and the like.
Specific examples of fluorine-based additives that can be used include Surflon series (manufactured by AGC Seimi Chemical Co., Ltd.) such as Surflon S-611 containing a perfluoroalkyl group, MegaFuck F-555, MegaFuck F-558, MegaFuck. A Mega-Fuck series (manufactured by DIC) such as F-563 and Unidyne series (manufactured by Daikin Industries) such as Unidyne DS-403N can be used.

  These fluorine-based additives are appropriately selected depending on the type of non-aqueous solvent such as polytetrafluoroethylene and oily solvent to be used, but one type or a combination of two or more types should be used. Is also possible.

The content of the fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group is preferably 0.1 to 20% by mass with respect to the micropowder of the fluorine-based resin. When the content of this compound is less than 0.1% by mass, the dispersion stability is deteriorated and the micropowder of the fluororesin tends to settle, and when it exceeds 20% by mass, the viscosity is increased, which is not preferable.
Furthermore, in consideration of the characteristics when a non-aqueous dispersion of fluororesin micropowder is added to a thermosetting resin or the like, 0.1 to 10% by mass is desirable, and further 0.1 to 7% 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 surface activity is combined with a fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group, as long as the effects of the present invention are not impaired. It is also possible to use an appropriate amount of an agent or a dispersant.
For example, nonionic, anionic, and cationic surfactants and dispersants, nonionic, anionic, and cationic polymer surfactants and butyral (PVB) resins, regardless of whether they are fluorine or non-fluorine Examples thereof include, but are not limited to, polymer dispersants.
Examples of the butyral (PVB) resin include a terpolymer composed of vinyl butyral / vinyl acetate / vinyl alcohol obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde (BA), butyral group, acetyl group, It is a structure having a hydroxyl group, and various butyral (PVB) resins having different hydroxyl amount and degree of butyralization can be used by changing the ratio of these three types of structures. Eslek BM-1 (Hydroxyl amount: 34 mol%, Butyralization degree 65 ± 3 mol%, Molecular weight: 40,000), etc., SK-10 (Hydroxyl amount: 25 mol%, Acetalization degree 65 ± 3) Mobital B145 from K (KS) series, SV series, Kuraray, etc. (Hydroxyl group amount: 21 to 26.5 mol%, acetalization degree 67.5 to 75.2 mol%), B16H (Hydroxyl group amount: 26.2 to 30.2 mol%, acetalization degree 66.9 to 73) .1 mol%, molecular weight: 1 to 20,000) and the like can be used.

Examples of the non-aqueous solvent used in 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, dip Pyrene 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, acetic acid Ethyl, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether, benzene, ethylbenzene, Diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xyle , Cymene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl 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-hydroxyethyl methacrylate, hydroxypropyl methacrylate Glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, N , N-dimethylformamide, N, N-dimethylacetamide, dioxolane, one type of solvent selected from the group consisting of various silicone oils, or those containing two or more types of these solvents.
Among these solvents, those that vary depending on the type of resin used and the like are preferably 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-mentioned solvent is mainly used, but it can be used in combination with other solvents or other solvents can be used, and is more suitable for use (various resin materials for 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 inhibited, increasing the viscosity and causing aggregation between particles. May cause.
In the present invention, the non-aqueous solvent used preferably has a water content by the Karl Fischer method of 8000 ppm or less [0 ≦ water content ≦ 8000 ppm]. In the present invention (including examples to be described later), the measurement of 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 setting the water content in this solvent to 8000 ppm or less, a non-aqueous dispersion of fluororesin micropowder having a fine particle size, low viscosity and excellent storage stability can be obtained, more preferably 5000 ppm. Below, more preferably, it is 3000 ppm or less, especially 2500 ppm or less. For the adjustment of the water content, a generally used dehydration method of a solvent such as an oily solvent can be used. For example, molecular sieves can be used.

  The non-aqueous dispersion of the fluororesin of the present invention thus configured comprises at least a fluororesin micropowder, a thermoplastic elastomer, and a fluorine additive containing at least a fluorine-containing group and a lipophilic group. By containing non-aqueous solvent, fine particle size and low viscosity, excellent storage stability, suitable for mixing with various resin materials, low dielectric constant and low dielectric loss tangent while achieving low adhesion strength and adhesive strength Thus, a non-aqueous dispersion of a fluororesin that can suppress the above is obtained.

[Fluoropolymer-containing thermosetting resin composition]
The fluororesin-containing thermosetting resin composition of the present invention is characterized by containing at least the non-aqueous dispersion of the fluororesin and a resin composition containing a thermosetting resin.
The content of the non-aqueous dispersion of the fluororesin depends on the amount of the fluororesin micropowder such as PTFE, thermoplastic elastomer, and non-aqueous solvent contained in the dispersion, and the composition of the thermosetting resin or the like. The non-aqueous solvent such as an oil-based solvent in the resin composition is finally removed after the preparation of the composition containing the thermosetting resin, during curing, etc. The content of the micro-powder of fluororesin such as PTFE is preferably 1 to 100 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of these resins. It is desirable to adjust and use the dispersion.
When the content of the micro-powder of fluororesin such as PTFE is 1 part by mass or more with respect to 100 parts by mass of the resin, electrical characteristics of low dielectric constant and low dielectric loss tangent can be exhibited, By setting it as 100 mass parts or less, the effect of this invention can be exhibited, without impairing the adhesiveness and heat resistance which a thermosetting resin has.
Further, the content of the thermoplastic elastomer, and the content of the fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group are each 0.1 to 0.1% of the fluororesin micropowder as described above. The range is 100% by mass, 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 resins, polyimide resins, polyamideimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate ester resins, 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 any particular limitation as long as they are suitable for use, such as insulation and adhesiveness in electronic devices.
Preferred resin compositions include those containing at least a cyanate ester resin and / or an epoxy resin, and these resins are particularly suitable base resins for thermosetting resin compositions, and are insulating and adhesive 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 a bifunctional aliphatic cyanate ester, at least a bifunctional aromatic cyanate ester, or a mixture thereof. For example, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-disi Polymers of at least one polyfunctional cyanate ester selected from anatonaphthalene and 2,7-dicyanatonaphthalene, bisphenol A type cyanate ester resin or those obtained by adding hydrogen, bisphenol F type cyanate ester Resin or those with hydrogen added, 6F bisphenol A At least one of acid ester resin, bisphenol E type dicyanate resin, tetramethylbisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, or cyanate novolac resin Can be mentioned. Commercial 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, naphthylene ether type epoxy resin, Glycidylamine type epoxy resin, cresol novolak 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, tri Examples include methylol type epoxy resins and halogenated epoxy resins.
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 resin as long as it has 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 above-mentioned cyanate ester resin (cyanate ester resin) and epoxy resin can be used alone or in combination, and in the case of use in combination, they are used in a mass ratio of 1:10 to 10: 1. can do.

In the present invention, when the cyanate ester resin or epoxy resin is used, an active ester compound can be used as an additive from the viewpoint 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, phloroglucin, Benzenetriol, dicyclopentadienyl diphenol, phenol novolac and the like.
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, YLH1030 (manufactured by Japan Epoxy Resin Corporation), and the like.
The amount of these active ester compounds used is determined by the type of the active ester compound used and the base resin of the thermosetting resin composition used.
Furthermore, an active ester compound curing accelerator can be used for the active ester compound as needed.
As the active ester compound curing accelerator, an organic metal salt or an organic metal complex is used. For example, an organic metal salt or an organic metal complex containing iron, copper, zinc, cobalt, nickel, manganese, tin, or 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. Organometallic salts; organometallic complexes such as lead acetylacetonate and cobalt acetylacetonate.
These active ester compound hardening accelerators are 0.05-5 mass parts with respect to 100 mass parts of said resin used from the point of reactivity, sclerosis | hardenability, and a moldability on the basis of the density | concentration of a metal, Preferably it is 0.00. 1 to 3 parts by mass can be included.

Moreover, when using the said epoxy resin in this invention, a hardening | curing agent can also be used as an additive from the point of reactivity, sclerosis | hardenability, and a moldability. Examples of the curing agent that can be used include ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine and other aliphatic amines, metaphenylenediamine, paraphenylenediamine, Aromatic amines such as 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenolsulfone, 4,4′-diaminodiphenolmethane, 4,4′-diaminodiphenol ether, mercaptopropionic acid Esters, mercaptans such as terminal mercapto compounds of epoxy resins, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2, -Alicyclic acids such as dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride Anhydrides, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like Salts, amine adducts obtained by the reaction of aliphatic amines, aromatic amines, and / or imidazoles with epoxy resins, hydrazines such as adipic dihydrazide, dimethylbenzylamine, 1,8-diazabicyclo [5 4.0] tertiary amines such as undecene-7 and organic phosphines such as triphenylphosphine Fin such include at least one such dicyandiamide.
The amount of these curing agents used is determined by the epoxy resin used and the type of curing agent used.
In the resin composition of the present invention, an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a colorant, a thickener, an antifoaming agent, a leveling agent, a coupling agent, an adhesion-imparting material, etc. Combinations of materials generally used in thermosetting resin compositions for devices can also be used.

  In the present invention, the fluororesin micropowder is uniform without agglomeration by adjusting the total resin concentration such as thermosetting resin required in the final fluororesin-containing thermosetting resin composition. It has a low relative dielectric constant and dielectric loss tangent, and there is no decrease in adhesion strength and adhesive strength, so it can exhibit excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy. It will be like that.

[Fluoro resin-containing thermosetting resin cured product]
In the present invention, the fluororesin-containing thermosetting resin composition having the above-described configuration can be molded and cured by a method similar to that of 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 thermosetting resin compositions such as known epoxy resin compositions, and the method specific to the fluororesin-containing thermosetting resin composition of the present invention is unnecessary. It is 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, molded product, adhesive, coating film, film and the like.
The fluororesin-containing thermosetting resin composition of the present invention and its cured product have electrical properties of low dielectric constant and low dielectric loss tangent without impairing the adhesion and heat resistance of thermosetting resins such as epoxy resins. It is excellent, and since the decrease in adhesion strength and adhesive strength can be suppressed by containing a thermoplastic elastomer, it is suitable for electronic substrate materials, insulating materials, adhesive materials, etc., and is used for electronic parts, for example. It is useful as a material for sealing materials, copper-clad laminates, insulating paints, composites, insulating adhesives, etc., especially for the formation of insulating layers in multilayer printed wiring boards for electronic devices, laminated boards for circuit boards, coverlay films It can be suitably used for prepregs and the like.

  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.

[Preparation of non-aqueous dispersion of fluororesin: Dispersions 1 to 4]
Among the blending compositions shown in Table 1 below, a predetermined amount was blended for blending numbers [1] to [4], and then sufficiently stirred and mixed. Thereafter, 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 diameter of PTFE (average particle diameter of cumulant method analysis in scattering intensity distribution) in dispersions 1 to 4 composed of the above blending numbers [1] to [4] was adjusted by FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). (See Table 2 below).

Furthermore, for dispersions 1 and 2 consisting of formulation numbers [1] to [4], formulation numbers [5] and [6] were added and sufficiently stirred and mixed to prepare dispersions 1 to 4. .
Moreover, when the moisture content of the obtained dispersions 1-4 was measured, each moisture content by the Karl Fischer method was in the range of 500-1700 ppm, respectively.

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

[Examples 1 and 2 and Comparative Examples 1 to 3: Preparation of 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. In addition, Comparative Example 3 was prepared as a resin-only composition to which no PTFE dispersion was added.
After mixing at the blending ratios shown in Examples 1 and 2 and Comparative Examples 1 to 3, the dispersion was stirred using a disper so that the PTFE dispersion and the resin were uniformly mixed, and the fluororesin-containing thermosetting resin composition was obtained. Obtained.
Here, the blends of Examples 1 and 2 and Comparative Examples 1 and 2 showed a very uniform state, and PTFE aggregates were not observed.

[Examples 3 and 4 and Comparative Examples 4 to 6: Preparation of fluorinated resin-containing thermosetting resin cured product]
The entire surface of one side of the polyimide film (thickness: 25 μm) is dried with the fluororesin-containing thermosetting resin composition obtained in Examples 1 and 2 and Comparative Examples 1 to 3 to a thickness of about 25 μm. The sample is coated with a coater to a uniform thickness, dried at about 120 ° C. for about 10 minutes, and then heated and cured at 180 ° C. for 60 minutes to produce a sample for evaluation of relative dielectric constant. did.

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

[Evaluation of adhesion strength]
After covering a roughened surface of copper foil (thickness 18 μm) with one side roughened as a spacer with a 100 μm thick mesh, the fluorine-containing resin contained in Examples 1 and 2 and Comparative Examples 1 to 3 is contained. After applying the thermosetting resin composition and drying the solvent at 50 ° C. for 5 minutes, the copper foil (thickness: 18 μm) having one surface roughened is covered at 160 ° C. with the roughened surface facing the composition side. After laminating, a sample for adhesion evaluation was prepared by heating and curing at 180 ° C. for 60 minutes.

  Evaluation of adhesion strength produced the test piece cut to 1 cm width, and performed T-type peeling with the push pull tester.

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

  As shown in Table 4 above, the cured fluorinated resin-containing cured products according to Examples 3 and 4 exhibit a lower relative dielectric constant than Comparative Example 6 that does not contain a fluorinated resin and are thermoplastic. As a result, the adhesion strength was higher than those of Comparative Examples 4 and 5 which did not contain an 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, and contains the fluororesin using the non-aqueous dispersion of the present invention. The thermosetting resin composition and its cured product can achieve a low dielectric constant and a low dielectric loss tangent while suppressing a decrease in adhesion strength and adhesive strength. It can be suitably used for adhesives, circuit board laminates, coverlay films, prepregs, and the like.

Claims (8)

  A non-aqueous fluororesin comprising at least a micropowder of fluororesin, a thermoplastic elastomer, a fluorine-containing additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous solvent Dispersion.   The fluororesin micropowder contains polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotri The non-aqueous dispersion of a fluororesin according to claim 1, which is a micropowder of one or more fluororesins selected from the group consisting of a fluoroethylene copolymer and polychlorotrifluoroethylene.   The non-aqueous dispersion of a fluororesin according to claim 1 or 2, wherein the fluororesin micropowder is contained in an amount of 5 to 70% by mass.   The said thermoplastic elastomer is 0.1-100 mass% with respect to the mass of the micropowder of fluororesin, The fluororesin of any one of Claim 1 thru | or 3 characterized by the above-mentioned. Non-aqueous dispersion.   5. The fluorine-containing additive containing at least the fluorine-containing group and the lipophilic group is contained in an amount of 0.1 to 20% by mass with respect to the mass of the fluoro-resin micropowder. A non-aqueous dispersion of the fluororesin according to any one of the above.   A fluororesin-containing thermosetting comprising at least the non-aqueous dispersion of the fluororesin according to any one of claims 1 to 5 and a resin composition containing a thermosetting resin. Resin composition.   A fluorine containing at least the non-aqueous dispersion of a fluorine-based resin according to any one of claims 1 to 5 and a resin composition containing a cyanate ester resin and / or an epoxy resin. -Based resin-containing thermosetting resin composition.   A fluorinated resin-containing thermosetting resin cured product obtained by curing the fluorinated resin-containing thermosetting resin composition according to claim 6.