TW201835201A - Nonaqueous dispersion of fluorine-based resin heat cure resin composition containing fluorine-based resin using the same and the cured product thereof polyimide precursor solution composition - Google Patents

Abstract

Provided are a non-aqueous dispersion of a fluorine-based resin, a heat-curable resin composition containing a fluorine-based resin using the same, a polyimide precursor solution composition, and the like, wherein the non-aqueous dispersion of the fluorine-based resin is suitable for use in an insulating layer of a printed wiring board, an adhesive for a circuit substrate, a laminate for a circuit board, a coverlay film, and prepreg, which has a minute particle diameter, low viscosity, and excellent storage stability, can be properly mixed with a resin material such as a heat-curable resin composition or the like, and can suppress the degradation of adhesion strength and bonding strength while achieving a low dielectric constant and a low dielectric tangent. The non-aqueous dispersion of the fluorine-based resin at least contains micro-powder of a fluorine-based resin, a urethane particle, a compound represented by the following formula (I), and a non-aqueous solvent. Formula (I) [l, m, and n are positive integers].

Description

   Non-aqueous dispersion of fluororesin, thermosetting resin composition using the fluororesin and its hardened product, and polyimide precursor solution composition   

The present invention relates to a non-aqueous dispersion of a fluorine-based resin having a fine particle size, low viscosity, and excellent storage stability, and a thermosetting resin composition using the fluorine-containing resin, a hardened product thereof, and a polyimide precursor solution. Composition and so on.

In recent years, with the advancement in the speed and functionalization of electronic devices, higher speeds in communication speed have been required. In this situation, various electronic equipment materials are required to have a low dielectric constant and a low dielectric tangent, as well as a low dielectric constant and a low dielectric tangent of a thermosetting resin that can be used, such as insulating materials or substrate materials. Low dielectric constant and low dielectric tangent.

Materials with low dielectric constant and low dielectric tangent, such as polytetrafluoroethylene (PTFE, dielectric constant 2.1), which has the most outstanding characteristics among resin materials, have attracted attention. In the material, a method of melt-mixing PTFE is proposed, for example, a composition containing at least 50% by mass of PTFE and a polyaryletherketone having an effective amount for imparting melt-processability to the composition. 20% by mass has at least 10 ⁸ Pa. Melt viscosity of s (for example, refer to Patent Document 1).

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

The method for solving this problem is, for example, a method proposed by the applicant of the present invention to prepare an oil-based solvent dispersion of PTFE and add it to a thermosetting resin material. For example, PTFE having a primary particle diameter of 1 μm or less contains 5 to 70 masses. %. Fluorine additives containing at least fluoro group and lipophilic group contain 0.1 to 40% by mass relative to the mass of polytetrafluoroethylene. The total moisture content of the Karl Fischer Method is less than 20,000 ppm. An oil-based solvent dispersion of PTFE and an oil-based solvent dispersion of PTFE for epoxy resin material addition are featured (see, for example, Patent Documents 2 and 3).

The resin material added with the above-mentioned PTFE can exert an effect in terms of low dielectric constant and low dielectric tangent, which are not available so far. However, because of the non-adhesiveness of PTFE, resins or resins and metals When waiting, 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 urgently desired.

In addition, thermosetting resin compositions using epoxy resins, cyanate resins, etc. are widely used in electrical applications because of their excellent heat resistance, electrical insulation, and adhesion. Electronic use.

Generally, a thermosetting resin composition using an epoxy resin, a cyanate resin, or the like is suitable for use as an electronic substrate material, an insulating material, or an adhesive material, for example, as a packaging material for an electronic component or a copper-clad layer Materials such as plywood, insulating coatings, composite materials, insulating adhesives, and circuit board adhesive compositions used in the manufacture of circuit boards, and laminates, coating films, and prepregs for circuit boards , Insulation layers of multilayer printed wiring boards for electronic equipment, etc.

These thermosetting resin compositions and insulating materials using them need to be colored white, black, or other colored in order to impart concealability, optical properties, light-shielding or light-reflecting properties, and other creative functions. Wait.

For example high voltage electrical. Multilayer printed wiring boards used as components for electronic component installation places or for semiconductor mounting packages are mainly based on black. Therefore, a thermosetting resin composition based on black is used. In addition, a white thermosetting resin composition is used as a printed wiring board for mounting light emitting elements such as LEDs (light emitting diodes), a reflective plate for light emitting elements, a reflective material for organic EL light emission, and a base material for a white film of a metal layer. And need to increase every year.

These thermosetting resin compositions colored in white, black, etc., and insulating material compositions using them, for example, 1) use a composition in which an inorganic filler and a hardening accelerator are mixed with an acid anhydride as an agent A, and Oxygen resin is an acid-hardening type epoxy resin composition for agent B. An epoxy resin composition featuring a coloring agent having a quinacridone structure and a diazo dye is mixed with the agent B and cured. High-voltage electrical and electronic parts (for example, refer to Patent Document 4), 2) In order to provide a prepreg having no color unevenness or agglomerates, or an insulating resin sheet, the (B) colorant is dissolved and / or dispersed in (A) ) A step (1) of dispersing an inorganic filler in a solvent dispersion liquid and, thereafter, a step (2) of dissolving a (C) novolak-type epoxy resin, and a method for producing a resin composition (see, for example, patent) Documents 5) and 3) White curable resin compositions that have high reflectance and can suppress the decrease in reflectance and deterioration due to aging over time, and are used in printed wiring boards and light emitting devices for mounting light-emitting elements such as LEDs. In the case of reflectors for components, In the case of a white curable resin composition that makes good use of light such as LEDs, a white thermosetting resin composition containing (A) rutile-type titanium oxide and (B) thermosetting resin (for example, refer to Patent Document 6), 4 ) In order to provide a light-reflective thermosetting resin composition having sufficient light reflectance, molding processability, and excellent heat resistance and colorability, a substrate for mounting an optical semiconductor element using the same, a method for manufacturing the same, and an optical semiconductor device, Thermosetting resin composition for light reflection made of epoxy resin, hardener and white pigment with specific physical properties (for example, refer to Patent Document 7), 5) In order to provide excellent insulation and heat resistance, it is possible to achieve a high level of balance and achieve a surface A thermosetting resin composition having flatness, adhesion, and hardening properties, and excellent in both high-temperature insulation resistance and solvent resistance necessary for a manufacturing process, a cured product thereof, and a display member using the same, and therefore contains (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant such as carbon black, and (d) selected from the group consisting of barium sulfate, silicon dioxide, and talc Characterized by at least one of the thermosetting resin composition (see Patent Document 8).

However, when the thermosetting resin composition described in the aforementioned Patent Documents 4 to 8 is colored with a coloring material such as an organic pigment or an inorganic pigment, the cured material, the insulating material, the coating film, or the flexibility may be affected. Electrical characteristics (dielectric constant, dielectric tangent) or insulation of printed wiring boards.

In particular, when carbon black is used for coloring to black, not only the insulation is reduced, but the dielectric constant and the dielectric tangent are deteriorated. Therefore, it is not suitable for applications such as high-speed communication and high-speed processing.

Therefore, the colored thermosetting resin composition and the like have technical problems or limits in terms of electrical characteristics (low dielectric constant, low dielectric tangent) or insulation properties. Currently, it is required to provide concealment, optical characteristics, and light shielding. Properties such as electrical properties, light reflectivity, and creativity, and thermosetting resin compositions that further improve electrical characteristics (low dielectric constant, low dielectric tangent) or insulation properties, insulation material compositions using them, and circuit boards Adhesive composition, laminated board for circuit board, coating film, prepreg, flexible wiring board, and the like.

In addition, polyimide containing polyimide films and the like has been widely used in electrical applications because of its excellent heat resistance, electrical insulation, chemical resistance, and mechanical properties. Electronic use. For example, when polyimide is used as a thin film, it is used as an insulating substrate for electronic circuit materials, and it is also processed into an adhesive film or an adhesive tape. In addition, when it is used as a coating agent, the polyfluorene imide precursor solution composition is coated and dried, and then heat-treated to perform fluorination to serve as an insulation layer (interlayer insulation material for a multilayer wiring substrate) of an electronic circuit. When used as a surface protective film, heat-resistant protective film, or abrasion-resistant film for organic EL or semiconductor devices.

Generally, polyimide films are bonded to copper foil using an adhesive, or processed into a thin film layer and a copper foil by a vapor deposition method, a plating method, a sputtering method, or a cast film method. The laminate (polyimide film with copper foil) is used as a base film for flexible printed multilayer circuit boards.

This copper-clad laminated board is processed by a user to form a copper foil to form a wiring pattern. The wiring pattern is protected by an insulating coating film or the like. In addition, a polyimide film is mainly used as a base material of the coating film.

Covering films using such polyimide films, flexible printed wiring boards, etc. need to be colored in order to impart concealability, optical characteristics, light-shielding properties, light-reflective properties, creative properties, and other functions. Into white, black, other colored.

For example, white polyimide materials, such as white polyimide films, are used as the base material of heat-resistant lightweight white materials, LEDs (light emitting diodes), organic EL light-emitting reflective materials, or white films of metal layers. It can be used for flexible printed wiring boards, etc. for mounting LED, organic EL or other light-emitting elements.

In addition, colored polyimide materials, such as black, have become thinner and lower cost in recent years. At the same time, the requirements for shielding and optical characteristics of electronic components or mounting parts that have been protected have increased. Therefore, they have shielding properties and light shielding properties. The need for colored polyimide materials such as black is increasing every year.

Polyimide materials such as polyimide films colored in white and black are, for example, 1) polyamines obtained by reacting a specific diamine component with an aromatic tetracarboxylic acid, mixed with A white pigment mixture is cast onto a support, and a polyimide precursor film is obtained by drying. A white polyimide film obtained by subjecting the polyimide precursor film to imidization (for example, refer to Patent Document 9) ), 2) A multilayer polyimide film having a polyimide layer containing a pigment laminated on one or both sides of the polyimide layer will form the polyimide layer containing the polyimide layer containing the pigment. Amine, a light-shielding or light-reflecting multilayer polyimide film composed of specific components (see, for example, Patent Document 10), 3) a resin containing polyimide having a specific repeating unit, a colored coloring material, and a white pigment The colored light-shielding polyfluorene imide film (for example, refer to Patent Documents 11) and 4) composed of the composition contains a black pigment (A) and silicon dioxide (B) having a benzimidazole skeleton. The total weight of the pigments (A) and (B) A black polyimide film having a weight ratio in a specific range (for example, refer to Patent Document 12), 5) a pigment containing at least two kinds of pigments, a polyimide film, and a gloss of the polyimide film, A polyimide polymer obtained by adding a polyimide film having a thermal expansion coefficient to a specific range (for example, refer to Patent Documents 13 and 6) to a specific diamine monomer and a specific diacid anhydride monomer. A matting agent composed of imine particles and a polyimide film as a coloring base material of one or more coloring pigments (see, for example, Patent Document 14).

However, when the colored polyimide materials such as the colored polyimide films described in the aforementioned Patent Documents 9 to 14 are colored with a coloring material such as an organic pigment or an inorganic pigment, they may affect the coating film or be flexible. Electrical characteristics (dielectric constant, dielectric tangent) or insulation of printed wiring boards.

In particular, when carbon black is used for coloring to black, not only the insulation is reduced, but the dielectric constant and the dielectric tangent are deteriorated. Therefore, it is not suitable for applications such as high-speed communication and high-speed processing.

Therefore, colored polyfluorene materials have technical problems or limitations in electrical characteristics (low dielectric constant, low dielectric tangent), or insulation properties. Currently, it is required to provide concealment, optical characteristics, light-shielding properties, or light. Reflective, creative and other functions, and further improve the electrical characteristics (low dielectric constant, low dielectric tangent) or insulating polyimide precursor solution composition, polyimide film using it, etc.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2001-49068 (Patent Application Scope, Examples, etc.)

[Patent Document 2] Japanese Patent Laid-Open No. 2015-199901 (Patent Application Scope, Examples, etc.)

[Patent Document 3] Japanese Patent Laid-Open No. 2015-199903 (Patent Application Scope, Examples, etc.)

[Patent Document 4] Japanese Patent Laid-Open No. 2001-294728 (Scope of Patent Application, Examples, etc.)

[Patent Document 5] Japanese Patent Laid-Open No. 2009-114377 (Patent Application Scope, Examples, etc.)

[Patent Document 6] Japanese Patent Laid-Open No. 2010-275561 (Patent Application Scope, Examples, etc.)

[Patent Document 7] Japanese Patent Laid-Open No. 2013-155344 (Patent Application Scope, Examples, etc.)

[Patent Document 8] Japanese Patent Laid-Open No. 2015-78290 (Patent Application Scope, Examples, etc.)

[Patent Document 9] Japanese Patent Laid-Open No. 2008-169237 (Patent Application Scope, Examples, etc.)

[Patent Document 10] International Publication WO2010 / 126047 (Patent Application Scope, Examples, etc.)

[Patent Document 11] Japanese Patent Application Publication No. 2012-167169 (Patent Application Scope, Examples, etc.)

[Patent Document 12] Japanese Patent Laid-Open No. 2013-28767 (Patent Application Scope, Examples, etc.)

[Patent Document 13] Japanese Patent Laid-Open No. 2014-141575 (Patent Application Scope, Examples, etc.)

[Patent Document 14] Japanese Patent Laid-Open No. 2015-44977 (Patent Application Scope, Examples, etc.)

In order to solve the above-mentioned problems of the past, the present invention, etc., the first series provides fine particle size, low viscosity, and excellent storage stability. It is suitable for mixing with various resin materials to achieve low dielectric constant and low dielectric tangent. The purpose of the non-aqueous dispersion of a fluororesin, a non-aqueous dispersion of a fluororesin, and a thermosetting resin composition using the fluorinated resin and its hardened product can be suppressed. The coloring is given other functions such as concealment, optical characteristics, light-shielding or light-reflecting properties, and creativity. It also has high insulation, heat resistance, and electrical characteristics (low dielectric constant, low dielectric tangent), Colorable thermosetting resin composition excellent in processability, insulating material composition using the same, circuit board adhesive composition, laminate for circuit board, coating film, prepreg, flexible wiring board For the purpose of thermosetting resin compositions such as fluorine-containing resins, insulating material compositions using the same, etc., the third series provides concealment and optical characteristics even when colored with pigments or dyes. , Other functions such as light-shielding, light-reflecting, creative, etc., are also highly insulated, and have excellent heat resistance, electrical characteristics (low dielectric constant, low dielectric tangent), and workability. Imine, a polyimide precursor solution composition suitable for a polyimide film, a coating film using the same, a flexible printed wiring board, and the like, and a polyimide film using the same.

As a result of careful review of the above-mentioned conventional problems and the like by the present inventors, by the following first to tenth inventions, a non-aqueous dispersion of the fluorine-based resin of the first purpose can be obtained and used. Thermosetting resin composition of fluorinated resin and its cured product, thermosetting resin composition of fluororesin of the second purpose, insulation material composition using the same, and polyimide precursor of the third purpose The solution composition, a polyimide film using the same, etc., complete the present invention.

That is, the first invention is a non-aqueous dispersion of a fluorine-based resin, which includes at least: fine powder of a fluorine-based resin, urethane fine particles, a compound represented by the following formula (I), and a non-aqueous solvent , [In the above formula (I), l, m, and n are positive integers].

The second invention is a non-aqueous dispersion of a fluorine-based resin, which includes at least fine powder of a fluorine-based resin, a thermoplastic elastomer, a compound represented by the above formula (I), and a non-aqueous solvent.

The fine powder of the fluorine-based resin is selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, and ethylene-chlorine. Trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred as a fine powder of one or more kinds of fluorine-based resins.

The fine powder of the fluorine-based resin preferably contains 5 to 70% by mass, and the mass of the fine particles of the urethane relative to the fine powder of the fluorine-based resin preferably contains 0.1 to 20% by mass.

The compound represented by the formula (I) is preferably contained in an amount of 0.1 to 20% by mass based on the mass of the fine powder of the fluorine-based resin.

The thermoplastic elastomer preferably contains 0.1 to 100% by mass based on the mass of the fine powder of the fluorine-based resin.

The thermosetting resin composition of a fluorine-containing resin according to the first invention or the second invention is characterized by comprising a non-aqueous dispersion of at least the fluorine-based resin of the first invention or the second invention, and containing cyanic acid The resin composition of an ester resin and / or an epoxy resin, and this hardened | cured material is characterized by hardening the thermosetting resin composition of each said fluorine-containing resin.

Further, the thermosetting resin composition of the fluorine-containing resin of the second invention is characterized by including at least the non-aqueous dispersion of the fluorine resin of the second invention and the resin composition containing the thermosetting resin, which is hardened. It is a product obtained by curing the above-mentioned thermosetting resin composition of each fluorine-containing resin.

The third invention is a thermosetting resin composition containing a fluorine-containing resin, which contains at least fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a cyanate resin and / or ring. Resin composition of oxygen resin.

The fourth invention is a thermosetting resin composition containing a fluorine-based resin, which is a dispersion of at least a fine powder of a fluorine-based resin and a fine powder of a fluorine-based resin containing a compound represented by the formula (I) and a non-aqueous solvent. Body; coloring material; and resin composition containing cyanate resin and / or epoxy resin.

The fifth invention is a thermosetting resin composition containing a fluorine-containing resin, which is a dispersion of a fluorine-based resin fine powder containing at least a fine powder containing at least a fluorine-based resin, a compound represented by the formula (I), and a non-aqueous solvent A coloring material dispersion containing at least a coloring material and a non-aqueous solvent or a coloring material solution; and a resin composition containing a cyanate resin and / or an epoxy resin.

The sixth invention is a fluororesin-containing thermosetting resin composition, which is a fluororesin containing at least fine powder containing at least a fluororesin, a compound represented by the formula (I), a coloring material, and a non-aqueous solvent. A fine powder coloring material dispersion; and a resin composition containing a cyanate resin and / or an epoxy resin.

The fine powder of the fluorine-based resin is selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, and ethylene-chlorine. Trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred as a fine powder of one or more kinds of fluorine-based resins.

The coloring material is preferably at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes. The coloring material is preferably at least one selected from the group consisting of carbon-based black pigments, oxide-based black pigments, and white pigments.

In the fluorine-based resin fine powder dispersion, the average particle diameter of the fluorine-based resin fine powder in a dispersed state is preferably 10 μm or less.

The third invention to the sixth invention of the insulating material composition and the circuit board adhesive composition are characterized in that each of the third invention to the sixth invention of the fluorine-containing resin is used for thermal curing. Resin composition.

The laminated board for a circuit board according to the third invention to the sixth invention is a layer for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil. The plywood is characterized in that the adhesive layer is an adhesive composition for a circuit board obtained by using the thermosetting resin composition of a fluorine-containing resin according to any one of the third invention to the sixth invention.

The insulating film is selected from the group consisting of polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyphenylene sulfide ( PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-based aromatic polyamidoamine, polylactic acid, nylon, polyparabanic acid, polyetheretherketone ( PEEK), more than one type of film is preferred.

The third invention ~ the coating film of the sixth invention are an insulating film and a coating film having an adhesive layer formed on at least one side of the insulating film, wherein the adhesive layer uses the third invention ~ The adhesive composition for circuit boards obtained from the thermosetting resin composition of the fluorine-containing resin according to any one of the sixth invention is characterized by.

The insulating film is selected from the group consisting of polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyphenylene sulfide ( (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamidoamine, polylactic acid, nylon, polyparaline acid, polyetheretherketone (PEEK) Films of more than one type in a group are preferred.

The prepreg according to the third invention to the sixth invention is one or more kinds of fibers selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, or aromatic polyamide-based fibers. The formed structure is characterized by being impregnated with the thermosetting resin composition of at least the fluorine-containing resin according to any one of the third invention to the sixth invention.

The seventh invention is a polyfluorene imide precursor solution composition, which comprises at least: a fine powder of a fluorine-based resin, the compound represented by the formula (I), a coloring material, and a polyimide precursor solution.

The eighth invention is a polyfluorene imide precursor solution composition, which is at least: a fluorine resin fine powder dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent. ; Coloring material; and polyimide precursor solution.

The ninth invention is a polyfluorene imide precursor solution composition, which includes at least a fine powder dispersion of a fluorine resin containing at least a fluorine-based resin, a compound represented by the formula (I), and a non-aqueous solvent. ; A coloring material dispersion or a coloring material solution containing at least a coloring material and a non-aqueous solvent; and a polyimide precursor solution.

The tenth invention is a polyfluorene imide precursor solution composition, which includes at least: a fine powder containing at least a fluorine-based resin, a compound represented by the formula (I), a coloring material, and a non-aqueous solvent. Powder coloring material dispersion; and polyimide precursor solution.

The fine powder of the fluorine-based resin is selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, and ethylene-chlorine. Trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred as a fine powder of one or more kinds of fluorine-based resins.

The coloring material is preferably at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes, and the coloring material is preferably at least one selected from the group consisting of carbon-based black pigments, oxide-based black pigments, and white pigments.

The polyfluorene imide precursor solution preferably contains at least a tetracarboxylic acid dihydrate and / or a derivative thereof and a diamine compound.

In the fluorine-based resin fine powder dispersion, the average particle diameter of the fluorine-based resin fine powder in a dispersed state is preferably 10 μm or less.

The seventh invention, the tenth invention, the polyimide, the polyimide film, and the polyimide insulation film are characterized in that the polyimide described in any one of the seventh to tenth inventions is used. Obtained from imine precursor solution composition.

The coating film and flexible printed wiring board of the seventh invention to the tenth invention are obtained by using the polyimide precursor solution composition according to any one of the seventh invention to the tenth invention. Polyimide film.

The fluorine-based resin of the first invention or the second invention of the non-aqueous dispersion system has a fine particle size, low viscosity, and excellent storage stability, and is suitable for mixing with various resin materials. Use the first invention or the second invention A non-aqueous dispersion of a fluororesin-containing thermosetting resin composition and a cured product thereof can achieve a low dielectric constant, a low dielectric tangent, and can suppress a decrease in adhesion strength and adhesion strength.

According to the third invention to the sixth invention, even if colored by a pigment or a dye, it can provide other functions such as concealment, optical characteristics, light-shielding properties, light-reflecting properties, creativity, etc., and high insulation. Colored thermosetting resin composition excellent in heat resistance, heat resistance, electrical characteristics (low dielectric constant, low dielectric tangent), processability, etc., insulating material composition using the same, adhesive composition for circuit board, circuit Suitable thermosetting resin compositions such as a substrate laminate, a coverlay film, a prepreg, and a flexible wiring board.

In addition, an insulating material composition using a thermosetting resin composition of a fluorine-containing resin according to the third invention to the sixth invention, an adhesive composition for a circuit board, a laminate for a circuit board, a coating film, and a prepreg , Flexible printed wiring boards, etc., even if they are colored with organic or inorganic pigments or dyes, and are given other functions such as concealment, optical characteristics, light-shielding or light-reflecting properties, and creativity. Obtain colored insulation material composition, circuit board adhesive composition, circuit board laminate, and coating with excellent insulation, heat resistance, electrical characteristics (low dielectric constant, low dielectric tangent), and excellent processability. Films, prepregs, flexible printed wiring boards, etc.

According to the seventh invention to the tenth invention, even if colored by a pigment or a dye, it can provide other functions such as concealment, optical characteristics, light-shielding properties, light-reflecting properties, creativity, etc., and high insulation. Colored polyimide, polyimide film with excellent properties such as heat resistance, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc., coating film using the same, flexible printed wiring A suitable polyimide precursor solution composition such as a plate.

In addition, polyimide, polyimide film, polyimide insulation film, coating film, and flexible printed wiring board using the polyimide precursor solution composition of the seventh invention to the tenth invention Even if it is colored with an organic pigment, an inorganic pigment, or a coloring material of a dye and is given functions such as concealment, optical characteristics, light-shielding or light-reflecting properties, creativity, etc., high insulation, heat resistance, and electrical properties can be obtained. Colored polyimide, polyimide film, polyimide insulation film, coating film, flexible printed wiring board, etc., with excellent characteristics (low dielectric constant, low dielectric tangent), and workability. .

10‧‧‧ insulating film

20‧‧‧ Adhesive resin layer (adhesive composition layer for circuit board)

30‧‧‧ metal foil

[FIG. 1] A schematic diagram showing an example of an embodiment of a laminated board for a circuit board according to the third invention to the sixth invention according to a sectional view.

[Fig. 2] A schematic view showing another example of the embodiment of the laminated board for a circuit board of the third invention to the sixth invention according to a sectional view.

[Fig. 3] A schematic view showing an example of the embodiment of the coating film of the third invention to the tenth invention in a cross-sectional state.

    [Form of Implementing Invention]    

Hereinafter, each embodiment of this 1st invention to this 10th invention is demonstrated in detail according to each invention. It should be noted that the components common to each invention will be described in detail only in the first invention and the like, and the common features will be omitted in the second and subsequent inventions.

    [The first invention: Non-aqueous dispersion of fluorine resin]    

The non-aqueous dispersion of a fluorine-based resin according to the first invention is characterized in that it contains at least fine powder of a fluorine-based resin, urethane fine particles, a compound represented by the following formula (I), and a non-aqueous solvent.

[In the above formula (I), l, m, and n are positive integers]

The fine powder of the fluorine-based resin that can be used in the first invention is, for example, selected from polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), and chlorine. At least one of the group consisting of trifluoroethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE) It is preferable that the fine powder of the fluorine-based resin has a primary particle diameter of 1 μm or less.

Among the fine powders of the above-mentioned fluorine-based resins, especially materials having a low dielectric constant and a low dielectric tangent, it is preferable to use polytetrafluoroethylene (PTFE, dielectric constant 2.1) having the most excellent characteristics among the resin materials.

The fine powder of such a fluorine-based resin is obtained by an emulsion polymerization method, and can be obtained, for example, by a method generally used in a fluororesin manual (edited by Takao Kurokawa, Nikkan Kogyo Shimbun). Then, the fine powder of the fluorine-based resin obtained by the emulsification polymerization is agglomerated and dried, and the secondary particles agglomerated with the primary particle diameter are recovered as fine powder, and various kinds of fine powder manufacturing methods generally used can be used.

The particle diameter of the fine powder of the fluorine-based resin is preferably a primary particle diameter of 1 μm or less, and the non-aqueous dispersion preferably has an average particle diameter of 1 μm or less.

For stable dispersion in a non-aqueous solvent, the primary particle diameter is preferably 0.5 μm or less, more preferably 0.3 μm or less, and a more uniform dispersion can be obtained.

In addition, if the average particle diameter of the fluorine-based resin fine powder in the non-aqueous dispersion is more than 1 μm, it becomes easy to settle and it is difficult to stably disperse, which is not preferable. It is preferably 0.5 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05 μm or more and 0.3 μm or less.

In the first invention, a method for measuring the primary particle diameter can be used by laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) measured by the scattering method, dynamic light scattering method, image imaging method, etc., but after drying, it becomes a fine powder of a fluorine-based resin in a powder state. Primary particles have strong cohesion with each other, and sometimes it is difficult to diffract by laser. The primary particle diameter is measured by a scattering method, a dynamic light scattering method, or the like. In this case, the value obtained by the imaging method may also be expressed.

In addition, the measurement method of the particle size of the fluorine-based resin in the non-aqueous dispersion can be used by laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) measured by scattering methods, dynamic light scattering methods, and image imaging methods.

The particle diameter measurement device may be, for example, a dynamic light scattering method using FPAR-1000 (made by Otsuka Electronics Co., Ltd.) or laser diffraction using Microtrac (made by Nikkiso Co., Ltd.). Scattering method or image imaging method using Mac-VIEW (manufactured by Mountun Corporation).

In addition, the fine powder of the fluorine-based resin used may be mixed with two or more kinds having different primary particle sizes, or may be mixed with two or more kinds of the fine-grained fluorine-based resin fine powders having different average particle sizes. Fine powders of two or more kinds of fluorine-based resins having different primary particle diameters or average particle diameters are used. By using fine powder of two or more kinds of fluorine-based resins having different particle diameters, viscosity can be adjusted or filling rate can be increased.

The fine powder of the fluorine-based resin may be one subjected to various surface treatments. For example, by using acid treatment, alkali treatment, ultraviolet irradiation treatment, ozone treatment, electron beam irradiation treatment, heat treatment, water washing, hot water washing, various gas treatments, etc., it is possible to remove the surfactant or the surfactant remaining on the surface of the fine powder of the fluorine resin. Unwanted components such as impurities may be activated.

In the first invention, it is preferable that the fine powder of the fluorine-based resin contains 5 to 70% by mass, and more preferably 10 to 60% by mass, with respect to the entire amount of the non-aqueous dispersion.

When the content is less than 5% by mass, the amount of the solvent is large, and the viscosity is extremely reduced. Therefore, the fine powder particles of the fluorine resin not only become easy to settle, but also when mixed with materials such as cyanate resin and epoxy resin. In some cases, the amount of the solvent is poor, for example, the time required to remove the solvent may be poor. In addition, when it exceeds 70% by mass, the fine powder of the fluorine-based resin becomes easily aggregated with each other, and it is extremely difficult to maintain a fine particle state in a stable and fluid state, which is not preferable.

Since the urethane fine particles used in the first invention are non-adhesive to PTFE, they are included in order to solve adhesion strength, decrease in adhesion strength, and the like when resins are adhered to each other or resins and metals, etc., and Even if the urethane fine particles are contained, the stability of the non-aqueous dispersion of the fluororesin and the like will not be impaired.

Examples of usable urethane microparticles include microparticles made of a polyurethane having a urethane bond, which are generally widely used, and are generally produced by a compound having an isocyanate group and a hydroxyl group.

In the non-aqueous solvent used, the urethane fine particles may be present in a particulate form, but not only hard urethane fine particles which are sufficiently crosslinked, but also elastomeric urethanes may be used. Ester fine particles. The shape of the urethane particles may be amorphous, spherical, or true spherical.

In addition, when the urethane fine particles are urethane-containing particles, any particles can be used. For example, urethane fine particles containing inorganic components such as urethane fine particles containing acrylate components or silicon dioxide may be used. Is a homopolymer or a copolymer. Specific examples include commercially available Daimicbeaz CM (manufactured by Daiichi Seika Kogyo Co., Ltd.), Art pearl (manufactured by Kegami Industry Co., Ltd.), Gran pearl (manufactured by AICA Industry Co., Ltd.), and the like.

Examples of the method for forming the urethane microparticles include a method of pulverizing a block of polyurethane to form a micronized particle, or a method of forming a micronized particle using suspension polymerization, emulsification polymerization, or the like. Generally used amine groups can be used. Method for producing formate fine particles. The surface of the fine particles may be coated with a hydrophobic silica or a fluorine-based compound-treated silica.

The particle diameter of the urethane fine particles is preferably one having a primary particle diameter of 10 m or less, and in a non-aqueous dispersion, one having an average particle diameter of 10 m or less.

In a non-aqueous solvent, the stable dispersion is preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less in primary particle diameter, and a more uniform dispersion can be obtained.

In addition, if the average particle size of the urethane fine particles in the non-aqueous dispersion is more than 10 μm, it becomes easy to settle and it is difficult to stably disperse, which is not preferable. It is preferably 3 μm or less, and even more preferably 1 μm or less. The measurement of the primary particle size of the urethane 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 above-mentioned methods for measuring the fine powder of the fluororesin.

In the first invention, it is preferable that the urethane fine particles contain 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and even more preferably 0.5 to 10, with respect to the mass of the fine powder of the fluorine-based resin. quality%.

When the content is less than 0.1% by mass, the addition of urethane fine particles significantly weakens the contribution to adhesion and adhesion, which is not preferable. On the other hand, when it exceeds 20% by mass, the electrical characteristics or physical characteristics of the urethane particles are strongly emitted, and the effect of the electrical characteristics due to the addition of PTFE is weakened, which is not preferable.

In the first invention, the urethane fine particles and the fine powder of the fluororesin may be dispersed simultaneously, or the urethane fine particles and the fine powder of the fluororesin may be individually dispersed and mixed.

The compound represented by the above (I) used in the first invention may be one in which fine powder of a fluorine-based resin is dispersed uniformly and finely in fine particles in a non-aqueous solvent. Its molecular structure is a tertiary polymer composed of vinyl butyral / vinyl acetate / vinyl alcohol, which reacts polyvinyl alcohol (PVA) with butyraldehyde (BA), and has a butyral group, an acetamyl group, and a hydroxyl group. Structure, by changing the ratio of these three structures (each ratio of l, m, n), it is possible to control the solubility in non-aqueous solvents, and non-aqueous systems in which fine fluorine-based resin powder is added to various resin materials Chemical reactivity in dispersion.

For the compound represented by the above (I), S-Lec B series, K (KS) series, SV series, Kuraray company Mowital series, etc. can be used as commercially available products.

Specifically, the product name made by Sekisui Chemical Industry Co., Ltd .; S-Lec BM-1 (hydroxyl amount: 34 mole%, butyralization degree 65 ± 3 mole%, molecular weight: 40,000), same as BH -3 (hydroxyl content: 34 mol%, butyralization degree 65 ± 3 mole%, molecular weight: 110,000), the same as BH-6 (hydroxyl amount: 30mol%, butyralization degree 69 ± 3 mole%, Molecular weight: 92,000), same as BX-1 (hydroxyl amount: 33 ± 3mol%, acetalization degree: 66 mole%, molecular weight: 100,000), same as BX-5 (hydroxyl amount: 33 ± 3mol%, acetalization) Degree 66 mole%, molecular weight: 130,000), same as BM-2 (hydroxyl amount: 31mol%, butyralization degree 68 ± 3 mole%, molecular weight: 52,000), same as BM-5 (hydroxyl amount: 34mol) %, Butyralization degree 65 ± 3 mole%, molecular weight: 53,000), the same as BL-1 (hydroxyl amount: 36mol%, butyralization degree 63 ± 3 mole%, molecular weight: 19,000), the same BL-1H (hydroxyl content: 30mol%, butyralization degree 69 ± 3 mole%, molecular weight: 20,000), the same as BL-2 (hydroxyl content: 36mol%, butyralization degree 63 ± 3 mole%) , Molecular weight: 2.7), same as BL-2H (hydroxyl amount: 29mol%, butyralization degree 70 ± 3 mole%, molecular weight: 28,000), same as BL-10 (hydroxyl amount: 28mol%, butyralization) Degree 71 ± 3 mole%, Sub-quantity: 15,000), the same as KS-10 (hydroxyl amount: 25mol%, acetalization 65 ± 3 mole%, molecular weight: 17,000), etc., or a product name made by Kuraray (stock); Mowital B145 (hydroxyl amount : 21 ~ 26.5 mole%, acetalization degree 67.5 ~ 75.2 mole%), same as B16H (hydroxyl amount: 26.2 ~ 30.2 mole%, acetalization degree 66.9 ~ 73.1 mole%, molecular weight: 10,000 ~ 20,000 )Wait.

These can be used alone or in combination of two or more.

Content of the compound represented by said (I) is 0.1-20 mass% with respect to the fine powder of a fluorine resin. When the content of this compound is less than 0.1% by mass, the dispersion stability is deteriorated, and the fine powder of the fluorine-based resin becomes liable to settle. When it exceeds 20% by mass, the viscosity becomes high, which is not preferable.

In addition, when considering the characteristics of a non-aqueous dispersion of a fine powder of a fluorine-based resin in a thermosetting resin or the like, it is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.1 to 5 mass%.

The non-aqueous dispersion of the fine powder of the fluorine-based resin in the first invention may be combined with the compound represented by the above (I) to the extent that the effects of the first invention are not impaired, and other surfactants or Dispersant.

Examples include non-fluorine-based and non-fluorine-based surfactants, such as nonionic, anionic, and cationic surfactants or dispersants, nonionic, anionic, and cationic surfactants or polymer dispersions. Agents and the like are not limited to these and can be used.

Examples of the non-aqueous solvent used in the non-aqueous dispersion of the first invention are selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, Cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isoamyl 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 Alcohol 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, 3 -Ethyl ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate , Ethyl ethoxypropionate, anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, bibenzyl ether, phenyl ether, butyl phenyl ether, benzene, ethyl benzene, diethyl benzene Amylbenzene, cumene, toluene, xylene, isopropyl toluene, mesitylene, methanol, ethanol, isopropyl alcohol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, Butyl monoglycidyl ether, phenyl monoglycidyl ether, methylglycidyl ether, ethylglycidyl ether, butylglycidyl ether, phenylglycidyl ether, cresol Monoglycidyl ether, Ethylphenol monoglycidyl ether, Butyl phenol monoglycidyl ether, Mineral spirit, 2-Hydroxyethyl acrylate, Tetrahydrofurfuryl acrylate, 4-Vinylpyridine, N-formyl 2-Pyrrolidone, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, epoxypropyl methacrylate, neopentyl glycol diacrylate, hexane Glycol diacrylate, trimethylolpropane triacrylate, methacrylate, methmethacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropoly Ether, N, N-dimethylformamide, N, N-dimethylacetamide, dioxane, various types of silicone oils, or solvents containing two or more kinds By.

Among these solvents, those which vary depending on the type of resin used, and the like are exemplified by methyl ethyl ketone, cyclohexanone, toluene, xylene, N-methyl-2-pyrrolidone, N, N-dimethyl Methylformamide, N, N-dimethylacetamide, dioxolane.

The first invention mainly uses the above-mentioned solvents, and may be used in combination with other solvents or other solvents, and is preferably selected depending on the use (various circuit board resin materials) and the like.

In addition, due to the polarity of the solvent used, those with higher compatibility with water are considered. However, when the amount of water is large, the dispersion of the fine powder of the fluororesin in the solvent may be hindered, which may cause an increase in viscosity or particles. Cohesion.

In the present invention, the non-aqueous solvent and the non-aqueous dispersion to be used are preferably 8000 ppm or less [0 ≦ water content ≦ 8000 ppm] by the water content of the Carr Fisher method. In the present invention (including examples described later), the measurement of the water content by the Carr Fisher method is based on JIS K 0068: 2001, and for example, it can be measured by MCU-610 (manufactured by Kyoto Electronics Industry Co., Ltd.). By setting the water content in the solvent and the water content of the non-aqueous dispersion to 8000 ppm or less, a non-aqueous dispersion of fine powder of a fluorine-based resin with a low viscosity and excellent storage stability can be formed. It is more preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 2500 ppm or less. In addition, for the adjustment of the water content, a dehydration method using a solvent such as an oily solvent generally used can be used, and for example, molecular sieve can be used.

The non-aqueous dispersion of the fluororesin of the first invention thus constituted contains micropowder of at least a fluororesin, fine particles of urethane, a compound represented by the above formula (I), and a non-aqueous solvent. Particle size, low viscosity, excellent storage stability, suitable for mixing with various resin materials to achieve low dielectric constant, low dielectric tangent, non-aqueous dispersion of fluorine-based resin that can suppress adhesion strength and then decrease strength.

    [The second invention: Non-aqueous dispersion of fluorine resin]    

The non-aqueous dispersion of a fluorine-based resin according to the second invention is characterized by containing at least a fine powder of a fluorine-based resin, a thermoplastic elastomer, a compound represented by the above formula (I), and a non-aqueous solvent.

In the second invention, only a thermoplastic elastomer is used in place of the urethane fine particles of the first invention, which is different from the first invention. Therefore, the thermoplastic elastomer is described, and the fluororesin used in the second invention is described. The fine powder, the compound represented by the formula (I), and the non-aqueous solvent have been described in detail in the first invention, and therefore descriptions thereof are omitted. Hereinafter, the thermoplastic elastomer used in the second invention will be described.

Since the thermoplastic elastic system used in the second invention has non-adhesion property of PTFE, when resins are bonded to each other, or resins and metals, etc., it is included in order to resolve adhesion strength, decrease in bonding strength, etc., and contains the heat Plastic elastomers do not impair the stability of non-aqueous dispersions of fluorine resins.

The thermoplastic elastomer of the second invention can be used as long as it is a plasticizable elastomer at the time of heating, and examples thereof include styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, and vinyl chloride systems. Thermoplastic elastomers, urethane-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polybutadiene (1,2-BR) -based thermoplastic elastomers, At least one of the acrylic elastomer and the silicone elastomer can be appropriately selected depending on the application of the non-aqueous dispersion of the fluorine resin.

Specific examples include styrene-butadiene copolymer (SBS), hydrogenated-styrene-butadiene copolymer (SEBS), hydrogenated-styrene-isoprene copolymer (SEPS), and polyester- Polyether copolymer (TPEE), polyurethane-polyether / polyester copolymer (TPU), nylon-polyether / polyester copolymer (TPA), PP, etc. There are olefin-based thermoplastic elastomers (TPO) and the like of olefin-based rubbers. Commercial products include SIS series (styrene-based thermoplastic elastomer, manufactured by JSR Corporation), TR series (styrene-butadiene thermoplastic elastomer, manufactured by JSR Corporation), and 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), Themorun (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 kinds.

The thermoplastic elastomer used in the second invention may be a non-aqueous solvent that is soluble or insoluble in use.

When it is insoluble in the non-aqueous solvent to be used, the thermoplastic elastomer is preferably used in the form of fine particles.

The primary particle diameter is preferably 10 μm or less, and in a non-aqueous dispersion, the average particle diameter is preferably 10 μm or less.

In a non-aqueous solvent, the stable dispersion is preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less in primary particle diameter, and a more uniform dispersion can be obtained.

In addition, when the average particle diameter of the fine particles of the thermoplastic elastomer in the non-aqueous dispersion is more than 10 μm, it becomes easy to settle and it is difficult to stably disperse, which is not preferable. It is preferably 3 μm or less, and even more preferably 1 μm or less. The measurement of the primary particle diameter of the fine particles of the thermoplastic elastomer and the measurement of the average particle diameter of the urethane particles in the non-aqueous dispersion can be performed in the same manner as the above-mentioned methods of measuring the fine powder of the fluorine-based resin.

In the second invention, the thermoplastic elastomer preferably contains 0.1 to 100% by mass, more preferably 0.3 to 80% by mass, and more preferably 0.5 to 50% by mass relative to the mass of the fine powder of the fluorine-based resin. .

When the content is less than 0.1% by mass, the contribution to the adhesion and adhesion is significantly weakened by the addition of the thermoplastic elastomer, which is not preferable. When it exceeds 100% by mass, the electrical properties or physical properties of the thermoplastic elastomer, the effect of plasticization during heating, and the like appear strongly, and the effect of the electrical properties or the physical properties becomes weak due to the addition of the fluorine-based resin. So bad.

In the second invention, the thermoplastic elastomer can be dissolved in a non-aqueous solvent for use in dispersing a fine powder of a fluorine-based resin, and can also be used to dissolve the thermoplasticity after preparing a dispersion of a fine powder of a fluorine-based resin. Elastomer to use. When the thermoplastic elastomer is insoluble in a non-aqueous solvent, the fine particles of the thermoplastic elastomer and the fluorine-based resin may be dispersed at the same time, and the fine particles of the thermoplastic elastomer and the fine powder of the fluorine-based resin may be separately dispersed and mixed. Wait.

The non-aqueous dispersion of a fluororesin of the second invention of the present invention, which is composed of fine powder of at least a fluororesin, a thermoplastic elastomer, a compound represented by the above formula (I), and a non-aqueous solvent, can be obtained. Particle size, low viscosity, excellent storage stability, suitable for mixing with various resin materials to achieve low dielectric constant, low dielectric tangent, and non-aqueous dispersion of fluororesin that can suppress adhesion strength and decrease in strength .

    [Thermosetting resin composition of the fluorine-containing resin of the first invention and the second invention]    

The thermosetting resin composition of the fluorine-containing resin according to the first invention and the second invention is characterized by including a non-aqueous dispersion of at least the fluorine-based resin of the first invention or the second invention, and a cyanate resin-containing resin. And / or epoxy resin composition.

The content of the non-aqueous dispersion of the above-mentioned fluorine-based resin is due to the fine powder of fluorine-based resin such as PTFE contained in the dispersion, urethane fine particles or thermoplastic elastomer, and the compound represented by the above formula (I). And the amount of non-aqueous solvents, or the use of cyanate resins, epoxy resins, and other components. The non-aqueous solvents such as oily solvents in the resin composition are After the composition of the oxygen resin is prepared, it is removed at the time of curing. Therefore, the content of the fine powder of fluorine resin such as PTFE is adjusted to 1 to 100 parts by mass relative to 100 parts by mass of these resins. , More preferably from 1 to 30 parts by mass, and a dispersion is preferred.

The content of the fine powder of the fluorine-based resin such as PTFE is set to 1 part by mass or more based on 100 parts by mass of the resin, and can exhibit the electric characteristics of low dielectric constant and low dielectric tangent, and is set to 100 parts by mass or less. The effect of the present invention can be exhibited without impairing the adhesiveness or heat resistance of the cyanate resin and the epoxy resin.

In the first invention, the content of the urethane fine particles and the content of the compound represented by the formula (I) are each in the range of 0.1 to 20% by mass relative to the fine powder of the fluorine-based resin, as described above. . The content of the thermoplastic elastomer of the second invention is in the range of 0.1 to 100% by mass based on the mass of the fine powder of the fluorine-based resin, and the content of the compound represented by the above formula (I) is as described above, relative to the fluorine-based resin. Resin fine powder is in the range of 0.1-20% by mass.

Examples of the resin composition used in the first invention and the second invention include those containing at least a thermosetting resin. Examples of the thermosetting resin include epoxy resin, polyimide resin, polyimide resin, triazine resin, phenol resin, melamine resin, polyester resin, cyanate resin, and modification of these resins. Resin, etc., these resins can be used alone or in combination of two or more. Those resins used as the base resin of the thermosetting resin composition can be used without particular limitation as long as they are suitable for users such as insulation or adhesion in electronic equipment.

Preferred resin compositions include those which are at least relative to cyanate resins and / or epoxy resins. These resins are particularly good base resins for thermosetting resin compositions, and are suitable for insulating properties in electronic equipment or Follow sex and so on.

Examples of the cyanate resin (cyanate ester resin) that can be used in the first invention and the second invention include at least two-functional aliphatic cyanate, at least two-functional aromatic cyanate, or These mixtures include, for example, selected from 1,3,5-tricyanoxybenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, and 1,6-dicyanooxy Polymer of at least one of naphthalene, 1,8-dicyanooxynaphthalene, 2,6-dicyanooxynaphthalene, and 2,7-dicyanooxynaphthalene, bisphenol A type cyanide Ester resin or these hydrogenated, bisphenol F-type cyanate resin or these hydrogenated, 6F bisphenol A dicyanate resin, bisphenol E-type dicyanate resin, tetramethylbisphenol At least one of F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, or cyano novolac resin. Moreover, you may use the commercial item of these cyanate resin.

Usable epoxy resins include, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, and naphthalene ring Oxygen resin, naphthalene ether epoxy resin, epoxypropylamine epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin Resin, heterocyclic epoxy resin, spiro-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, etc.

These epoxy resins can be used singly or in combination of two or more kinds.

The epoxy resin that can be used in the first invention and the second invention is not limited to the above resins as long as it has one or more epoxy groups in one molecule, and is preferably bisphenol A, hydrogenated bisphenol A, Cresol novolac series.

In the present invention, each of the cyanate resin (cyanate ester resin) and epoxy resin may be used alone or in combination. When used in combination, the cyanate resin (cyanate ester resin) and epoxy resin may be used in a range of 1:10 to 10: 1 by mass.

When using the said cyanate resin and epoxy resin in this 1st invention and this 2nd invention, an active ester compound can be used as an additive from a viewpoint of reactivity, hardenability, and moldability.

The active ester compound that can be used is generally a compound having two or more active ester groups in one molecule, 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, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol. Phenol 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, resorcinol, pyroglycerol, dicyclopentadienediphenol, phenol novolac, etc. .

These active ester compounds may be used singly or in combination of two or more kinds. 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 to be used is determined by the base resin of the thermosetting resin composition used and the type of the active ester compound used.

Further, among the aforementioned active ester compounds, if necessary, an active ester compound hardening accelerator can be used.

As the active ester compound hardening accelerator, an organometallic salt or an organometallic complex can be used. For example, an organometallic salt or an organometallic complex containing iron, copper, zinc, cobalt, nickel, manganese, tin, or the like can be used. Specifically, the cyanate ester hardening accelerator includes manganese decalinate, iron decalinate, copper decalinate, zinc decalinate, cobalt decalinate, iron octoate, copper octoate, zinc octoate, and octanoic acid. Organometallic salts of cobalt, etc .; organometallic complexes of lead acetamidine pyruvate, cobalt acetamidine pyruvate, and the like.

These active ester compound hardening accelerators are based on the concentration of the metal, and from the viewpoints of reactivity, hardenability, and formability, they are contained in an amount of 0.05 to 5 parts by mass relative to 100 parts by mass of the resin used previously, and preferably contained. 0.1 ~ 3 parts by mass.

Moreover, when using the said epoxy resin in this 1st invention and this 2nd invention, a hardening agent can be used as an additive from a viewpoint of reactivity, hardenability, and moldability. Examples of usable hardeners include aliphatics such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine. Amine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl Aromatic amines such as methane, 4,4'-diaminodiphenyl ether, thiols such as mercaptopropionate, terminal mercapto compounds such as epoxy resin, polyazelaic anhydride, methyl tetrahydro o-phenylene Dicarboxylic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2, Alicyclic acid anhydrides, phthalic anhydride, such as 3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride , Aromatic anhydrides such as trimellitic anhydride, pyromellitic anhydride, etc., imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and their salts, and the above Aliphatic amines, aromatic amines, and / or amine adducts obtained by the reaction of imidazoles and epoxy resins , Hydrazines such as Adipic acid dihydrazide, dimethylbenzylamine, tertiary amines such as 1,8-diazabicyclo [5.4.0] undecene-7 , At least one of organic phosphines such as triphenylphosphine, dicyandiamide, and the like.

The amount of these hardeners to be used depends on the epoxy resin used and the type of hardener used.

In the resin composition of the first invention and the second invention, an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a colorant, a tackifier, a defoamer, a flattening agent, and a coupling agent may be further used in combination. Mixtures, adhesiveness-imparting materials, and the like are generally used in thermosetting resin compositions for electronic devices.

In the first invention and the second invention, by adjusting the total resin concentration of a cyanate resin, an epoxy resin, and the like necessary for the final thermosetting resin composition of the fluorine-containing resin, fine powder of the fluorine-based resin can be made. It does not aggregate and exists uniformly, and the dielectric constant and dielectric tangent are low, and the adhesive strength and bonding strength are not reduced. Therefore, it can exhibit excellent characteristics such as adhesion, heat resistance, dimensional stability, and flame resistance.

    [Thermosetting resin cured product of the fluorine-containing resin of the first invention and the second invention]    

The thermosetting resin composition of the fluorine-containing resin of the first invention and the second invention can be molded and hardened by the same method as a conventional thermosetting resin composition such as an epoxy resin composition, and can be hardened. Thing. As the molding method and the curing method, the same method as the conventional thermosetting resin composition such as an epoxy resin composition can be used. The method inherent to the thermosetting resin composition of the fluorine-containing resin of the present invention is not required, and there is no particular limitation. .

The cured product obtained by curing the thermosetting resin composition of the fluorine-containing resin of the first invention and the second invention may be in the form of a laminate, a molded product, an adhesive, a coating film, or a film.

The thermosetting resin composition of the fluorine-containing resin of the first invention and the second invention and the cured product thereof do not impair the adhesiveness or heat resistance of the thermosetting resin such as an epoxy resin, and have low dielectric properties. Constant, excellent electrical properties with low dielectric tangent, and contain urethane particles to suppress adhesion strength and decrease bonding strength, so it is suitable for electronic substrate materials, insulating materials, bonding materials, etc. Packaging materials for parts, copper-clad laminates, insulation coatings, composite materials, insulation adhesives, etc., especially suitable for forming the insulation layer of multilayer printed wiring boards for electronic equipment, laminates for circuit boards, and coatings Film, prepreg, etc.

    [The third invention to the sixth invention: a thermosetting resin composition of a fluorine-containing resin]    

The thermosetting resin composition of a fluorine-containing resin according to the third invention is characterized in that it contains at least a fine powder of a fluorine-based resin, a compound represented by the formula (I), a coloring material, and a cyanate resin and / or epoxy resin. For a resin composition of a resin, the fourth invention includes at least a dispersion of a fluorine-based resin fine powder containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I) and a non-aqueous solvent, a coloring material, and a cyanide-containing material. The resin composition of an ester resin and / or an epoxy resin is characterized in that the fifth invention includes at least a fluorine resin containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent. The 6th invention is characterized by a fine powder dispersion, a coloring material dispersion or a coloring material solution containing at least a coloring material and a non-aqueous solvent, and a resin composition containing a cyanate resin and / or an epoxy resin. A dispersion of a fluorine-based resin fine powder coloring material containing at least a fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a non-aqueous solvent, and a cyanate resin and / or epoxy The lipid composition is characterized by a resin.

Hereinafter, the third to sixth inventions will be described in detail for the thermosetting resin composition of each fluorine-containing resin. In addition, the fine powder of the fluorine-based resin used in the third invention to the sixth invention, the compound represented by the formula (I), a non-aqueous solvent, a cyanate resin, an epoxy resin, and the like are the same as those in the first invention. In this case, the description is omitted, and if it is not the same, the details are as follows.

    [The third invention: a thermosetting resin composition of a fluorine-containing resin]    

The fine powder of the fluorine-based resin used in the third invention can be used in the detailed description of the first invention, and the content thereof is preferably 5 to 70% by mass based on the total solid content of the thermosetting resin composition. It is more preferably 10 to 60% by mass.

When the content is less than 5% by mass, the properties of the fluororesin cannot be sufficiently imparted to the final thermosetting resin or the like, and when the content exceeds 70% by mass, the mechanical strength of the final thermosetting resin or the like is insufficient. Extremely weak, etc., so poor.

In the third invention, the compound represented by the formula (I) used may be used in the detailed description of the first invention, and its content is preferably 0.01 to 30% by mass based on the fine powder of the fluorine-based resin. When the content of this compound is less than 0.01% by mass, the dispersion stability is deteriorated, and the fluorine-based fine powder becomes easy to settle. When it exceeds 30% by mass, the viscosity of the thermosetting resin composition becomes high, which is not preferable.

In addition, when considering the characteristics of the obtained thermosetting resin and the like, it is more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 2% by mass.

In the third invention (to the tenth invention), as described in the first invention, in combination with the compound represented by the formula (I), other surfactants or dispersants may be used.

    <Coloring material>    

The coloring material used in the third invention includes at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes.

Inorganic pigments, organic pigments, and dyes that can be used, as long as they are used to color heat-curing resin materials such as coating films and flexible printed wiring boards, and provide concealment, optical characteristics, light-shielding or light-reflective properties, and creativity There are no particular restrictions on the use of such properties as electrical properties, and it is preferred that the electrical properties and processability properties such as insulation, low dielectric constant, and low dielectric tangent are not impaired, so that the effects of the present invention can be exerted more effectively. From the viewpoint, at least one selected from the group consisting of a carbon-based black pigment, an oxide-based black pigment, and a white pigment is used as the inorganic pigment and the organic pigment.

Examples of the carbon-based black pigment include carbon blacks such as furnace black, acetylene black, thermal black, and channel black, biotite, graphite powder, and graphite powder marketers.

The oxide-based black pigment is, for example, selected from the group consisting of cobalt oxide, ferric tetroxide, ferrous oxide, manganese oxide, titanium black, chromium oxide, bismuth oxide, tin oxide, copper oxide or copper-iron-manganese, aniline black, Black, iron manganese bismuth black, cobalt iron chromium black, copper chromium manganese black, iron chromium black, manganese bismuth black, manganese yttrium black, iron manganese oxide spinel black, copper chromium spinel black, pyrite, At least one of the group consisting of magnetite, mica-like iron oxide, metal oxide containing titanium black and iron, and composite metal oxide.

Among these black pigments, carbon black, which is excellent in light-shielding properties, is commercially available as # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, manufactured by Mitsubishi Chemical Corporation. # 44, # 45, # 47, # 52, # 85, # 95, CF9, MA7, MA8, MA11, MA100, MA220, MA230, etc., Printex25, 35, 40, 45, 55, 150T, made by Evonik Industries, Printex series such as U, V, P, L6, etc., and black pigments for improving electrical reliability. It is better to use commercially available products such as Lumogen black series and Paliogen black series made by BASF. Alternatively, an aluminum flake pigment (black interference aluminum pigment) having excellent heat shielding properties may be used.

White pigments can use titanium oxide, aluminum oxide, barium sulfate, magnesium oxide, aluminum nitride, boron nitride (hexagonal cubic), barium titanate, zirconia, calcium oxide, zinc oxide, zinc sulfide, calcium sulfate, alkali Zinc molybdate, basic calcium zinc molybdate, molybdenum white, kaolin, silicon dioxide, talc, powder mica, powder glass, powder aluminum, powder nickel, calcium carbonate, etc.

Among these white pigments, titanium oxide, which has a large hiding power, and silicon dioxide, which has high insulation properties, are more preferable. These can be used in combination. By using both of them, both the insulation and the reflection properties can be improved. Examples of the titanium oxide include anatase-type titanium oxide and rutile-type titanium oxide. Among these, when used for LEDs, anatase titanium oxide that reflects the wavelengths of near-ultraviolet LEDs and blue LEDs is more preferred. Examples of the finely powdered silica include crystalline silica, fusible silica, and fumed silica.

In addition, the surface of titanium oxide is treated with alumina, silicon dioxide, etc., and a silane-based coupling agent or titanate-based coupling agent, which can suppress the oxidative decomposition reaction of organic matter caused by the combination of titanium oxide and photocatalyst, so it is more effective. Extend the life of insulating materials and coating films using thermosetting resin compositions.

Examples of the inorganic pigments and organic pigments other than the carbon-based black pigments, oxide-based black pigments, and white pigments include azo pigments, disazo pigments, isoindolinone pigments, quinophthalone pigments, and isoindolines. Pigments, anthraquinone pigments, anthrone pigments, xanthene pigments, diketopyrrolopyrrole pigments, anthraquinone (anthrone) pigments, fluorenone pigments, quinacridone pigments, indigo pigments, dioxazine pigments, phthalocyanine pigments And azomethine pigments. Examples of the inorganic pigment include manganese oxide. Aluminum oxide and chromium oxide. Tin oxide, iron oxide, cadmium sulfide. Red series of selenium sulfide, cobalt oxide, zirconium dioxide. Vanadium oxide and chromium oxide. Blue, vanadium pentoxide and other zirconium. Silicon. Rhenium and vanadium. Tin and chromium. titanium. Yellow color of antimony, chromium oxide, cobalt. Chromium, alumina. Green system of chromium, aluminum. Manganese and iron. Silicon. Peach color system such as zirconium.

These inorganic pigments and organic pigments containing carbon-based black pigments, oxide-based black pigments, white pigments, and the like do not impair the properties such as processability, and can effectively exert concealability, optical characteristics, light-shielding properties, or light reflection. From the viewpoints of other functions such as performance and creativity, those having a primary particle diameter of 1 μm or less are preferred.

Usable dyes include, for example, oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, or acid mordant dyes having any of various forms. Moreover, when using the said dye lake, it can also take the form of a salt-forming compound, such as a dye and a nitrogen-containing compound.

The dye to be used is preferably a diamine compound such as an aromatic diamine used in a thermosetting resin composition, which has a reactive substituent, and is preferably one having a sulfonic acid group or a carboxylic acid group in the molecule. For example, acid dyes (diamines are basic substances, so even acid dyes are excluded from weak bases). Generally, in the molecules of thermosetting resins, the dye is only dissolved and dispersed, and in the case of a diamine compound such as an aromatic diamine, the dye is partially bonded to the thermally cured polymer matrix due to heat treatment. It becomes difficult to move in a thermosetting resin, and solvent resistance can be improved more.

In the first invention, the use of thermosetting resin materials (insulating materials, insulating films, coating films, flexible printed wiring boards, etc.) is considered among inorganic pigments, organic pigments, and dyes used as coloring materials. From the viewpoint of containing the shielding property, light shielding property, or reflective property of the coloring material, the best coloring material is selected as described above.

In the third invention, the coloring material used is considered for the use of a thermosetting resin material (thermosetting resin film, thermosetting resin insulating film, coating film, flexible printed wiring board, etc.), concealment, optical characteristics, and light shielding And other functions such as light reflectivity, creativity, etc., determine the more suitable amount, and never impair the electrical properties and processability of insulation, low dielectric constant, and low dielectric tangent. From the viewpoint of containing other functions such as concealment, optical characteristics, light-shielding, light-reflecting properties, and creativity of the purpose of containing the coloring material, the lower limit of the solid content of the thermosetting resin composition is 0.1% by mass or more, which is better. It is 1% by mass or more, and the upper limit is 30% by mass or less, and more preferably 20% by mass or less, from the viewpoint of not impairing characteristics such as mechanical strength of the final thermosetting resin and the like.

    [Resin composition]    

Examples of the resin composition used in the third invention include at least a cyanate resin and / or an epoxy resin. Those resins that are used as the base resin of the thermosetting resin composition can be used without particular limitation as long as they are suitable for users such as insulation and adhesion in electronic equipment.

Usable cyanate resins (cyanate resins), epoxy resins, mass ratios (in the range of 1:10 to 10: 1), active ester compounds, their hardening accelerators, and epoxy resins when used in combination The hardener, the respective contents thereof, and the like can be used in the cyanate resin, epoxy resin, active ester compound, and the like detailed in the above-mentioned first and second inventions, and therefore description thereof is omitted.

In the resin composition of the third invention, as described in detail in the first invention and the second invention, an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a colorant, a tackifier, and the like may be further used in combination. Antifoaming agents, leveling agents, coupling agents, adhesion-imparting materials, and the like, materials generally used in thermosetting resin compositions for electronic devices.

In the third invention, the non-aqueous solvent detailed in the first invention can be used for viscosity adjustment and the like of the thermosetting resin composition.

Among the non-aqueous solvents used in the third invention, it is preferably changed depending on the material used or the use of the thermosetting resin, and examples include acetanilide, dioxane, o-cresol, and m-formaldehyde. Phenol, p-cresol, N-methyl-2-pyrrolidone, N-acetamido-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylformamide Fluorene, γ-butyrolactone, cyclobutane, halogenated phenols, xylene, acetone.

The content of these non-aqueous solvents is adjusted to a suitable content suitable for viscosity adjustment and the like of the thermosetting resin composition.

The thermosetting resin composition of a fluorine-containing resin according to the third invention is characterized by including at least the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the cyanate resin-containing resin. The resin composition of the epoxy resin is, for example, added to the non-aqueous solvent, a predetermined amount of the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, the resin containing the cyanate ester, and In addition to mixing the resin composition of the epoxy resin, in addition to stirring by a disperser or a homogenizer, an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill can be used. , Jet mills, and other mixers and dispersers.

In the thermosetting resin composition of the fluorine-containing resin of the third invention, fine powder of the fluorine-based resin, the compound represented by the above formula (I), the above-mentioned coloring material, and the content are added to a non-aqueous solvent. The resin composition of the cyanate resin and / or epoxy resin is mixed, and by adjusting the total resin concentration of cyanate resin, epoxy resin, etc. necessary for the final thermosetting resin composition, the fluorine Resin powders and coloring materials do not aggregate, can exist uniformly, have low dielectric constant and dielectric tangent, and can exhibit excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy.

The thermosetting resin composition of a fluorine-containing resin according to the third invention includes at least the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the cyanate resin and / or ring. The resin composition of an oxygen resin can be formed and cured to form a cured product, an insulating material, etc. by molding and curing in the same manner as a conventional thermosetting resin composition such as an epoxy resin composition. As the molding method and the curing method, the same method as the conventional thermosetting resin composition such as an epoxy resin composition can be used. The method inherent to the thermosetting resin composition of the fluorine-containing resin of the third invention is not required, and there is no particular need. limited.

The thermosetting resin composition of the fluorine-containing resin of the third invention can use various additives such as a surfactant, a dispersant, and a defoamer, and silica particles, as long as the effects of the invention are not impaired. Or filler materials such as acrylic particles or elastomers.

In the thermosetting resin composition of the fluorine-containing resin of the third invention, the thermosetting resin composition preferably uses a moisture content of the Carr Fisher method, and is preferably 5000 ppm or less [0 ≦ water content ≦ 5000 ppm]. Moisture incorporation from materials or moisture in the manufacturing stage is considered, but by setting the moisture content of the final thermosetting resin composition to 5000 ppm or less, fine powder of fluororesin or coloring material (pigment) does not agglomerate It can exist uniformly, and a thermosetting resin composition having more excellent storage stability can be obtained.

    [The fourth invention: a thermosetting resin composition of a fluorine-containing resin]    

The thermosetting resin composition of a fluorine-containing resin according to the fourth invention is characterized in that it contains at least the fine powder of the fluorine-based resin and the fluorine-based resin containing the compound represented by the formula (I) and the non-aqueous solvent. For the powder dispersion, the coloring material, and the resin composition containing the cyanate resin and / or epoxy resin, the details of the components and the like are the same as those of the third invention and the like, and therefore description thereof is omitted.

In the fourth invention, as compared with the third invention, a dispersion of a fine powder of a fluorine resin containing at least a fine powder of a fluorine-based resin, a compound represented by the formula (I), and a non-aqueous solvent is used. In addition, by adding a predetermined amount of a coloring material and a resin composition containing the cyanate resin and / or epoxy resin, and mixing, etc., a fine powder of the fluorine-based resin and the coloring material are not formed in the composition. A thermosetting resin composition such as sedimentation, uniform fine particle dispersion, and the like.

The fluorine-based resin fine powder dispersion of the fourth invention can be, for example, a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet. Dispersers such as mills are produced by stirring, mixing, and dispersing, but in the dispersed state, fine powders of fluorine-based resins are diffracted by dynamic light scattering or laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is preferably 10 m or less. Generally, primary particles are aggregated into secondary particles and become fine powder with a large particle size. By dispersing the secondary particles of the fine powder of this fluorine-based resin to a particle size of 10 μm or less, for example, by using a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, Dispersers such as a bead mill, a wet jet mill, and a high-pressure homogenizer are used to disperse, and stable dispersions can be obtained even when stored for a long time with a low viscosity.

The average particle diameter is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. Because it can become a more stable dispersion.

The thermosetting resin composition of the fluorine-containing resin of the fourth invention is the same as the thermosetting resin composition of the fluorine-containing resin of the third invention described above, within a range that does not impair the effects of the invention. Various additives such as surfactants, dispersants, and defoamers, filler materials such as silica particles, acrylic particles, and elastomers are used.

The thermosetting resin composition of the fourth invention (including the fifth invention and the sixth invention described later) containing a fluorine-containing resin is the same as the thermosetting resin composition of the third invention described above. The water content of the snow method is preferably 5000 ppm or less [0 ≦ water content ≦ 5000 ppm]. Moisture incorporation from materials or moisture in the manufacturing stage is considered, but by setting the moisture content of the final thermosetting resin composition to 5000 ppm or less, fine powder of fluororesin or coloring material (pigment) does not agglomerate It can exist uniformly, and a thermosetting resin composition having more excellent storage stability can be obtained.

    [The fifth invention: a thermosetting resin composition of a fluorine-containing resin]    

The thermosetting resin composition of a fluorine-containing resin according to the fifth invention is characterized in that it contains at least: fine powder containing at least a fluorine-based resin and a compound represented by formula (I) and fine powder of a fluorine-based resin containing the non-aqueous solvent. A coloring material dispersion or a coloring material solution containing at least a coloring material and a non-aqueous solvent; and a resin composition containing the above-mentioned cyanate resin and / or epoxy resin. The invention and the like are the same, so descriptions thereof are omitted.

Compared with the third and fourth inventions, the fifth invention is a fluorine resin fine powder dispersion prepared in advance by using a fine powder containing at least a fluorine-based resin, a compound represented by formula (I), and a non-aqueous solvent; and at least A coloring material dispersion or a coloring material solution containing a coloring material and a non-aqueous solvent is added to the dispersion or the solution, and the resin composition containing the above-mentioned cyanate resin and / or epoxy resin is added and mixed. A thermosetting resin composition can be obtained in which a fine powder of a fluorine-based resin and a coloring material do not aggregate or settle in the composition, and can uniformly disperse fine particles.

The coloring material dispersion of the fifth invention is obtained by dispersing an inorganic pigment and an organic pigment containing the carbon-based black pigment, oxide-based black pigment, and white pigment in a non-aqueous solvent, if necessary, As long as the effect of the present invention is not impaired, dispersion may be performed using a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, or the like.

The device used for the dispersing is the same as the fine powder dispersion of the above-mentioned fluorine-based resin. For example, a disperser, a homogenizer, or a mixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, Dispersers such as wet jet mills are produced by stirring, mixing, and dispersing.

In the dispersion state of the coloring material described above, the coloring material (pigment) is diffracted by dynamic light scattering or laser diffraction. It is preferable that the volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is 3 μm or less. By dispersing this coloring material (pigment) to a particle size of 3 μm or less, for example, by using a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, Dispersers such as wet jet mills and high-pressure homogenizers are used for dispersion, and stable dispersions can be obtained even in the case of long-term storage with low viscosity.

The average particle diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. Because it can become a more stable dispersion.

The coloring material solution of the fifth invention can be obtained by dissolving various dyes such as the oil-soluble dye, acid dye, direct dye, basic dye, mordant dye, or acid mordant dye in a non-aqueous solvent.

Devices used for dissolution, such as mixers such as dispersers, homogenizers, or ultrasonic irradiation devices, can be used when the devices can be stirred, mixed, and dissolved. When coloring materials (dyes) with low solubility are used In this case, the non-aqueous solvent may be dissolved while being heated while being stirred.

    [Sixth invention: Thermosetting resin composition of fluorine-containing resin]    

The thermosetting resin composition of a fluorine-containing resin according to the sixth invention is characterized in that it contains at least fine powder of a fluorine-based resin and a compound represented by formula (I), a coloring material, and the above-mentioned non-aqueous solvent. For a fine powder coloring material dispersion and a resin composition containing the cyanate resin and / or epoxy resin, the details of the components and the like are the same as those of the first invention and the like, and therefore descriptions thereof are omitted.

Compared with the third, fourth, and fifth inventions, the sixth invention uses the fine powder of fluorine resin containing at least a fluorine-based resin and the compound represented by formula (I), a coloring agent, and a non-aqueous solvent to color the powder in advance. Material dispersion, by adding the above-mentioned quantitative amount of the resin composition containing cyanate resin and / or epoxy resin to this dispersion, mixing, etc., to obtain fine powder of fluororesin and coloring material composition A thermosetting resin composition capable of uniformly dispersing fine particles without causing aggregation or sedimentation.

The above-mentioned fluorine-based resin fine powder coloring material dispersion of the sixth invention can be obtained by dispersing the fine powder of the fluorine-based resin, the compound represented by the formula (I) and the coloring agent in a non-aqueous solvent, and it is necessary In this case, as long as the effect of the present invention is not impaired, a surfactant or a dispersant, a pigment derivative (a synergist), an antifoaming agent, or the like can be used for dispersion.

The device used for dispersing is the same as the fine powder dispersion or coloring material dispersion of the above-mentioned fluorine-based resin. For example, a disperser, a homogenizer, a mixer, or an ultrasonic disperser, a three-roll mill, or a wet ball mill can be used. , Bead mill, wet jet mill and other dispersers, etc., are produced by stirring, mixing and dispersing.

Since the above-mentioned fluororesin fine powder coloring material dispersion system contains both a dispersion of the fluororesin fine powder and the coloring material, it is difficult to simply adjust the average of the dispersion, similar to the fluororesin fine powder dispersion or the coloring material dispersion. The particle diameter is preferably a filter or a mesh, and the maximum particle diameter is preferably 10 μm or less. Because it can become a more stable dispersion.

In the third invention to the sixth invention, by implementing the inventions of the third invention to the sixth invention, a fine powder of a fluororesin and a coloring material can be obtained in the composition without aggregation or sedimentation. A thermosetting resin composition such as uniform fine particle dispersion.

The third to sixth inventions are those using the above-mentioned non-aqueous solvents, but they may be used in combination with other solvents or other solvents. The use of the thermosetting resin composition (wiring boards containing circuit boards) , Coating film, insulating material, etc.) choose the better one.

    [Preparation of hardened materials, insulating materials, etc. obtained from the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention]    

The hardened material, insulating material, etc. obtained from the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention can be the same as the thermosetting resin composition of the conventional epoxy resin composition and the like. It can be molded and hardened to form hardened materials, insulating materials, etc. For the molding method and the curing method, the same method as the conventional thermosetting resin composition such as an epoxy resin composition can be adopted. The fine powder of the fluorine-based resin and the coloring material are dispersed by uniform fine particles, and the pigment or dye is used to give concealment. Properties such as electrical properties, optical properties, light-shielding or light-reflecting properties, creativity, etc. can also be obtained with high insulation, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability and other excellent coloring Insulating materials such as hardened materials and thermosetting resin insulation films.

In the method for manufacturing a thermosetting resin insulating film, for example, fine powder of a fluorine-based resin is dispersed to produce a predetermined color, such as a case of a black or white thermosetting resin, a thermosetting resin film, or a thermosetting resin insulating material. The substrate and the surface of the substrate for a thermosetting resin film are coated with the thermosetting resin composition obtained as described above to form a film (coating film), and the film is subjected to heat treatment to remove the solvent and hardening treatment. .

The usable base material is not particularly limited in shape or material as long as it has a compact structure to such an extent that it does not allow liquid or gas to penetrate, and it may suitably be listed as: In addition, the film itself is a conventional film-forming substrate for belts, molds, rolls, rollers, etc., and the surface is formed with electronic parts or wires having a thermosetting resin film as an insulating and protective film, or a circuit board, and a film is formed on the surface. Sliding members or products, forming a thermosetting resin film, forming a multilayer film, or a thin film or copper foil when laminating a copper-clad substrate.

In addition, as a method for applying the thermosetting resin composition to these substrates, for example, a spray method, a roll coating method, a spin coating method, a bar coating method, an inkjet method, a screen printing method, a narrow method, or the like can be suitably used. The slit coating method and the like are conventional methods.

Films, films, and insulating materials made of a thermosetting resin composition formed on a substrate can be heated at a relatively low temperature such as room temperature under reduced pressure or normal pressure. Method for defoaming.

Films and the like made of a thermosetting resin composition formed on a substrate can be heated to remove the solvent, and after curing, a thermosetting resin, a thermosetting resin film, and a thermosetting resin insulating material can be formed.

The thermosetting resin, the thermosetting resin film, and the thermosetting resin insulation material are suitably adjusted in thickness depending on the application. For example, a thickness of 0.1 to 200 μm, preferably 3 to 150 μm, and more preferably 5 to 130 μm can be used. Resin film, film.

Fine powder concentration of the fluorine-based resin in the colored thermosetting resin film, colored thermosetting resin film, colored thermosetting resin insulating material, etc. obtained from the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention described above. It is not particularly limited, and is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 10 to 35% by mass relative to the entire mass of the cured product that hardens the thermosetting resin composition of the present invention. %about. When the concentration of the fine powder of the fluorine-based resin is too small, the addition effect of the fine powder of the fluorine-based resin is not effective, and when the concentration of the fine powder of the fluorine-based resin is too large, the mechanical properties of the thermosetting resin are reduced.

The concentration of the coloring material of the fluorine-based resin in the coloring thermosetting resin insulating material such as a colored thermosetting resin insulating film is not particularly limited, and it is relative to the entire mass of the cured product that hardens the thermosetting resin composition of the present invention. It is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 20% by mass. When the concentration of the coloring material is too small, the effects of concealment, optical characteristics, light-shielding, light reflection, and creativity cannot be exhibited. When the concentration of the coloring material is excessively large, the electrical characteristics and mechanical characteristics of the thermosetting resin are reduced.

The colored thermosetting resin film obtained from the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention described above, for example, a white thermosetting resin such as a white film obtained by using a white pigment such as titanium oxide as a pigment Materials, of which heat-resistant and lightweight white materials, specifically, can be used as a substrate for LED (light-emitting diode), organic EL light-emitting reflector or white film of metal layer, and can be suitably used for LED or organic EL or A flexible printed wiring board or the like on which other light emitting elements are mounted.

In addition, the black thermosetting resin material such as the black thermosetting resin film obtained from each of the thermosetting resin compositions of the third to sixth inventions is excellent in shielding properties, optical characteristics, and light-shielding properties in electronic components or mounting components protected by the thermosetting resin materials. By.

    <Adhesive composition for circuit board of the third invention to the sixth invention>    

The adhesive composition for circuit boards of the third invention to the sixth invention is obtained by using the thermosetting resin composition of each of the fluorine-containing resins of the third to sixth inventions, and may further contain a dispersion in the cyanic acid. Rubber component in ester resin or epoxy resin.

In the third to sixth inventions, the adhesive composition for a circuit board is required to have sufficient flexibility (Flexible, below) in order to be used in the production of wiring or a flexible printed circuit board having a flexible substrate. Similarly), in order to supplement such flexibility, it is preferable to further include a rubber component in the adhesive composition for circuit boards.

Usable rubber components include natural rubber (NR) or synthetic rubber, preferably styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), ethylene Propylene diene monomer (EPDM) rubber, polybutadiene rubber, and denatured, modified polybutadiene rubber, etc., preferably EPDM rubber with an ethylene content of 10 to 40% by mass, or SBR, NBR and the like are particularly preferred as EPDM rubbers which can reduce the dielectric constant and dielectric loss coefficient of the resin composition.

The content of these rubber components is preferably 1 to 80 parts by mass based on 100 parts by mass of the resin (cyanate resin or epoxy resin) from the viewpoint of exerting the effects of the present invention, and the viewpoint of adhesion and heat resistance. It is 10 to 70 parts by mass, and more preferably 20 to 60 parts by mass.

The adhesive composition for each circuit board of the third invention to the sixth invention can have the constitution of the third invention to the sixth invention. For example, the third invention can be obtained by mixing the fine powder of the fluorine-based resin and the above. The compound represented by formula (I), a coloring material, and a resin composition made of a cyanate resin or an epoxy resin can be produced by a usual method, and it is preferably dispersed by fine powder of a fluorine-based resin in the fourth invention. A method of adding a coloring material and a resin composition containing a cyanate resin and / or an epoxy resin and a rubber component to a body, and mixing or coloring the fluorine-based resin fine powder dispersion of the fifth invention with a coloring material dispersion In the material solution, a resin composition containing a cyanate resin and / or an epoxy resin and a rubber component is added and mixed. A fluorinated resin fine powder coloring material dispersion of the sixth invention is added with a cyanate ester-containing dispersion. A resin composition of a resin and / or an epoxy resin and a rubber component is produced by a method of mixing.

In the adhesive composition for circuit boards of the third invention to the sixth invention, inorganic particles such as a phosphorus-based flame retardant may be further contained in order to supplement flame retardant properties. The inorganic particles such as the phosphorus-based flame retardant are 1 to 30 parts by mass, and preferably 5 to 20 parts by mass based on 100 parts by mass of the cyanate resin or epoxy resin.

In addition, the adhesive composition for each circuit board of the third to sixth inventions may contain, in addition to the above-mentioned components, a hardening accelerator, an antifoaming agent, a coloring agent, and a phosphor in an appropriate amount in addition to the above components, if necessary. , Conventionally known additives such as modifiers, discoloration inhibitors, inorganic fillers, silane coupling agents, light diffusing agents, and thermally conductive fillers.

Hardening (reaction) accelerators other than the above can be used, for example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo (5,4,0) Tertiary amines such as monocarbene-7 and their salts, phosphines such as triphenylphosphine, phosphonium salts such as triphenylphosphonium bromide, aminotriazoles, tin octoate, dibutyltin dilaurate Metal catalysts such as tin based, such as acid esters, zinc based, such as zinc octoate, and acetoacetone such as aluminum, chromium, cobalt, and zirconium. These hardening (reaction) accelerators can be used alone or in combination of two or more.

The adhesive composition for each circuit board of the third invention to the sixth invention can be molded and cured in the same manner as the conventional cyanate resin composition and epoxy resin composition to form a cured product. The molding method and the curing method can be the same as those of the conventional cyanate resin and epoxy resin composition. The adhesive composition for a circuit board of the present invention does not require an inherent method, and is not particularly limited.

The adhesive composition for circuit boards of the present invention can be further formed into various forms such as a laminate, a molded product, an adhesive, a coating film, and a film.

The adhesive composition for each circuit board of the third invention to the sixth invention is made of fine powder of fluorine resin, coloring material stably and uniformly dispersed without color unevenness, and without aggregates. The color is black or white. The thermosetting resin composition can obtain an adhesive composition for a circuit board, so the dielectric constant and dielectric tangent are low, and it has excellent properties such as adhesion, heat resistance, dimensional stability, and flame resistance, and is suitable for a circuit board. The adhesive material can be used, for example, in the manufacture of a circuit board laminate, a coverlay film, a prepreg, a bonding sheet, and the like. The aforementioned coating film, prepreg, adhesive film, etc. can be applied to circuit substrates, such as flexible printed circuit boards (FPCBs) of flexible metal foil laminates, which are manufactured using the adhesive for circuit substrates of the present invention In the case of a composition, it is possible to achieve an adhesive composition for a circuit board that has lower dielectric constant and dielectric tangent, and also has excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy.

    <Laminates for Circuit Boards of the Third Invention to the Sixth Invention>    

The laminated board for each circuit board of the third to sixth inventions is a laminated board for a circuit board including at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil. This adhesive layer is characterized by the adhesive composition for circuit boards of the 3rd invention-6th invention of the said structure.

FIG. 1 is a schematic view showing a cross section of a metal foil laminate (FPCB) which is an example of an embodiment of a laminate for a circuit board of the third to sixth inventions.

The laminated board A for a circuit substrate of the present embodiment includes at least a metal foil 30 laminated on an insulating film 10, and an adhesive resin layer 20 interposed between the insulating film 10 and the metal foil 30, and the adhesive resin layer 20 The adhesive composition for circuit boards which is colored black, white, or the like with no color unevenness and no agglomerates, is constituted (bonded).

Fig. 2 is a schematic view showing a cross section of a metal foil laminate (FPCB), which is another example of an embodiment of a laminate for a circuit board of the third to sixth inventions.

The laminated board B for circuit substrates in this embodiment replaces the one-sided structure of FIG. 1. As shown in FIG. 2, a two-sided structure is used, which includes at least both sides of the insulating film 10, and the metal foils 30 and 30 are laminated, respectively. Among the adhesive resin layers 20 and 20 between the insulating film 10 and the metal foils 30 and 30, the adhesive resin layers 20 and 20 are colored black, white, and the like with colorless unevenness and no agglomerates as described above. The circuit board is constituted (bonded) with an adhesive composition.

The laminated film for each circuit board of the third invention to the sixth invention of FIGS. 1 and 2 and the like, the insulating film 10 used is not particularly limited as long as it has electrical insulation, and it can be used having heat resistance and bending Properties, mechanical strength and thermal expansion coefficient of similar metals.

The usable insulating film 10 is selected from, for example, polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), and polyethylene naphthalate (PEN). , Polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamidoamine, polylactic acid, nylon, polyparabanic acid, polyether One or more types of films composed of ether ketone (PEEK) are preferably polyimide (PI) films.

In addition, the film formed from these materials is preferably a film which can be further surface-treated with a low-temperature plasma or the like on the surface of the film from the viewpoint of further improving the adhesion to the interface with the adhesive resin layer 20 described above.

The thickness of the insulating film 10 can be selected within a suitable range in consideration of sufficient electrical insulation and the thickness and flexibility of the metal foil laminate. The thickness is preferably 5 to 50 μm, and more preferably 7 to 45 μm.

The adhesive resin layer 20 is constituted (bonded) with the above-mentioned adhesive composition for circuit substrates, and its thickness is from the viewpoints of interface adhesion with the insulating film, flexibility of the laminate, and adhesive strength. , Preferably 1 to 50 μm, and more preferably 3 to 30 μm.

Examples of the metal foil 30 include metal foils having conductivity, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and alloys thereof. From the viewpoints of conductivity, ease of handling, and price, copper foil or stainless steel foil is suitably used. The copper foil can be used by a rolling method or an electrolytic method.

The thickness of the metal foil is considered from the viewpoints of electrical conductivity, interface adhesion with the insulating film, flexibility of the laminate, improvement of bending resistance, and the ease of forming fine patterns during circuit processing. It is possible to set a preferable range such as a viewpoint, for example, a range of 1 to 35 μm is preferable, a range of 5 to 25 μm is more preferable, and a range of 8 to 20 μm is particularly preferable.

The metal foil used has a matte surface roughness Rz (ten-point average roughness), preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and particularly preferably 0.2 to 2.0. μm.

The laminated board (for example, FIG. 1 or FIG. 2) of each of the circuit substrates of the third to sixth inventions thus constituted is produced, for example, by coating on the insulating film 10 to form the circuit substrate of the present invention having the above constitution. After forming the adhesive resin layer 20 with the adhesive composition, drying the adhesive resin layer 20 to a semi-hardened state. Next, a method of laminating the metal foil 30 on the adhesive resin layer 20 and performing thermal compression bonding (thermal lamination), It can be used to produce circuit boards with low dielectric constant and low dielectric tangent, which have excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardance, and have no agglomerates. They are colored black and white. Laminated boards. At this time, the flexible metal foil laminate is post-cured to completely harden the adhesive resin layer 20 in a semi-hardened state, thereby obtaining a final flexible metal foil laminate.

    [The coating film of the third invention to the sixth invention]    

Next, the coating film of the third invention to the sixth invention is an insulating film and a coating film having an adhesive layer formed on at least one side of the insulating film, and the adhesive layer is the third invention of the above structure ~ The adhesive composition for circuit boards of the 6th invention.

FIG. 3 is a schematic view showing an example of the embodiment of the coating film of the present invention of the third invention to the sixth invention (and the seventh invention to the tenth invention described later) in a sectional state.

The covering film C of this embodiment is used as a surface protective film for a flexible printed wiring board (FPC) or the like. The insulating film 40 has an adhesive resin layer 50 formed thereon, and the adhesive resin layer 50 is bonded. There are separators (peel-off films) 60 such as paper or PET films that serve as protective layers. In addition, this separator (release film) 60 may be provided if necessary in consideration of workability, storage stability, and the like.

The insulating film 40 to be used is the same as the insulating film 10 used for the circuit board laminate of the third to sixth inventions described above, and examples thereof include polyimide (PI) and liquid crystal polymer (LCP). ), Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE) , Polyester, Para-Aromatic Polyamine, Polylactic Acid, Nylon, Poly Parabanic Acid, and Polyetheretherketone (PEEK).

Moreover, from the viewpoint of further improving the adhesion of the interface with the above-mentioned adhesive resin layer 50, the film formed from such materials is preferably a film that is used on the surface of the film and further surface-treated with a low-temperature plasma or the like. .

In particular, when considering the heat resistance, dimensional stability, and mechanical properties of the coating film, a polyimide (PI) film is preferred, and in particular, a polyimide film treated with a low-temperature plasma is used for the coating film. Better.

The thickness of the insulating film 40 can be selected in a preferable range in consideration of sufficient electrical insulation, protection, flexibility, and the like, and is preferably 5 to 200 μm, and more preferably 7 to 100 μm.

The adhesive resin layer 50 is constituted (bonded) with the adhesive composition for each circuit board of the third invention to the sixth invention described above, and has a thickness ranging from adhesion to the interface with the insulating film and adhesion strength. From the viewpoint of waiting, it is preferably 1 to 50 μm, and more preferably 3 to 30 μm.

Each of the coating films of the third to sixth inventions constituted in this way is used for each of the circuit boards of the third to sixth inventions of the third to sixth inventions, which are colored with no color unevenness and no aggregates as described above. The adhesive composition is applied to the insulating film 40 using a double roll coater, a reverse roll coater, etc., so that an adhesive layer is formed and dried to a semi-hardened state (the composition is dried) State or a part of the state where the hardening reaction is performed), and secondly, the separator (release film) 60 which is layered into the above-mentioned protective layer can be manufactured with low dielectric constant and dielectric tangent, and also has adhesiveness, heat resistance, Coating film with excellent characteristics such as dimensional stability and flame retardancy.

    [Prepregs according to the third invention to the sixth invention]    

The prepregs of the third to sixth inventions are characterized in that they are selected from one or more types selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, or aromatic polyamide-based fibers. The structure formed by the fibers is impregnated with at least the adhesive composition for each circuit board of the third to sixth inventions of the third to sixth inventions, which is colored to be colorless, uneven, or agglomerated as described above.

The prepreg according to the third invention to the sixth invention can be used as a constituent material of a multilayer flexible printed wiring board, etc., and is a dust-free, low-flow prepreg, and can provide impregnation of the above-mentioned adhesive composition. After the fibers are dried, a sheet or the like in a semi-hardened state is formed.

The fibers used in this prepreg include one or more types of fibers selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, or aromatic polyamide-based fibers, and specifically, One or more fibers selected from the group consisting of E glass fiber, D glass fiber, NE glass fiber, H glass fiber, T glass fiber, and aromatic polyamide fiber. In particular, in order to reduce the dielectric constant and the dielectric loss coefficient of the prepreg to the maximum, use NE glass fibers with a lower dielectric constant and dielectric loss coefficient than other glass fibers (dielectric constant about 4.8 (Dielectric loss coefficient is about 0.0015).

The prepreg system has a thickness of 15 to 500 μm. When used in a circuit board, a thinner thickness of about 15 to 50 μm is preferred.

The prepreg system of the third invention to the sixth invention constructed as described above can provide a low dielectric constant and a low dielectric tangent by using it as an interlayer constituent material and a bonding material having both layers of flexible printed wiring boards and the like. It is a prepreg that has excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy, and has no agglomerates. It is colored black or white.

    [Electronic device of the third invention to the sixth invention]    

The electronic device of the third invention to the sixth invention is a thermosetting resin insulating material obtained by using the thermosetting resin composition of each of the fluorine-containing resins of the third to sixth inventions, for example, and can be used for applications requiring excellent electrical characteristics. (Low dielectric constant, low dielectric tangent), electrical insulation of various electronic devices, such as thin mobile phones, game consoles, router devices, WDM devices, personal computers, televisions, home servers, thin displays, hard drives, printers Watches and DVD devices are the insulating materials such as the body or parts of various electronic devices.

The third to sixth inventions are colored with pigments or dyes obtained from the thermosetting resin composition of the fluorine-containing resin of the third to sixth inventions described above, even if they are concealed, optical characteristics, light-shielding properties, or The functions such as light reflectivity and creativity are also heat resistance, mechanical properties, sliding properties, insulation properties, low dielectric constant, low dielectric tangent, and other electrical characteristics and excellent processability. A hardened product of a thermosetting resin composition colored in black, white, or the like, an insulating material, a flexible printed wiring board including the above-mentioned circuit board using a circuit board adhesive composition, a coating film, an electronic device, and Films and insulating materials using these thermosetting resin compositions are suitable for use in insulating films, interlayer insulating films for wiring substrates, surface protective layers, sliding layers, peeling layers, fibers, filter materials, wire covering materials, and bearings , Coatings, heat-insulating shafts, brackets, seamless belts, etc. for various belts, tapes, hoses, etc.

    [The seventh invention to the tenth invention: Polyfluorene imide precursor solution composition]    

The polyimide precursor solution composition of the present invention is constituted by the following seventh to tenth inventions, respectively.

The seventh invention is characterized by including at least: a fine powder of a fluorine-based resin, the compound represented by the above formula (I), a coloring material, and a polyimide precursor solution, and the eighth invention includes at least: a fluorine-based resin The fine powder and the fluorine resin fine powder dispersion of the compound represented by the formula (I) and a non-aqueous solvent; a coloring material; and a polyimide precursor solution; characterized in that the ninth invention is at least: Fine powder of fluororesin and fine powder dispersion of fluororesin of compound represented by formula (I) and non-aqueous solvent; coloring material dispersion or coloring material solution containing at least a coloring material and a non-aqueous solvent; polyimide A precursor solution; characterized in that the tenth invention is at least: a dispersion of a fluorine-based resin fine powder coloring material containing at least a fine powder of a fluorine-based resin and a compound represented by the above formula (I), a coloring material, and a non-aqueous solvent; And polyimide precursor solution;

Hereinafter, the polyimide precursor solution composition of each of the seventh to tenth inventions will be described in detail. The fine powder of the fluorine-based resin used in the seventh invention to the tenth invention, the compound represented by the formula (I), a non-aqueous solvent, a coloring material, and the like are the same as those in the first invention or the third invention. In some cases, this description is omitted, and in different cases, etc., the details are as follows.

    [Seventh invention: Polyfluorene imide precursor solution composition]    

The fine powder of the fluorine-based resin used in the seventh invention can be the fine powder of the fluorine-based resin detailed in the first invention. The preferable particle size of the fine powder of the fluorine-based resin is the same as that of the first invention. Similarly, it can be appropriately selected depending on the application, but when the stability of the polyimide precursor solution composition or the characteristics of the obtained polyimide are fully utilized, the smaller particle size is preferred. The primary particle diameter of the fine powder of the fluorine-based resin is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 1 μm or less. The lower limit of the primary particle diameter is preferably as low as possible, but it is preferably 0.05 μm or more and 0.3 μm or less based on manufacturability, cost, and the like.

The method for measuring the primary particle diameter of the fine powder of the fluorine-based resin, the measurement device, and the like are the same as those of the first invention described above, and are therefore omitted.

In addition, the fine powder of the fluorine-based resin used is as described in detail in the first aspect of the present invention, and it may be used by mixing two or more types having different primary particle diameters from each other, or by mixing an average of the fine powder of the fluorine-based resin in a dispersed state. Two or more kinds of particle sizes different from each other may be used by mixing fine powders of two or more kinds of fluorine-based resins having different primary particle sizes or average particle sizes. By using fine powder of two or more kinds of fluorine-based resins having different particle diameters, the viscosity can be adjusted, the filling rate can be increased, or the state of the surface of polyimide or the like can be controlled.

The fine powder of the fluorine-based resin is as described in detail in the first aspect of the present invention, and may be subjected to various surface treatments.

In the seventh invention, the fine powder of the fluorine-based resin is preferably contained in an amount of 5 to 70% by mass, and more preferably 10 to 60% by mass based on the total solid content of the polyimide precursor solution composition.

When the content is less than 5% by mass, the properties of the fluororesin cannot be sufficiently imparted to the final polyimide and the like, and when the content exceeds 70% by mass, the mechanical properties of the final polyimide and the like The strength is extremely weak, etc., so it is not good.

The compound represented by the above-mentioned (I) used in the seventh invention can use the structure detailed in the first invention described above and has a butyral group, an ethyl fluorenyl group, and a hydroxyl group. By changing the ratio of these three structures ( Each ratio of l, m, n), can control the solubility in non-aqueous solvents, compatibility with polyimide precursor solution, and chemical reactivity.

Content of the compound represented by said (I) is 0.01-30 mass% with respect to the fine powder of a fluorine-type resin. When the content of this compound is less than 0.01% by mass, the dispersion stability is deteriorated, and the fluorine-based fine powder becomes easy to settle. When it exceeds 30% by mass, the viscosity of the polyfluorene imide precursor solution becomes high, which is not preferable.

In addition, when considering the characteristics of the obtained polyimide, it is more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 2% by mass.

The coloring material used in the seventh invention includes at least one selected from the group consisting of inorganic pigments, organic pigments, and dyes detailed in the third invention.

Inorganic pigments, organic pigments, and dyes that can be used are colored polyimide materials such as polyimide films, coating films, flexible printed wiring boards, etc., to provide concealment, optical characteristics, and light shielding. There are no particular restrictions on the use of functional properties such as electrical properties, light reflectivity, and creativity. It is preferable that the electrical properties and processability such as insulation, low dielectric constant, and low dielectric tangent are not impaired. From the viewpoint that the effects of the seventh invention can be more exerted, at least one selected from the group consisting of a carbon-based black pigment, an oxide-based black pigment, and a white pigment is used as the inorganic pigment and organic pigment detailed in the third invention.

In the seventh invention, polyimide materials (polyimide film, polyimide insulation film, coating film, and flexible printing) are considered among inorganic pigments, organic pigments, and dyes used as coloring materials. For wiring board, etc.), the coloring material is used for the purpose of shielding, light-shielding, or reflective properties, and the best coloring material is selected as described above.

In the seventh invention, the coloring material used is to consider the application, concealment, and optical properties of the polyimide material (polyimide film, polyimide insulation film, coating film, flexible printed wiring board, etc.) Properties, light-shielding properties, light-reflective properties, creative properties, etc., determine the appropriate amount, and never damage the electrical properties such as insulation, low dielectric constant, and low dielectric tangent. The performance, because of the concealment, optical properties, light-shielding or light-reflecting, creativeness, and other functions of the coloring material, the lower limit is relative to the total solid content of the polyimide precursor solution composition. 0.1% by mass or more, more preferably 1% by mass or more, and the upper limit is not more than 30% by mass, and more preferably 20% by mass or less, from the viewpoint of not impairing characteristics such as mechanical strength of the final polyimide.

    <Polyimide precursor solution>    

The polyimide precursor solution used in the seventh invention can be used as long as it is a polyimide precursor used for general polyimide generation, for example, it contains at least tetracarboxylic dianhydride and / or A derivative thereof, a diamine compound, and a nonaqueous solvent are prepared by reacting a tetracarboxylic dianhydride and / or a derivative thereof with a diamine compound in the presence of a nonaqueous solvent. In the first invention, the "polyimide precursor solution" includes the concept of a non-aqueous solvent to be used.

Examples of usable tetracarboxylic dianhydrides and / or derivatives thereof include 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2, 2'-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) dianhydride, hydrazone-3,4,9,10-tetracarboxylic dianhydride, both Pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA ), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ) Ether dianhydride, ethylene tetracarboxylic dianhydride, ethylene glycol dianhydrotrimellitic acid ester, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo -3-furyl) naphtho [1,2-c] furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Tetracarboxylic dianhydride derivatives of acid dianhydrides, tetracarboxylic dianhydrides of the same skeleton, tetracarboxylic acid chlorides, the tetracarboxylic acids and lower alcohols and esters having 1 to 4 carbon atoms, etc. Use or mix two or more types.

Preferably, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) is used.

The content of the tetracarboxylic dianhydride and / or its derivative may be changed in accordance with manufacturability, use of polyimide, and required characteristics.

Examples of usable diamine compounds include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, and diaminopropyl Tetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-amine Propylpropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine Amine, 3-methylheptamethylene diamine, 5-methyl nonamethylene diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3 , 3'-diaminodiphenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylphosphonium, 1, 5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-dimethyl Benzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylpropane, 2,4-diaminotoluene, Bis (4-amino-3-carboxyphenyl) methane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] fluorene, 2,4-bis (β-amino -Third butyl) toluene, bis (p-β-amino-third butylphenyl) ether, bis (p-β-methyl-6-aminophenyl) benzene, bis-p- (1 1,1-dimethyl-5-amino-pentyl) benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, bis (p -Aminocyclohexyl) methane, 2,17-diaminoeicosane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane , 1,12-diaminooctadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, etc. These can be used alone or in combination of two or more.

Preferably, p-phenylenediamine (PPD), bis (4-amino-3-carboxyphenyl) methane (MBAA), 4,4'-diaminodiphenyl ether (ODA), 2,2- Bis [4- (4-aminophenoxy) phenyl] propane (BAPP).

The content of this diamine compound varies depending on the manufacturability, the use of polyimide, and the required characteristics.

The combination of the aforementioned tetracarboxylic dianhydride and / or its derivative with a diamine compound is preferably 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 4,4' -A combination of diamine diphenyl ether (ODA), s-BPDA and p-phenylenediamine (PPD), etc.

In the seventh invention, the non-aqueous solvent described in detail in the first invention can be used for viscosity adjustment of the polyfluorene imide precursor solution or the composition of the polyfluorene imide precursor solution.

Among the non-aqueous solvents, those which are changed depending on the material used or the use of polyimide are preferably exemplified by acetanilide, dioxolane, o-cresol, m-cresol, p- Cresol, N-methyl-2-pyrrolidone, N-ethylfluorenyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethylene, γ-butyrolactone, cyclobutane, halogenated phenols, xylene, acetone.

The content of the non-aqueous solvent used in the polyfluorene imide precursor solution used in the seventh invention is the remaining amount of the tetracarboxylic dianhydride and / or its derivative and the diamine compound.

    <Seventh invention: Polyimide precursor solution composition>    

The polyimide precursor solution composition of the seventh invention is characterized in that it includes at least the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the polyimide precursor solution. For example, the tetracarboxylic dianhydride and / or its derivative and a diamine compound are dissolved in a non-aqueous solvent, and the polymerized polyimide precursor solution is added with a predetermined amount of fine powder of the fluorine-based resin, The compound (butyral resin) represented by the above (I) and the coloring material are mixed and prepared.

The polyimide precursor solution composition of this seventh invention is added to a polyimide precursor solution of a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and the coloring material, and added in advance. Mixing in a predetermined amount can prevent fine powders and coloring materials of the fluorine-based resin from agglomerating or settling in the composition, and uniform dispersion of fine particles.

For the preparation of the polyimide precursor solution used in the seventh invention, a conventional method or predetermined conditions can be suitably used. For example, tetracarboxylic acid di which has a predetermined composition ratio can be added to a non-aqueous solvent. The anhydride and / or its derivative and the diamine compound are prepared by stirring. The total concentration of the tetracarboxylic dianhydride and / or its derivative and diamine compound in the polyimide precursor solution can be set according to various conditions. Usually, the total amount of the reaction solution (the total amount of the polyimide precursor solution) ), Preferably 5 to 30% by mass. The reaction conditions when stirring these are not particularly limited, but the reaction temperature is preferably set to 80 ° C or lower, particularly preferably 5 to 50 ° C. When the reaction temperature is too low, the reaction does not proceed or it takes too much time until the reaction proceeds. On the other hand, when the reaction temperature is too high, problems such as sulfonium imidization may occur. The reaction time is preferably from 1 to 100 hours.

The polyimide precursor solution composition may be, for example, a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet mill. A disperser such as a mixer is produced by stirring, mixing, and dispersing.

In addition, the polyimide precursor solution composition of the seventh invention can use various additives such as a surfactant, a dispersant, and a defoamer, and silicon dioxide within a range that does not impair the effects of the seventh invention. Filler materials such as particles or acrylic particles, elastomers, etc.

The polyimide precursor solution composition of the seventh invention is preferably such that the moisture content of the Carr Fisher method is 5000 ppm or less [0 ≦ water content ≦ 5000 ppm]. Considering the moisture content of the material or the moisture content in the manufacturing stage, etc. By setting the moisture content of the final polyimide precursor solution composition to 5000 ppm or less, fine powder of fluororesin or coloring material (pigment) can be made. It does not aggregate and can exist uniformly, and a polyimide precursor solution composition having more excellent storage stability can be obtained.

    [The eighth invention: a polyimide precursor solution composition]    

The polyimide precursor solution composition of the eighth invention includes at least: a fluorine-based resin fine powder dispersion containing at least the fine powder of the fluorine-based resin and the compound represented by the formula (I) and the non-aqueous solvent; The coloring material and the polyimide precursor solution are characterized in that the details of the above components and the like are the same as those of the first invention and the seventh invention, and therefore description thereof is omitted.

Compared with the seventh invention, the eighth invention uses a dispersion of a fine powder of fluorine resin containing at least a fluorine-based resin, a compound represented by formula (I), and a non-aqueous solvent in advance, and this dispersion is used. By adding the pigment and coloring material to the polyimide precursor solution, by mixing, etc., a fine powder of fluorine resin and the coloring material can be obtained without aggregation or sedimentation in the composition, and a uniform dispersion of fine particles can be obtained. Composition of hydrazone imide precursor solution.

The fluorine-based resin fine powder dispersion of the eighth invention may be a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet. Dispersers such as mills are produced by stirring, mixing, and dispersing. In the dispersed state, the fine powder of the fluorine-based resin uses dynamic light scattering or laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is preferably 10 μm or less. Generally, primary particles are aggregated and become fine powder with a large particle diameter of secondary particles. By dispersing the secondary particles of the fine powder of this fluorine-based resin to a particle size of 10 μm or less, by using a mixer such as a disperser, a homogenizer, or the like, an ultrasonic disperser, a three-roll mill, or a wet ball mill , Bead mill, wet jet mill, high-pressure homogenizer, etc. to disperse, can obtain a low viscosity, and stable dispersion when stored for a long time.

The average particle diameter is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. Become a more stable dispersion.

The polyimide precursor solution composition of the eighth invention is the same as the polyimide precursor solution composition of the seventh invention described above, and an interface can be used within a range that does not impair the effects of the present invention. Various additives such as active agents, dispersants, and defoamers; filler materials such as silica particles or acrylic particles; or elastomers.

The polyimide precursor solution composition of the eighth invention (including the ninth invention and the tenth invention described later) is the same as the polyimide precursor solution composition of the first invention, The water content by the Carr Fisher method is preferably 5000 ppm or less [0 ≦ water content ≦ 5000 ppm]. Considering the moisture content of the material or the moisture content in the manufacturing stage, etc. By setting the moisture content of the final polyimide precursor solution composition to 5000 ppm or less, fine powder of fluororesin or coloring material (pigment) can be made. It does not aggregate and can exist uniformly, and a polyimide precursor solution composition having more excellent storage stability can be obtained.

    [The ninth invention: a polyimide precursor solution composition]    

The polyimide precursor solution composition of the ninth invention includes at least: a fluorine resin fine powder dispersion containing at least a fine powder of a fluorine-based resin and a compound represented by the formula (I) and the above-mentioned non-aqueous solvent; The coloring material and the non-aqueous solvent are coloring material amount dispersions or coloring material solutions; and the polyimide precursor solution is characterized. The details of the above components and the like are the same as those of the first and seventh inventions. This description is omitted.

The ninth invention is, compared to the seventh and eighth inventions, a fluorine resin fine powder dispersion prepared in advance by containing at least a fluorine-based resin fine powder, a compound represented by formula (I), and a non-aqueous solvent; and at least A coloring material dispersion or a coloring material solution containing a coloring material and a non-aqueous solvent can be obtained by adding the dispersion or the solution to the polyimide precursor solution and mixing the same amount to obtain a fluorine-based resin. Polyimide precursor solution composition in which fine powder and coloring material do not agglomerate or settle in the composition, and uniform fine particles are dispersed.

The coloring material dispersion of the ninth invention is obtained, for example, by dispersing an inorganic pigment and an organic pigment containing the carbon-based black pigment, oxide-based black pigment, and white pigment in a non-aqueous solvent, and if necessary, As long as the effect of the present invention is not impaired, a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, or the like can be used for dispersion.

The device used for the dispersing is the same as the fine powder dispersion of the above-mentioned fluorine-based resin. For example, a disperser, a homogenizer, or a mixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, Dispersers such as wet jet mills are produced by stirring, mixing, and dispersing.

In the dispersion state of the coloring material described above, the coloring material (pigment) is diffracted by dynamic light scattering or laser diffraction. It is preferable that the volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is 3 μm or less. By dispersing this coloring material (pigment) to a particle size of 3 μm or less, for example, by using a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, Dispersers such as wet jet mills and high-pressure homogenizers are used for dispersion, and stable dispersions can be obtained even in the case of long-term storage with low viscosity.

The average particle diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. Because it can become a more stable dispersion.

The coloring material solution of the ninth invention can be obtained by dissolving various dyes such as the oil-soluble dye, acid dye, direct dye, basic dye, mordant dye, or acid mordant dye in a non-aqueous solvent.

Devices used for dissolution, such as mixers such as dispersers, homogenizers, or ultrasonic irradiation devices, can be used when the devices can be stirred, mixed, and dissolved. When coloring materials (dyes) with low solubility are used In this case, the non-aqueous solvent may be dissolved while being heated while being stirred. A precursor solution composition can be obtained.

    [The 10th invention: Polyimide precursor solution composition]    

The polyimide precursor solution composition of the tenth invention includes at least: fine powder containing at least a fluorine-based resin and a compound and a coloring material represented by the formula (I) and a fluorine-based resin containing the non-aqueous solvent. In the case of the powdered coloring material dispersion and the polyimide precursor solution, the details of the components and the like described above are the same as those of the seventh invention and the like, and therefore description thereof is omitted.

Compared with the seventh, eighth, and ninth inventions, the tenth invention is a fluorine resin containing at least a fluorine-based resin fine powder and a compound represented by formula (I), a coloring agent, and a non-aqueous solvent. The powder coloring material dispersion can be obtained by adding a predetermined amount of dispersion to the polyfluorene imide precursor solution, mixing, etc., to obtain fine powder of fluororesin and coloring material which will not agglomerate or settle in the composition. And uniformly dispersed polyimide precursor solution composition such as fine particles.

The fluororesin fine powder coloring material dispersion of the tenth invention is obtained by dispersing fine powder of a fluororesin together with a compound represented by formula (I) and a coloring agent in a non-aqueous solvent, but it is necessary. In this case, as long as the effect of the present invention is not impaired, a surfactant or dispersant, a pigment derivative (a synergist), an antifoaming agent, or the like may be used for dispersion.

The device used for dispersing is the same as the fine powder dispersion or coloring material dispersion of the above-mentioned fluorine-based resin. For example, a disperser, a homogenizer, a mixer, a ultrasonic disperser, a three-roll mill, or a wet type can be used. Dispersers such as ball mills, bead mills, and wet jet mills are produced by stirring, mixing, and dispersing.

The above-mentioned fluororesin fine powder coloring material dispersion system includes a dispersion of both a fluororesin fine powder and a coloring material. Therefore, it is difficult to simply adjust the average particle size of the fluororesin fine powder dispersion or the coloring material dispersion. Diameter, it is preferable to use a filter, a mesh, or the like so that the maximum particle diameter is 10 μm or less. Because it can become a more stable dispersion.

By implementing the inventions of the seventh to tenth inventions, polyimide precursors such as fine powders of fluorine resins and coloring materials that do not agglomerate or settle in the composition, and uniformly disperse fine particles can be obtained.物 溶液 组合 物 The solution composition.

The seventh to tenth inventions are those using the above-mentioned non-aqueous solvents, but they can also be used in combination with other solvents or other solvents because of the use of polyimide (wiring boards containing circuit boards, Coating film, insulating material, etc.) are preferably selected.

    [Modulation of polyimide, polyimide film, polyimide insulation film, etc. obtained from the polyimide precursor solution composition of the seventh invention to the tenth invention]    

The polyimide, polyimide film, polyimide insulating film, and the like of the seventh invention to the tenth invention are prepared by the polyimide precursor solution of the seventh invention to the tenth invention. Polyimide precursors in the composition are imidized to disperse fluorine-based resins and coloring materials with uniform fine particles, etc., and are colored with pigments or dyes to provide concealment, optical properties, light-shielding properties, or light reflectivity. It can also provide functions such as creativity, high insulation, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, and other colored polyimide, polyimide film, and polyimide.醯 Imine insulation film, coating film, flexible wiring board, etc.

In the seventh to tenth inventions, the method for producing polyimide may include, for example, the production of fine powder containing at least a fluorine-based resin and the compound represented by the formula (I), a coloring material, and a non-aqueous solvent. A step of dispersing a fluorine resin fine powder coloring material dispersion; a step of mixing at least a tetracarboxylic acid dihydrate and / or a derivative thereof and a diamine compound to prepare a polyfluorene imide precursor solution composition; mixing the fluorine resin micro A step of preparing a polyimide precursor solution composition from the powder coloring material dispersion and the polyimide precursor solution composition; obtaining a polyimide by hardening the polyimide precursor solution composition The method for producing polyimide and the method for producing a polyimide film may include, for example, production of a polyimide precursor through the same steps as the method for producing a polyimide. A solution composition, and a method for producing a polyimide by coating the polyimide precursor solution composition and subjecting it to a hardening treatment to obtain a polyimide film; Examples of the method for producing an imine insulating film include, for example, a step of preparing a polyimide precursor solution composition through the same steps as the method for producing a polyimide, and coating the polyimide precursor solution. The composition is subjected to a hardening treatment to obtain a polyimide insulating film, which is a method for producing a polyimide insulating film. Moreover, in each said manufacturing method, hardening process (method of amidation) is not specifically limited, It can be performed using a conventional method.

For example, when a fluorine-based resin is dispersed to produce a predetermined color, for example, a black or white polyimide, a polyimide film, or a polyimide insulation material can be prepared by using a polyimide substrate or a polyimide substrate. The surface of the base material for a fluorene imine film is coated with the polyaminium precursor solution composition obtained above to form a film (coating film). The film is heat-treated, the solvent is removed, and a hardening treatment is performed (醯 imidization reaction).

The usable base material is not particularly limited in shape or material as long as it has a compact structure to such an extent that it does not allow liquid or gas to penetrate, and it may suitably be listed as: In addition, the film itself is a conventional film-forming substrate for belts, molds, rolls, rollers, etc., and the surface is formed with electronic parts or wires with a polyimide film as an insulating and protective film, or an electric wire, and a film is formed on the surface. When sliding parts or products, forming a thermosetting resin film, and forming a multilayer film or a copper-clad laminated substrate, one of the films or copper foil is used.

In addition, as a method of applying the polyimide precursor solution composition to such a substrate, for example, a spray method, a roll coating method, a spin coating method, a bar coating method, an inkjet method, a web, etc. can be suitably used. The lithographic printing method, the slit coating method, and the like are themselves known methods.

The film, film, insulating material, etc. formed from the polyimide precursor solution composition formed on the substrate can be, for example, under reduced or normal pressure at room temperature or below. The defoaming is performed by heating at a relatively low temperature.

Films and the like formed from the polyfluorene imide precursor solution composition formed on the substrate are subjected to heat treatment to remove the solvent, and after being subjected to a hardening treatment (fluorine imidization), polyfluorene, Polyimide film, polyimide insulation material. Rather than heat treatment directly at a high temperature, it is better to remove the solvent at a relatively low temperature of 100 to 140 ° C or lower at first, and then increase the temperature to the maximum heat treatment temperature. The maximum heat treatment temperature can be a temperature range of 200 to 600 ° C, but it is preferably 300 to 500 ° C, and more preferably 250 to 500 ° C. Further, instead of or in combination with heat treatment, a catalyst such as an amine compound may be used to carry out the imidization reaction. In addition, a carboxylic acid anhydride or the like, which is a dehydrating agent for removing water generated in the process of amidine imidization, can also be used.

Polyimide, polyimide film, and polyimide insulation materials are used in conjunction with the application, and the thickness can be adjusted appropriately. For example, the thickness can be 0.1 to 200 μm, preferably 3 to 150 μm, more preferably 5 to 130 μm Polyimide film, film. When the heating temperature is lower than 250 ° C, the fluorene imidization does not proceed sufficiently, and when the heating temperature exceeds 450 ° C, problems such as deterioration of mechanical properties due to thermal decomposition and the like occur. In addition, when the film thickness exceeds 200 μm, problems such as insufficient evaporation of the solvent, deterioration of mechanical properties, and occurrence of foaming during heat treatment may occur.

The colored polyimide film, colored polyimide film, colored polyimide insulation material, etc. of the fluorinated resin in the polyimide precursor solution composition of the seventh invention to the tenth invention. The concentration of the fine powder is not particularly limited, and is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass relative to the entire mass of the cured product after curing the polyimide precursor solution composition of the present invention. It is more preferably about 10 to 35% by mass. If the concentration of the fine powder of the fluorine-based resin is too small, there is no effect of adding the fine powder of the fluorine-based resin, and when the concentration of the fine powder of the fluorine-based resin is too large, the mechanical properties of polyimide may be reduced.

The concentration of the coloring material of the fluorine-based resin in the colored polyimide insulating material such as a colored polyimide insulating film is not particularly limited. The concentration of the polyimide precursor solution composition of the present invention is hardened. The entire mass of the subsequent hardened material is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 5 to 20% by mass. When the concentration of the coloring material is too small, the effects of concealment, optical characteristics, light-shielding, light reflection, and creativity are not exhibited. When the concentration of the coloring material is too large, the electrical and mechanical properties of polyimide may decrease. .

The colored polyimide film obtained from the polyimide precursor solution composition of the seventh to tenth inventions described above, for example, a white polyimide film obtained by using a white pigment such as titanium oxide as a pigment, etc. White polyimide material can be used as a heat-resistant and lightweight white material. Specifically, it can be used as a light-emitting diode (LED), a reflective material for organic EL light emission, or as a base material for white films of metal layers. It is suitable for assembling flexible printed wiring boards of LEDs, organic ELs, or other light-emitting elements.

In addition, the black polyimide material, such as a black polyimide film obtained from the polyimide precursor solution composition of each of the seventh to tenth inventions, is a shielding property in electronic parts or mounting parts protected. With excellent optical properties and light-shielding properties.

    [Flexible printed wiring board containing circuit board]    

The flexible printed wiring board containing a circuit board according to the seventh invention to the tenth invention is a colored polyimide film obtained by using the polyimide precursor solution composition of each of the seventh to tenth inventions. As a feature.

The flexible printed wiring board containing a circuit board of the present invention, such as a flexible printed circuit board (FPC), can be bonded to the polyimide by using an adhesive composition such as epoxy resin, cyanate resin, or the like. An insulating polyimide film and a metal foil obtained from the precursor solution composition are used to produce a metal foil laminate (CCL), and the metal foil is applied with a circuit to produce it.

The thickness of the polyimide film of the present invention, which becomes the aforementioned insulating film, can be selected within a preferred range, taking into consideration sufficient electrical insulation, the thickness of the metal foil laminate, and flexibility, and is preferably 5 to 50 μm. , More preferably 7 to 45 μm.

The thickness of the adhesive composition is preferably from 1 to 50 μm, and more preferably from 3 to 30 μm from the viewpoints of interface adhesion with the polyimide film, flexibility of the laminate, and adhesion strength.

Examples of the metal foil include those containing a conductive metal foil, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and alloys thereof. From the viewpoints of conductivity, ease of handling, and price, copper foil or stainless steel foil is more suitable. The copper foil may be produced by a rolling method or an electrolytic method.

The thickness of the metal foil is considered from the viewpoints of electrical conductivity, interface adhesion with the insulating film, flexibility of the laminate, improvement of bending resistance, and the ease of forming fine patterns during circuit processing. It is possible to set a preferable range such as a viewpoint, for example, a range of 1 to 35 μm is preferable, a range of 5 to 25 μm is more preferable, and a range of 8 to 20 μm is particularly preferable.

The metal foil used has a matte surface roughness Rz (ten-point average roughness), preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and particularly preferably 0.2 to 2.0. μm.

The flexible printed wiring board including a circuit board according to the seventh invention to the tenth invention configured as described above is obtained by using a polyimide precursor solution composition obtained from each of the first to fourth inventions.醯 Imine film, as an insulating film, can be colored with pigments or dyes. Even if it is provided with functions such as concealment, optical characteristics, light-shielding or light reflection, creativity, etc., it has high insulation, heat resistance, A flexible printed wiring board including a circuit board which is excellent in electrical characteristics (low dielectric constant, low dielectric tangent), and workability.

    [Coated film]    

Next, the coating film of the seventh invention to the tenth invention is characterized in that it is an insulating polyimide film obtained from the polyimide precursor solution composition of each of the seventh to tenth inventions. An adhesive layer is formed on at least one side of the polyimide film.

The adhesive layer used is an adhesive composition such as an epoxy resin, a cyanate resin, or the like used for the circuit board.

The coating film of the seventh invention to the tenth invention is used as a surface protection film for flexible printed wiring board (FPC), etc., and an adhesive layer is formed on the obtained polyimide film. A separator (peel-off film) such as a protective layer of paper or a PET film is bonded to the agent layer. In addition, this separator (release film) is provided when necessary in consideration of workability, storage stability, and the like.

The thickness of the foregoing polyimide film is based on sufficient electrical insulation and protection, and flexibility, and can be selected within a preferred range, preferably 5 to 200 μm, and more preferably 7 to 100 μm. The thickness of the adhesive composition is preferably from 1 to 50 μm, and more preferably from 3 to 30 μm from the viewpoints of interface adhesion with the insulating film, adhesion strength, and the like.

The coating film of the seventh to tenth inventions thus constituted is a polyimide film obtained by using the polyimide precursor solution composition of each of the seventh to tenth inventions described above, using a double roll A coating machine, a reverse roll coater, etc., to form an adhesive layer made of the adhesive composition by coating, and then drying to a semi-hardened state (a state where the composition is dried or a part of which undergoes a hardening reaction), Secondly, by forming a separator (release film) of the above-mentioned protective layer by layer, a coating film having low dielectric constant and dielectric tangent, and excellent characteristics such as heat resistance, dimensional stability, and electrical characteristics can be manufactured.

    [Electronic device of the seventh invention to the tenth invention]    

The electronic device of the seventh invention to the tenth invention uses a polyimide insulation material obtained from the polyimide precursor solution composition of each of the seventh to tenth inventions. Electrical characteristics (low dielectric constant, low dielectric tangent), and electrical insulation of various electronic devices, such as thin mobile phones, game consoles, router devices, WDM devices, personal computers, televisions, home servers, thin displays, hard drives , Printers, DVD devices are the insulation materials of the main body or parts of various electronic devices.

In the present invention, the pigment obtained from the polyimide precursor solution composition of the seventh to tenth inventions is colored with a pigment or dye, and even if concealed, optical, light-shielding, light-reflecting, creative, etc. The functions are also polyimide or polyimide film with excellent heat resistance, mechanical properties, sliding properties, insulation properties, low dielectric constant, low dielectric tangent, and other electrical properties. In addition to flexible printed wiring boards, coating films, and electronic devices containing the above circuit boards, the polyimide insulation material is suitable for use with polyimide or polyimide films and polyimide insulation materials. Used for various belts such as insulating films, interlayer insulating films for wiring substrates, surface protective layers, sliding layers, peeling layers, fibers, filter materials, wire covering materials, bearings, coatings, heat-insulating shafts, brackets, seamless belts, etc. , Tape, hose, etc.

    [Example]    

Hereinafter, the first to tenth inventions will be described in detail with reference to Examples and Comparative Examples. The first to tenth inventions are not limited to the following examples and the like.

    [The first invention: Preparation of non-aqueous dispersion of fluororesin: Dispersion 1 to 4]    

Among the blending compositions shown in Table 1 below, after the blending numbers [1] to [4] were blended and quantified, the mixture was sufficiently stirred and mixed. Then, the obtained PTFE mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill.

The average particle diameter of the PTFE in the dispersions 1 to 4 formed by the above-mentioned blending numbers [1] to [4] (average particle diameter analyzed by the cumulative method in the scattering intensity distribution) is determined by FPAR-1000 (Otsuka Electronics Measured by the dynamic light scattering method (manufactured by JSC) (see Table 2 below).

In addition, the dispersions 1 and 2 formed by the blending numbers [1] to [4] were added to the blending number [5], and the mixtures were sufficiently stirred and mixed to prepare dispersions 1 to 4.

In addition, when measuring the water content of the obtained dispersions 1 to 4, the water content by the Carr Fisher 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 one week, and the sedimentation state of the particles was visually confirmed. All the sediments were free of sedimentation and maintained in a good state.

    [Examples 1, 2 and Comparative Examples 1 to 3: Preparation of Thermosetting Resin Composition of Fluorine-Based Resin]    

The obtained dispersions 1 to 4 were used to prepare a thermosetting resin composition of a fluorine-containing resin at a blending prescription shown in Table 3 below. In addition, Comparative Example 3 was prepared as a composition in which a resin without adding a PTFE dispersion was added.

After mixing at the blending ratios shown in Examples 1, 2 and Comparative Examples 1 to 3, the PTFE dispersion and resins were mixed uniformly using a disperser to obtain a thermosetting resin composition of a fluorine-containing resin.

Here, the blends of any of Examples 1, 2, and Comparative Examples 1 and 2 showed a very uniform state, and no aggregates of PTFE and the like were observed.

    [Examples 3, 4 and Comparative Examples 4 to 6: Preparation of a thermosetting resin cured product of a fluorine-containing resin]    

Using a coater, the thermosetting resin composition of the fluorine-containing resin obtained in Examples 1, 2, and Comparative Examples 1 to 3 was coated on one side of a polyimide film (thickness: 25 μm), and the dried The thickness was about 25 μm, and the thickness was uniform. After drying at about 120 ° C. for about 10 minutes, this was heated at 180 ° C. for 60 minutes to harden to prepare a sample for evaluating the dielectric constant.

    [Evaluation of Dielectric Constant]    

The dielectric constant was measured at 1 GHz using an Impedence Analyzer in accordance with the test specification of JIS C6481-1996.

    [Evaluation of adhesion strength]    

A mesh with a thickness of 100 μm was used as a spacer on the roughened surface of a single-sided roughened copper foil (thickness: 18 μm), and then coated with those obtained in Examples 1, 2, and Comparative Examples 1 to 3. The thermosetting resin composition of a fluorine-containing resin was dried at 50 ° C. for 5 minutes, and then the roughened side of the roughened copper foil (thickness 18 μm) on one side was coated toward the composition side at 160 After lamination was performed at a temperature of 60 ° C., it was heated at 180 ° C. for 60 minutes to harden, and a sample for adhesion evaluation was prepared.

The evaluation of the adhesion strength was performed by cutting a test piece having a width of 1 cm, and performing T-type peeling using a push / pull tester (Push / Pull).

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

As shown in Table 4 above, the cured thermosetting resins of the fluorinated resins of Examples 3 and 4 of the first invention show a lower dielectric constant than that of Comparative Example 6 without fluorinated resins. At the same time, when compared with Comparative Examples 4 and 5 containing no urethane fine particles, the results showed higher adhesion strength.

    [The second invention: Preparation of non-aqueous dispersion of fluorine resin: Dispersion 5 to 8]    

Among the blending compositions shown in the following Table 5, after the blending numbers [6] to [9] were blended, they were quantified, and then thoroughly stirred and mixed. Then, the obtained PTFE mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill.

The average particle diameter of the PTFE in the dispersions 5 to 8 formed by the above-mentioned blending numbers [6] to [9] (average particle diameter analyzed by the cumulative method in the scattering intensity distribution) is determined by FPAR-1000 (Otsuka Electronics The measurement was performed by the dynamic light scattering method (manufactured by JSC) (see Table 6 below).

In addition, the dispersions 5 and 6 formed by blending the numbers [6] to [9] were added to the blending numbers [10] and [11], and they were sufficiently stirred and mixed to prepare dispersions 5 to 8.

In addition, when the moisture content of the obtained dispersions 5 to 8 was measured, each moisture content by the Carr Fisher method was within the range of 800 to 1800 ppm.

After the obtained dispersions 5 to 8 were stored in a closed container at 40 ° C for one week, the sedimentation state of the particles was visually confirmed. All the sediments were free of sedimentation and kept in a good state.

    [Examples 5, 6 and Comparative Examples 7 to 9: Preparation of thermosetting resin composition of fluorine-containing resin]    

The obtained dispersions 5 to 8 were used to formulate a thermosetting resin composition of a fluorine-containing resin according to the blending prescription shown in Table 7 below. In addition, Comparative Example 9 was prepared as a composition of a resin to which only a PTFE dispersion was not added.

After mixing at the blending ratios shown in Examples 5, 6 and Comparative Examples 7-9, the PTFE dispersion and resin were mixed uniformly using a disperser to obtain a thermosetting resin composition of a fluorine-containing resin.

Here, the blends of any of Examples 5, 6, and Comparative Examples 7 and 8 showed a very uniform state, and no aggregates of PTFE and the like were observed.

    [Examples 7, 8 and Comparative Examples 10 to 12: Preparation of hardened material of thermosetting resin of fluorine-containing resin]    

Using a coater, the thermosetting resin composition of the fluorine-containing resin obtained in Examples 5, 6, and Comparative Examples 7 to 9 was coated on one side of a polyimide film (thickness: 25 μm). The thickness was about 25 μm, and the thickness was uniform. After drying at about 120 ° C. for about 10 minutes, this was heated at 180 ° C. for 60 minutes to harden to prepare a sample for evaluating the dielectric constant.

    [Evaluation of Dielectric Constant]    

The dielectric constant was measured at 1 GHz using an Impedence Analyzer in accordance with the test specification of JIS C6481-1996.

    [Evaluation of adhesion strength]    

On a roughened surface of a single-sided roughened copper foil (thickness: 18 μm), a net having a thickness of 100 μm was coated as a spacer, and then the fluorine-containing system obtained in Examples 5, 6 and Comparative Examples 7 to 9 was applied. The thermosetting resin composition of the resin was dried at 50 ° C for 5 minutes, and then the roughened surface of the roughened copper foil (thickness 18 µm) on one side was coated toward the composition side at 160 ° C. After lamination, it was heated at 180 ° C for 60 minutes to harden, and a sample for adhesion evaluation was produced.

The evaluation of the adhesion strength was performed by cutting a test piece having a width of 1 cm, and performing T-type peeling using a push / pull tester (Push / Pull).

The evaluation results of dielectric constant and adhesion strength are shown in Table 8 below.

As shown in Table 8 above, the cured thermosetting resins of the fluorinated resins of Examples 7 and 8 of the second invention show lower dielectric constants than those of Comparative Example 9 without fluorinated resins. At the same time, compared with Comparative Examples 7 and 8 which did not include a thermoplastic elastomer, the results showed higher adhesion strength.

    [The third invention to the sixth invention: Preparation of fluorine resin fine powder dispersion, fluorine resin fine powder coloring material dispersion, and coloring material dispersion]    

The fluorine-based resin fine powder dispersion and fluorine-based resin fine particles used in each of the thermosetting resin compositions of the examples and comparative examples used in the third to sixth inventions are prepared by the respective preparation methods shown below. Powder coloring material dispersion, coloring material dispersion.

    (Preparation of fluorine resin fine powder dispersion)    

According to the blending prescription shown in Table 9 below, the compound represented by the formula (I) was sufficiently stirred and mixed in a non-aqueous solvent, and then PTFE fine powder as a fine powder of a fluorine-based resin was added, followed by stirring and mixing. Then, the obtained PTFE mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare a fluorine-based resin fine powder dispersion A.

    (Preparation of dispersion of fluorine resin fine powder coloring material)    

According to the blending formula shown in Table 10 below, in a non-aqueous solvent, the compound represented by formula (I) is sufficiently stirred and mixed, and then dissolved, and then a PTFE fine powder as a fine powder of a fluorine-based resin is added, and a coloring material After black pigment or white pigment, it is further stirred and mixed. Then, the obtained PTFE + pigment mixed liquid was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare pigment-containing fluorine resin fine powder dispersion materials B and C.

When the average particle diameter of the PTFE of the obtained fluororesin fine powder dispersion A was measured by a dynamic light scattering method of FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the obtained PTFE of the dispersion A was 0.30 μm.

    (Modulation of coloring material dispersion)    

According to the blending formula shown in Table 11 below, in a non-aqueous solvent, the compound represented by the formula (I) was sufficiently stirred and mixed, and then dissolved, and then a black pigment or a white pigment as a coloring material was added, followed by stirring and mixing. Then, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3 mm by using a horizontal-type bead mill to prepare a coloring material dispersion D and E.

    [Examples 9 to 18 and Comparative Examples 13 to 18: Preparation of thermosetting resin composition]    

The fluororesin fine powder dispersion, fluororesin fine powder coloring material dispersion, and coloring material dispersion prepared as described above were mixed with the blending prescription shown in Table 12 below, and then each mixture was stirred with a disperser to obtain each heat. Hardened resin composition.

About each obtained thermosetting resin composition, the sedimentation property and redispersibility were evaluated by the following evaluation method.

These results are shown in Table 12 below.

    (Evaluation method of sedimentation and redispersibility)    

For each thermosetting resin composition, the sedimentation state of various particles (fine fluorine resin powder, pigment particles) was allowed to stand at room temperature (25 ° C) for 30 minutes, and then visually confirmed, and based on the following evaluation criteria, Functional evaluation was performed for each state of sedimentation and redispersibility.

Evaluation criteria for sedimentation:

○: Those who did not see the sedimentary layer in the lower part

△: The sedimentation layer is seen in the lower part (easy to redisperse)

×: Those who see the sedimentary layer in the lower part (not easy to redisperse)

Evaluation criteria for redispersibility:

○: The sediment is easily redispersed during stirring

×: The sediment is not easy to redisperse when stirring

From the results in Table 12 above, it can be seen that in Examples 9 to 18 in the range of the third invention to the seventh invention, in Examples 10, 12, 15, and 17 using titanium oxide, although some sediments were seen, they were all It is easy to re-disperse and has no problem in usability.

On the other hand, in Comparative Examples 13 to 15, Comparative Examples 13 and 14 are non-fluorine-based resin fine powders and ordinary thermosetting resin compositions containing no coloring material (pigment), and have no evaluation of sedimentation and redispersibility. Comparative Examples 15 to 18 are thermosetting resin compositions containing a coloring material (black pigment, white pigment) containing fluorine-free resin fine powder.

In addition, when measuring the moisture content of each of the obtained thermosetting resin compositions of Examples 9 to 18 and Comparative Examples 13 to 18, each moisture content of the Carr Fisher method was within a range of 800 to 2500 ppm.

    [Examples 19 to 28, Comparative Examples 19 to 24: Evaluation of insulation material composition]    

The thermosetting resin composition obtained in Examples 9 to 18 and Comparative Examples 13 to 18 was used as an insulating material composition. The polyimide film (thickness: 25 μm) was coated on one side of the entire surface, and was dried by a coater. The subsequent thickness was about 25 μm, which became a uniform thickness. After drying at about 120 ° C. for about 10 minutes, this was heated at 180 ° C. for 60 minutes to harden, and an evaluation sample after the insulation material composition was hardened was produced.

    (Evaluation of electrical characteristics)    

According to the test specification of JIS C6481-1996, the dielectric constant of the evaluation sample obtained was measured at 1 GHz using an impedance analyzer (Impedence Analyzer). The volume resistivity was measured in accordance with the test standard of JIS C2151. The results are shown in Table 5 below.

As shown in Table 13 above, even if carbon black was contained as a black pigment, the evaluation samples of the insulating material compositions in Examples 19, 21, 23, 24, 26, and 28 after hardening were compared with those containing no pigment. In Examples 13, 14 and Comparative Examples 15 and 16 containing carbon black as a black pigment, it was found that the dielectric constant was low and the volume resistivity was also high. In addition, even when titanium oxide was contained, the insulation material compositions in Examples 21, 23, 26, and 28 were hardened, and it was found that the dielectric constants were lower than those of Comparative Examples 21 and 23.

    [Evaluation of Adhesive Compositions for Circuit Boards]    

The thermosetting resin compositions obtained in Examples 9 to 18 and Comparative Examples 13 to 18 were used as the adhesive composition for circuit boards.

    (Examples 29 to 38, Comparative Examples 25 to 308: Laminates for circuit boards)    

The adhesive composition for each circuit board obtained in Examples 9 to 18 and Comparative Examples 13 to 18 was coated on one side of a polyimide film (thickness: 25 μm) using a coater, so that the thickness after drying became The thickness was about 10 μm and the thickness was uniform. After forming the adhesive resin layer, this was dried to form a semi-hardened state. Then, the same adhesive resin layer was also formed on the surface of the opposite side of the said polyimide film, and the adhesive sheet was produced.

Next, copper foils (thickness: about 12 μm, matte surface roughness (Rz): 1.6 μm) were laminated on both sides of the aforementioned adhesive sheet, and then crimped at a pressure of 40 kgf / cm ² at 170 ° C. After being cured at 170 ° C. for 5 hours, a laminated board for a circuit board was produced.

The obtained laminates for circuit boards of Examples 29 to 38 and Comparative Examples 25 to 30 were used as evaluation samples.

    (Examples 39 to 48, Comparative Examples 31 to 36: Coating film)    

The adhesive composition for each circuit board obtained in Examples 9 to 18 and Comparative Examples 13 to 18 was coated on one side of a polyimide film (thickness: 25 μm) using a coater, so that the thickness after drying became The thickness was about 25 μm, and the thickness was uniform. After drying at about 120 ° C. for about 10 minutes, a release coating paper having a thickness of 125 μm was laminated to produce a coating film.

The coating films of Examples 39 to 48 and Comparative Examples 31 to 36 were laminated in the order of polyimide film of the coating film / adhesive surface of the coating film / copper foil (12 μm), and then this was laminated at 180 The sample was evaluated by hot pressing at a temperature of 40 ° C and a pressure of 40 kgf / cm ² for 60 minutes.

    (Evaluation of electrical characteristics)    

According to the test specification of JIS C6481-1996, the dielectric constant was measured at 1 GHz using an impedance analyzer (Impedence Analyzer).

    (Evaluation method of heat resistance)    

A sample having a size of 50 mm × 50 mm was adjusted, and after being subjected to a moisture absorption treatment at 120 ° C., 0.22 MPa, and 12 hours, it was treated at 260 ° C. for 1 minute, and the state of the sample was observed with the naked eye. The evaluation criterion was "○" when there was no abnormality such as peeling, deformation, or swelling, and "X" when there was abnormality such as peeling, deformation, or swelling.

    (Evaluation method of intensity)    

A sample cut into a size of 100 mm × 10 mm was prepared, and the adhesive strength of an adhesive layer formed using TENSILON was measured.

The evaluation results of the laminate for a circuit board are shown in Table 14 below, and the evaluation results of the coating film are shown in Table 15 below.

    [Evaluation of prepreg]         (Examples 49 to 58, Comparative Examples 37 to 42: prepreg)    

NE glass cloth having a thickness of about 100 μm was impregnated with the adhesive composition for each circuit board obtained in Examples 9 to 18 and Comparative Examples 13 to 18, and then dried at about 120 ° C. for about 10 minutes, and the entire manufacturing thickness was about 125 μm. Thermosetting prepreg.

The prepregs of Examples 49 to 58 and Comparative Examples 37 to 42 were laminated in the order of polyimide film (12.5 μm) / prepreg / polyimide (12.5 μm), and this was laminated at 180 The sample was evaluated by hot pressing at a temperature of 40 ° C and a pressure of 40 kgf / cm ² for 60 minutes.

    (Evaluation of electrical characteristics)    

According to the test specification of JIS C6481-1996, the dielectric constant was measured at 1 GHz using an impedance analyzer (Impedence Analyzer).

    (Evaluation method of heat resistance)    

A sample having a size of 50 mm × 50 mm was adjusted, and after being subjected to a moisture absorption treatment at 120 ° C., 0.22 MPa, and 12 hours, it was treated at 260 ° C. for 1 minute, and the state of the sample was observed with the naked eye. The evaluation criterion was "○" when there was no abnormality such as peeling, deformation, or swelling, and "X" when there was abnormality such as peeling, deformation, or swelling.

    (Evaluation method of intensity)    

A sample cut into a size of 100 mm × 10 mm was prepared, and the adhesive strength of an adhesive layer formed using TENSILON was measured.

The evaluation results of the prepreg are shown in Table 16 below.

As shown in Tables 14 and 15 above, the laminates for circuit substrates of Examples 29 to 38 using the thermosetting resin composition of Examples 9 to 18 as the adhesive composition for circuit substrates and those of Examples 39 to 48 were used. Although the coating film is colored black or white, it is compared with the heat-curable resin composition of Comparative Examples 13 to 18 as the circuit board adhesive composition of Comparative Examples 25 to 30, and the laminate for circuit substrates of Comparative Examples 31 to 31. As for the coating film of ~ 36, it was found that those having a low dielectric constant and equivalent heat resistance or adhesion were obtained.

In addition, as shown in Table 16 above, the prepregs of Examples 49 to 58 using the thermosetting resin compositions of Examples 9 to 18, although colored black or white, were hotter than those using Comparative Examples 13 to 18. It was found that the prepregs of Comparative Examples 37 to 42 of the cured resin composition had lower dielectric constants and equivalent heat resistance or adhesion.

    [The seventh invention to the tenth invention: Preparation of fluorine resin fine powder dispersion, coloring material dispersion, and polyimide precursor solution]    

The fluororesin fine powder dispersion used for each polyimide precursor solution composition of the examples and comparative examples used in the seventh to tenth inventions was prepared by the respective preparation methods shown below. , Fluorine resin fine powder coloring material dispersion, coloring material dispersion, polyfluorene imide precursor solution.

    (Preparation of fluorine resin fine powder dispersion)    

According to the blending formula shown in Table 17 below, the compound represented by the formula (I) was sufficiently stirred and mixed in a non-aqueous solvent, and then PTFE fine powder as a fine powder of a fluorine-based resin was added, followed by stirring and mixing. Then, the obtained PTFE mixed liquid was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare a fluorine-based resin fine powder dispersion A.

(Preparation of dispersion of fluorine resin fine powder coloring material)

According to the blending formula shown in Table 18 below, in a non-aqueous solvent, the compound represented by formula (I) is sufficiently stirred and mixed, and then dissolved, and then a PTFE fine powder as a fine powder of a fluorine-based resin is added, and a coloring material is added After black pigment or white pigment, it is further stirred and mixed. Then, the obtained PTFE + pigment mixed liquid was dispersed with zirconia beads having a diameter of 0.3 mm by using a horizontal bead mill to prepare pigment-containing fluorine resin fine powder coloring material dispersions B and C.

When the average particle diameter of the PTFE of the obtained fluororesin fine powder dispersion A was measured by a dynamic light scattering method of FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the obtained PTFE of the dispersion A was 0.32 μm.

    (Modulation of coloring material dispersion)    

The compound represented by the formula (I) was sufficiently stirred and mixed in a non-aqueous solvent at a blending formula shown in Table 19 below, and a black pigment or a white pigment as a coloring material was added, followed by stirring and mixing. Then, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3 mm by using a horizontal-type bead mill to prepare a coloring material dispersion D and E.

    (Preparation of polyimide precursor solution)    

400 parts by mass of N, N-dimethylformamide, 27 parts by mass of p-phenylenediamine, and 3,3 ', 4,4'-biphenyl tetraphenyl were added to a glass container having a stirrer and a nitrogen pipe. After 73 parts by mass of the carboxylic acid dihydrate was mixed and sufficiently stirred, a polyimide precursor solution having a solid content concentration of 18% by mass was obtained.

    [Examples 59 to 63 and Comparative Examples 43 to 45]    

The fluororesin fine powder dispersion, the fluororesin fine powder coloring material dispersion, the coloring material dispersion, and the polyimide precursor solution prepared as described above are mixed in the blending formula shown in Table 20 below, and then fully mixed. Each polyimide precursor solution composition was obtained by stirring with a disperser.

About each obtained polyimide precursor solution composition, the sedimentation property and redispersibility were evaluated by the following evaluation method.

These results are shown in Table 20 below.

    (Evaluation method of sedimentation and redispersibility)    

For each of the polyimide precursor solution compositions, the sedimentation state of various particles (fine fluorine resin powder, pigment particles) was allowed to stand at room temperature (25 ° C) for 30 minutes, and then visually confirmed. For each evaluation criterion, functional evaluation was performed for each state of sedimentation and redispersibility.

Evaluation criteria for sedimentation:

○: Those who did not see the sedimentary layer in the lower part

△: The sedimentation layer is seen in the lower part (easy to redisperse)

×: Those who see the sedimentary layer in the lower part (not easy to redisperse)

Evaluation criteria for redispersibility:

○: The sediment is easily redispersed during stirring

×: The sediment is not easy to redisperse when stirring

From the results in Table 20 above, it can be seen that in Examples 59 to 63 in the range of the seventh invention to the tenth invention, in Examples 60 and 62 using titanium oxide, although some sediments were seen, they were easily redispersed. No problem with usability.

In contrast, in Comparative Examples 43 to 45, Comparative Example 43 is a general polyimide precursor solution (composition) containing no fluorine-based resin fine powder and coloring material (pigment), and has no settling property and redispersibility. In addition, Comparative Examples 44 and 45 are polyimide precursor solution compositions containing a coloring material (pigment) containing no fluorine-based resin fine powder.

In addition, when measuring the water content of each of the polyimide precursor solution compositions of Examples 59 to 63 and Comparative Examples 43 to 45, the water content of the Carr Fisher method was 800 to 3000 ppm, respectively. Within range.

    (Polyurethane Film / Polyurethane Film Modulation)    

Each of the polyimide precursor solution compositions of Examples 59 to 63 and Comparative Examples 43 to 45 obtained above was applied to a glass plate as a substrate by a coater, and the pressure was reduced to 25 ° C at 25 ° C. After 50 minutes of defoaming and pre-drying, under normal pressure and nitrogen environment, 45 minutes at 120 ° C, 30 minutes at 150 ° C, 15 minutes at 200 ° C, 10 minutes at 250 ° C, and 400 ° C Heat treatment was performed for 10 minutes to form a polyimide film having a thickness of 30 μm. The polyimide film was peeled from the glass substrate to obtain a polyimide film.

About each of the obtained polyimide films, the state, dielectric constant, and volume resistivity of the polyimide film were evaluated and measured by the following methods.

Each of these evaluations. The measurement results are shown in Table 21 below.

    (Evaluation method of state of polyimide film)    

The state of the polyfluorene imide film was visually observed, and the state was evaluated based on the following evaluation criteria.

Evaluation benchmark:

○: No foreign matter such as PTFE agglomerates, forming a smooth surface

×: Foreign matter such as aggregate of PTFE was confirmed

    (Measurement method of dielectric constant of polyimide film)    

The obtained polyimide films were measured for dielectric constant at 25 ° C and 1 GHz using an impedance analyzer (Impedence Analyzer) in accordance with the test specifications of JIS C6481-1996.

    (Measurement method of volume resistivity of polyimide film)    

Each obtained polyimide film was measured according to the test specification of JIS C2151.

From the results of Table 21, it can be seen that the dielectric constants of Examples 59 to 63 are the same as those of Comparative Example 43 made of polyfluorene. In contrast, although Comparative Examples 44 and 45 increased the dielectric constant, it was confirmed that Examples 59 to 63 were equivalent or suppressed from rising.

    [Industrial availability]    

The non-aqueous dispersion system of the fluorine resin of the first invention and the second invention has a fine particle diameter, low viscosity, and excellent storage stability, and is suitable for mixing with various resin materials. The non-aqueous dispersion of the fluorine resin of the present invention is used. The thermosetting resin composition of the fluorine-containing resin and its hardened material have a low dielectric constant and a low dielectric tangent, and can suppress the decrease in adhesion strength and adhesion strength. Therefore, it can be applied to the insulation layer of multilayer printed wiring boards, Adhesives for circuit boards, laminates for circuit boards, coating films, prepregs, and the like.

In the thermosetting resin composition of the fluorine-containing resin according to the third invention to the sixth invention, the non-aqueous dispersion system of the fluorine-based resin is colored with a coloring material of an organic pigment, an inorganic pigment, or a dye. Even if it is concealed, Optical properties, light-shielding properties, light-reflective properties, creative properties, etc. can also be obtained with high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), and excellent coloring heat such as processability. A hardened resin composition or the like, and a flexible printed wiring board containing a circuit board, a coating film, or a thermosetting resin suitable for an insulating film, a related insulating film for a wiring board, or the like using the thermosetting resin composition. Electronic equipment using the insulating material of the composition, and surface protective layers, sliding layers, peeling layers, fibers, filter materials, wire covering materials, bearings, coatings, heat-insulating shafts, and the like of the thermosetting resin composition insulating materials, Various belts, tapes, hoses, etc. for brackets and seamless belts.

In the polyimide precursor solution composition of the seventh invention to the tenth invention, the non-aqueous dispersion system of the fluororesin is colored with a coloring material of an organic pigment, an inorganic pigment, or a dye, even if it is concealed and optical. Features such as properties, light-shielding, light-reflecting, creative, etc., can also get high insulation, and heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability and other excellent colored polyfluorene Imine, polyimide film, etc. In addition, a flexible printed wiring board containing a circuit board, a coating film, or an insulating film or a wiring board that uses the polyimide or polyimide film Electronic equipment using polyimide insulation materials such as related insulation films, and surface protective layers, sliding layers, release layers, fibers using polyimide, polyimide films, polyimide insulation materials, etc. , Filter materials, wire covering materials, bearings, paints, heat-insulating shafts, brackets, seamless belts, various belts, tapes, hoses, etc.

Claims (10)

A non-aqueous dispersion of a fluorine-based resin, comprising at least fine powder of a fluorine-based resin, fine particles of a urethane, a compound represented by the following formula (I), and a non-aqueous solvent, [In the above formula (I), l, m, and n are positive integers]. A non-aqueous dispersion of a fluorine-based resin comprising at least fine powder of a fluorine-based resin, a thermoplastic elastomer, a compound represented by the following formula (I), and a non-aqueous solvent, [In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition of a fluorine-containing resin, comprising at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a resin containing a cyanate resin and / or an epoxy resin Composition, [In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition containing a fluorine-based resin, which comprises at least: a fluorine-based resin fine powder dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent; a coloring material ; And a resin composition containing a cyanate resin and / or an epoxy resin; [In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition containing a fluorine-based resin, which comprises at least: a fluorine-based resin fine powder dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent; A coloring material dispersion or a coloring material solution of a coloring material and a non-aqueous solvent; and a resin composition containing a cyanate resin and / or an epoxy resin; [In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition containing a fluorine-based resin, comprising at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a non-aqueous solvent fine powder of a fluorine-based resin. Dispersion; and resin composition containing cyanate resin and / or epoxy resin; [In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a polyimide precursor solution, [In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least: a fluorine-based resin fine powder dispersion containing at least a fluorine-based resin fine powder, a compound represented by the following formula (I), and a non-aqueous solvent; a coloring material; And polyimide precursor solution, [In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least: a fluorine-based resin fine powder dispersion containing at least a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent; Material and non-aqueous solvent coloring material dispersion or coloring material solution; and polyimide precursor solution; [In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least a fine powder of a fluorine-based resin containing at least a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a non-aqueous solvent. Body; and polyimide precursor solution; [In the above formula (I), l, m, and n are positive integers].