TWI794172B - Non-aqueous dispersion of fluorine-based resin, thermosetting resin composition of fluorine-containing resin using the same and its cured product, polyimide precursor solution composition - Google Patents

Abstract

The present invention provides microparticles with low viscosity and excellent storage stability. It is suitable for mixing with resin materials such as thermosetting resin compositions to achieve low dielectric constant and low dielectric tangent, which can suppress adhesion strength and adhesion. Insulation layers of printed wiring boards with reduced strength, adhesives for circuit boards, non-aqueous dispersions of fluorine-based resins applicable to applications such as laminates for circuit boards, coating films, prepregs, and fluorine-containing resins using them Thermosetting resin composition of resin, polyimide precursor solution composition, etc.

A non-aqueous dispersion of a fluororesin, comprising at least fine powder of a fluororesin, urethane microparticles, a compound represented by the following formula (I), and a nonaqueous solvent.

〔上述式(I)中，l、m、n為正之整數〕。

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

Description

Non-aqueous dispersion of fluorine-based resin, thermosetting resin composition of fluorine-containing resin using the same and its cured product, polyimide precursor solution composition

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

In recent years, along with the progress of high speed and high function of electronic equipment, high speed of communication speed and the like are demanded. In this situation, the low dielectric constant and low dielectric tangent of various electronic equipment materials are required, and the low dielectric constant and low dielectric tangent of thermosetting resins that can be used for insulating materials and substrate materials are also required. Low dielectric constant, low dielectric tangent, etc.

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

Such melt mixing is not suitable for mixing with thermosetting resin materials and the like because the resin is mixed in a state where the resin is softened by heating.

The method to solve this problem, for example, the applicant of this application proposes to make an oily solvent dispersion of PTFE and add it to a thermosetting resin material, etc., for example, PTFE with a primary particle size of 1 μm or less contains 5 to 70 mass %, Relative to the mass of polytetrafluoroethylene, at least fluorine-containing and lipophilic-based fluorine-based additives contain 0.1 to 40% by mass, and the overall moisture content by the Karl Fischer Method is 20000ppm or less The oil-based solvent-based dispersion of PTFE and the oil-based solvent-based dispersion of PTFE for adding epoxy resin materials are featured (for example, refer to Patent Document 2 and Patent Document 3).

The resin material added with PTFE as mentioned above is effective in low dielectric constant and low dielectric tangent, but due to the non-adhesiveness of PTFE, the relationship between resins or resins and metals is difficult. In follow-up, etc., there is a problem that the adhesion strength and adhesive strength are slightly lowered, and further improvement of the adhesion strength, adhesive strength, etc. is urgently desired.

In addition, thermosetting resin compositions using epoxy resins, cyanate resins, etc. are widely used in electrical appliances due to their excellent heat resistance, electrical insulation, and adhesion. electronic use.

Generally, thermosetting resin compositions such as epoxy resins and cyanate resins are used, and their hardened products are suitable for use as electronic substrate materials, insulating materials, adhesive materials, etc., such as packaging materials for electronic parts, copper-clad layers Materials such as plywood, insulating paint, composite material, and insulating adhesive, and adhesive compositions for circuit boards used in the manufacture of circuit boards, and laminates, coating films, and prepregs for circuit boards using them , Insulation layer of multi-layer printed wiring board of electronic equipment, etc.

These thermosetting resin compositions, insulating materials using them, etc. need to be colored in white, black, or other colors in order to impart concealment, optical properties, light-shielding or light-reflecting properties, and other functions such as creativity. wait.

Such as high voltage electrical. Multilayer printed wiring boards used for component parts used in installation places of electronic parts and packages for semiconductor mounting are mainly based on black, so thermosetting resin compositions based on black are used. In addition, the 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 metal layer film. And need to increase every year.

These thermosetting resin compositions colored white, black, etc., and insulating material compositions using them include, for example, 1) a composition in which an acid anhydride is mixed with an inorganic filler and a hardening accelerator as the A agent, and a ring Oxygen resin is an anhydride-curable epoxy resin composition as agent B, which is formed by mixing a colorant with a quinacridone structure and an epoxy resin composition characterized by a diazo dye in agent B, and curing it High-voltage electrical and electronic parts (for example, refer to Patent Document 4), 2) In order to provide a prepreg or an insulating resin sheet without color unevenness or aggregates, including dissolving and/or dispersing the (B) colorant in (A ) process (1) of dispersing the inorganic filler in the dispersion liquid of the solvent and, thereafter, the process (2) of dissolving the (C) novolak-type epoxy resin (for example, refer to the patent Documents 5) and 3) are white curable resin compositions that have high reflectance and can suppress coloring due to reduction in reflectance over time and deterioration, and are used for printed wiring boards and light emitting devices on which light-emitting elements such as LEDs are mounted. In the case of reflectors for devices, white thermosetting resins containing (A) rutile-type titanium oxide and (B) thermosetting resins are used to provide white curable resin compositions that efficiently utilize light from LEDs, etc. Composition (for example, refer to Patent Document 6), 4) In order to provide a thermosetting resin composition for light reflection that has sufficient light reflectance and moldability, and is excellent in heat resistance and colorability, and a substrate for mounting an optical semiconductor element using the same and its production method and optical semiconductor device, therefore, a light-reflecting thermosetting resin composition containing an epoxy resin with specific physical properties, a curing agent, and a white pigment (for example, refer to Patent Document 7), 5) In order to provide insulation, It is a thermosetting resin composition that is excellent in heat resistance, can achieve surface flatness, adhesion, and curability at a high level of balance, and is excellent in both high-temperature insulation resistance and solvent resistance required in the manufacturing process, and its curing Products and display components using the same, therefore contain (a) carboxyl group-containing resin as a thermosetting component, (b) epoxy resin, (c) black colorants such as carbon black, and (d) selected from barium sulfate , a thermosetting resin composition characterized by at least one of silica and talc (for example, refer to Patent Document 8), and the like.

However, when the thermosetting resin compositions described in the above-mentioned patent documents 4 to 8 are colored by coloring materials such as organic pigments or inorganic pigments, it may affect the cured product, insulating material, coating layer film or flexibility. The electrical characteristics (dielectric constant, dielectric tangent) or insulation of printed wiring boards.

In particular, when carbon black is used for black coloring, not only the insulating property is lowered, but also the dielectric constant and dielectric tangent are deteriorated, so there is a problem that it is not suitable for applications such as high-speed communication and high-speed processing.

Therefore, colored thermosetting resin compositions, etc., have technical problems or limitations in electrical properties (low dielectric constant, low dielectric tangent) or insulation, and are currently required to impart concealment, optical properties, and light-shielding properties. Performance or light reflectivity, creativity, etc., and further improved electrical characteristics (low dielectric constant, low dielectric tangent) or insulating thermosetting resin composition, insulating material composition using it, and circuit board. Adhesive compositions, laminates for circuit boards, coating films, prepregs, flexible wiring boards, etc.

In addition, in the past, polyimides containing polyimide films and the like have been widely used in electrical appliances due to their excellent heat resistance, electrical insulation, chemical resistance, and mechanical properties. electronic use. For example, when polyimide is used as a film, it is used as an insulating substrate for electronic circuit materials, and it is also processed into an adhesive film or adhesive tape. In addition, when used as a coating agent, the polyimide precursor solution composition is coated and dried, and then imidized by heat treatment, and used as an insulating layer of an electronic circuit (interlayer insulating material for a multilayer wiring board) , Surface protective film, heat-resistant protective film, wear-resistant film, etc. of organic EL elements or semiconductor elements.

Usually, polyimide film is bonded with copper foil using an adhesive, or processed into a film layer and copper foil by evaporation, plating, sputtering, or casting. Laminate (polyimide film with copper foil), and used as a base film for flexible printed multilayer circuit boards.

This copper-clad laminate is processed by copper foil to form a wiring pattern, etc., and the wiring pattern is covered and protected by an insulating coating film or the like. In addition, a polyimide film is mainly used as a base material of this coating film.

Covering films such as polyimide films or flexible printed wiring boards using these polyimide films need to be colored in order to impart other functions such as concealment, optical properties, light-shielding properties, light reflection properties, and creativity. Into white, black, other colored and so on.

White polyimide materials such as white polyimide films are used as heat-resistant lightweight white materials, LEDs (light-emitting diodes), reflective materials for organic EL light-emitting, or base materials for metal layer white films. , can be suitably used for flexible printed wiring boards on which LEDs, organic ELs, or other light-emitting elements are mounted.

In addition, colored polyimide materials such as black have become thinner and lower in cost in recent years, and at the same time, the requirements for shielding and optical properties of electronic parts or mounting parts to be protected have increased. Therefore, they have shielding and light-shielding properties. The demand for colored polyimide materials such as black is increasing year by year.

Such polyimide materials such as polyimide films colored white or black are, for example, 1) mixed with polyamic acid obtained by reacting a specific diamine component with an aromatic tetracarboxylic acid. The mixed solution of the white pigment is flow-cast on the support, and the polyimide precursor film is obtained through drying, and the white polyimide film obtained by imidizing the polyimide precursor film (for example, refer to Patent Document 9 ), 2) On one or both sides of the polyimide layer, a multilayer polyimide film with a polyimide layer containing a pigment is laminated, and the polyimide film that constitutes the polyimide layer containing a pigment Amine, a multilayer polyimide film with light-shielding or light-reflective properties composed of specific components (for example, refer to Patent Document 10), 3) resin containing polyimide with specific repeating units, colored coloring materials, and white pigments The colored light-shielding polyimide film composed of the composition (for example, refer to Patent Document 11), 4) contains the perylene black pigment (A) and silicon dioxide (B) with a benzimidazole skeleton, compared to the polyimide film Overall, a black polyimide film in which the total weight and weight ratio of the above-mentioned pigments (A) and (B) are within a specific range (for example, refer to Patent Document 12), 5) pigment addition containing at least two or more pigments Polyimide film, the glossiness and thermal expansion coefficient of the polyimide film are added to the polyimide film with a pigment in a specific range (for example, refer to Patent Document 13), 6) make the specific diamine monomer and the specific diamine The polyimide polymer obtained by the reaction of acid anhydride monomers, the polyimide film as a colored base material including a matting agent composed of polyimide particles and one or more kinds of colored pigments (for example, refer to Patent Document 14).

However, when the colored polyimide materials such as the colored polyimide films described in the above-mentioned patent documents 9 to 14 are colored by coloring materials such as organic pigments or inorganic pigments, it may affect the coating layer film or the flexibility. Electrical properties (dielectric constant, dielectric tangent) or insulation of permanent printed wiring boards.

In particular, when carbon black is used for black coloring, not only the insulating property is lowered, but also the dielectric constant and dielectric tangent are deteriorated, so there is a problem that it is not suitable for applications such as high-speed communication and high-speed processing.

Therefore, colored polyimide materials, etc., have technical problems or limitations in electrical properties (low dielectric constant, low dielectric tangent) or insulation, and are currently required to impart concealment, optical properties, light-shielding properties or light Reflective, creative, etc. functions, and further improved electrical properties (low dielectric constant, low dielectric tangent) or insulating polyimide precursor solution composition, polyimide film using it, etc.

[Prior Art Literature] [Patent Document]

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

[Patent Document 2] Japanese Unexamined Patent Application Publication No. 2015-199901 (Scope of Claim, Examples, etc.)

[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2015-199903 (Scope of application, Examples, etc.)

[Patent Document 4] Japanese Unexamined Patent Publication No. 2001-294728 (Claims, Examples, etc.)

[Patent Document 5] Japanese Unexamined Patent Publication No. 2009-114377 (Claims, Examples, etc.)

[Patent Document 6] Japanese Unexamined Patent Application Publication No. 2010-275561 (Claims, Examples, etc.)

[Patent Document 7] Japanese Unexamined Patent Application Publication No. 2013-155344 (Claims, Examples, etc.)

[Patent Document 8] Japanese Unexamined Patent Application Publication No. 2015-78290 (Scope of Claim, Examples, etc.)

[Patent Document 9] Japanese Unexamined Patent Application Publication No. 2008-169237 (Claims, Examples, etc.)

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

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

[Patent Document 12] Japanese Unexamined Patent Application Publication No. 2013-28767 (Claims, Examples, etc.)

[Patent Document 13] Japanese Unexamined Patent Application Publication No. 2014-141575 (Claims, Examples, etc.)

[Patent Document 14] Japanese Unexamined Patent Application Publication No. 2015-44977 (Scope of Claim, Examples, etc.)

The present invention is an invention that solves the above-mentioned problems in the past and the current situation. The first series provides fine particle size, low viscosity, excellent storage stability, is suitable for mixing with various resin materials, and achieves low dielectric constant and low dielectric tangent. The non-aqueous dispersion of fluorine-based resin that can suppress the decrease in adhesion strength and adhesive strength, the thermosetting resin composition of fluorine-containing resin using the same, and its cured product are provided by the second series even with pigments or dyes. Coloring is also endowed with other functions such as concealment, optical properties, light-shielding properties, light reflection properties, creativity, etc., and is also highly insulating, and has heat resistance, electrical properties (low dielectric constant, low dielectric tangent), Colored thermosetting resin composition excellent in processability, insulating material composition using it, adhesive composition for circuit board, laminated board for circuit board, coating film, prepreg, flexible wiring board For the purpose of thermosetting resin compositions of fluorine-containing resins such as fluorine-containing resins, insulating material compositions using them, etc., the third series provides concealment, optical properties, light-shielding properties, or light reflection even if it is colored by pigments or dyes. It is also a colored polyimide with high insulation, excellent heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc., suitable for polyimide It is aimed at polyimide film, coating layer film using it, polyimide precursor solution composition of flexible printed wiring board, etc., polyimide film using it, etc.

As a result of the inventors of the present invention earnestly examining the above-mentioned conventional problems, etc., the non-aqueous dispersion of the fluorine-based resin of the above-mentioned first object can be obtained by the following first invention to the tenth invention, and a non-aqueous dispersion using the same can be obtained. Thermosetting resin composition of fluorine-containing resin and cured product thereof, thermosetting resin composition of fluorine-containing resin of the above-mentioned second object, insulating material composition using the same, polyimide precursor of the above-mentioned third object The solution composition, the polyimide film using it, and the like have completed the present invention.

〔上述式(I)中，l、m、n為正之整數〕。 That is, the first invention of the present invention is a non-aqueous dispersion of a fluororesin, which at least includes: fine powder of a fluororesin, urethane microparticles, 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 of the present invention is a non-aqueous dispersion of fluororesin, which at least includes: fine powder of fluororesin, thermoplastic elastomer, compound represented by the above formula (I), and non-aqueous solvent.

The fine powder of the aforementioned fluorine-based resin is selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorine Fine powders of at least one fluorine-based resin composed of trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred.

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

The compound represented by the aforementioned 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 fluororesin.

The aforementioned thermoplastic elastomer is preferably contained in an amount of 0.1 to 100% by mass based on the mass of the fine powder of the fluororesin.

The thermosetting resin composition of the fluorine-containing resin of the first invention or the second invention is characterized by comprising at least the non-aqueous dispersion of the fluorine-based resin of the first invention or the second invention and cyanic acid The resin composition of ester resin and/or epoxy resin, the cured product is characterized in that it is obtained by curing the thermosetting resin composition of each of the above-mentioned fluorine-containing resins.

Also, the thermosetting resin composition of the fluorine-containing resin of the second invention is characterized in that it comprises at least: the non-aqueous dispersion of the fluorine-containing resin of the second invention and a resin composition containing a thermosetting resin, the cured It is characterized in that it is formed by hardening the thermosetting resin composition of the above-mentioned fluorine-containing resins.

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

The fourth invention of the present invention is a thermosetting resin composition of a fluorine-containing resin, which is at least comprising: a fine powder of a fluorine-containing resin, a compound represented by the above formula (I) and a non-aqueous solvent in which a fine powder of a fluorine-based resin is dispersed. bodies; coloring materials; and resin compositions containing cyanate resins and/or epoxy resins.

The fifth invention of the present invention is a thermosetting resin composition of a fluorine-containing resin, comprising at least: a fine powder of a fluorine-containing resin, a compound represented by the above formula (I), and a non-aqueous solvent dispersed in a fine powder of a fluorine-based resin. and 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.

The sixth invention of the present invention is a thermosetting resin composition of a fluorine-containing resin comprising at least: a fluorine-based resin containing at least fine powder of a fluorine-based resin, a compound represented by the above-mentioned formula (I), a coloring material, and a non-aqueous solvent A fine powder coloring material dispersion; and a resin composition containing cyanate resin and/or epoxy resin.

The fine powder of the aforementioned fluorine-based resin is selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorine Fine powders of at least one fluorine-based resin composed of trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred.

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

In the aforementioned fluororesin fine powder dispersion, the average particle diameter of the dispersed fluororesin fine powder is preferably 10 μm or less.

The insulating material composition and the adhesive composition for circuit boards of the third invention to the sixth invention are characterized in that they are thermosetting using the fluorine-containing resin described in any one of the third invention to the sixth invention, respectively. Obtainer of resin composition.

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

The aforementioned insulating film is selected from polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide ( PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para (para) aromatic polyamide, polylactic acid, nylon, polyparabanic acid, polyether ether ketone ( PEEK), more than one type of film in groups is preferred.

The coating layer film of the third invention to the sixth invention of the present invention is an insulating film and a coating layer film having an adhesive layer formed on at least one side of the insulating film, wherein the adhesive layer is obtained by using the third invention~ An adhesive composition for a circuit board obtained by thermosetting the resin composition of the fluorine-containing resin described in any one of the sixth invention is characterized.

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

The prepreg of the third invention to the sixth invention is made of one or more types of fibers selected from the group consisting of carbon fiber, cellulose fiber, glass fiber, or aramid fiber The formed structure is characterized by impregnating at least the thermosetting resin composition of the fluorine-containing resin described in any one of the third invention to the sixth invention.

The seventh invention is a polyimide precursor solution composition comprising at least fine powder of fluororesin, the compound represented by the above formula (I), a coloring material and a polyimide precursor solution.

The eighth invention of the present invention is 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 above-mentioned formula (I), and a non-aqueous solvent ; Coloring material; and polyimide precursor solution.

The ninth invention of the present invention is a polyimide precursor solution composition comprising at least: a fluororesin micropowder dispersion containing at least a fluororesin micropowder, a compound represented by the above 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 of the present invention is a polyimide precursor solution composition comprising at least: fine powders of fluorine-based resins, compounds represented by the above formula (I), coloring materials, and fluorine-based resin micropowders of non-aqueous solvents. powder coloring material dispersion; and polyimide precursor solution.

The fine powder of the aforementioned fluorine-based resin is selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorine Fine powders of at least one fluorine-based resin composed of trifluoroethylene copolymer and polychlorotrifluoroethylene are preferred.

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

The aforementioned polyimide precursor solution preferably contains at least tetracarboxylic acid dihydrate and/or its derivatives and a diamine compound.

In the aforementioned fluororesin fine powder dispersion, the average particle diameter of the dispersed fluororesin fine powder is preferably 10 μm or less.

The polyimide, the polyimide film, and the polyimide insulating film of the seventh invention to the tenth invention are characterized in that the polyamide described in any one of the seventh invention to the tenth invention is used respectively. Obtainer of imine precursor solution composition.

The coating layer film and the flexible printed wiring board of the seventh invention to the tenth invention are characterized in that they are obtained by using the polyimide precursor solution composition described in any one of the seventh invention to the tenth invention Polyimide film.

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

According to the third invention to the sixth invention, even if it is colored by pigments or dyes, it can provide other functions such as concealment, optical characteristics, light-shielding properties, light reflection, creativity, etc., and it is also highly insulating. Colored thermosetting resin composition excellent in resistance, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc., insulating material composition using it, adhesive composition for circuit board, circuit board Thermosetting resin composition suitable for substrate laminates, coating films, prepregs, flexible wiring boards, etc.

In addition, insulating material compositions using thermosetting resin compositions of fluorine-containing resins of the third invention to the sixth invention, adhesive compositions for circuit boards, laminates for circuit boards, coating films, and prepregs , flexible printed wiring boards, etc., even if they are colored by organic pigments or inorganic pigments or dye coloring materials, they can be endowed with other functions such as concealment, optical characteristics, light-shielding or light reflection, and creativity. Colored insulating material composition, adhesive composition for circuit board, laminated board for circuit board, coating Layer film, prepreg, flexible printed wiring board, etc.

According to the 7th invention to the 10th invention, even if it is colored by pigments or dyes, it can provide other functions such as concealment, optical characteristics, light-shielding properties, light reflection, creativity, etc., and it is also highly insulating. Colored polyimide, polyimide film, coating film using it, flexible printed wiring, etc., which are excellent in properties, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc. A polyimide precursor solution composition suitable for boards and the like.

Also, polyimide, polyimide film, polyimide insulating film, coating layer film, flexible printed wiring board using the polyimide precursor solution composition of the seventh invention to the tenth invention Even if it is colored by organic pigments, inorganic pigments, and dye coloring materials, it is endowed with functions such as concealment, optical properties, light-shielding or light reflection, and creativity, and can obtain high insulation, heat resistance, and electricity. Colored polyimide, polyimide film, polyimide insulating film, coating film, flexible printed wiring board, etc. with excellent properties (low dielectric constant, low dielectric tangent) and processability .

10‧‧‧Insulating film

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

30‧‧‧Metal foil

[ Fig. 1 ] is 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 in a cross-sectional form.

[ Fig. 2 ] is a schematic diagram showing another example of the embodiment of the laminated board for a circuit board of the third invention to the sixth invention in a cross-sectional form.

[ Fig. 3 ] is a schematic diagram showing an example of an embodiment of the coating layer film of the third invention to the tenth invention in cross-section.

[Mode of Implementing the Invention]

Hereinafter, each embodiment of the first invention to the tenth invention will be described in detail according to each invention. In addition, the components common to the inventions are only described in detail initially in the first invention and the like, and the detailed description of the common parts in the second invention and the like will be omitted.

[The first invention: non-aqueous dispersion of fluororesin]

The nonaqueous dispersion of fluororesin of the first invention is characterized by containing at least fine powder of fluororesin, urethane microparticles, a compound represented by the following formula (I), and a nonaqueous solvent.

〔上述式(I)中，l、m、n為正之整數〕

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

The fine powder of 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), chlorine At least one of the group consisting of trifluoroethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polychlorotrifluoroethylene (PCTFE) The fine powder of the fluorine-based resin preferably has a primary particle size of 1 μm or less.

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

The fine powder of such a fluororesin is obtained by an emulsion polymerization method, and can be obtained by a generally used method such as a method described in a fluororesin handbook (edited by Takaomi Kurokawa, Nikkan Kogyo Shimbun Co., Ltd.). Then, the above-mentioned fine powder of fluororesin obtained by emulsion polymerization is aggregated and dried, and the aggregated secondary particles with the primary particle size are recovered as fine powder. Various commonly used fine powder manufacturing methods can be used.

The particle size of the fine powder of the fluororesin is preferably a primary particle size of 1 μm or less, and an average particle size of 1 μm or less in a non-aqueous dispersion.

In terms of stable dispersion in non-aqueous solvents, the primary particle size is preferably set at 0.5 μm or less, more preferably at 0.3 μm or less, so that a more uniform dispersion can be obtained.

Also, when the average particle size of the fluororesin fine powder in the non-aqueous dispersion exceeds 1 μm, sedimentation tends to occur and stable dispersion becomes difficult, which is not preferable. It is preferably not more than 0.5 μm, more preferably not more than 0.3 μm, especially preferably not less than 0.05 μm and not more than 0.3 μm.

In the first invention, the measurement method of the primary particle size can be used by laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) measured by scattering method, dynamic light scattering method, image imaging method, etc., but the fine powder of fluorine-based resin that becomes powder state after drying, due to The cohesion of primary particles is relatively strong, and sometimes it is difficult to diffract by laser. Measuring primary particle size by scattering method or dynamic light scattering method. In this case, the value obtained by the imaging method can also be shown.

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

The above-mentioned particle size measuring device includes, for example, a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) or a laser diffraction method using Microtrac (manufactured by Nikkiso Co., Ltd.). Scattering method or image forming method using Mac-VIEW (manufactured by Mountech Co., Ltd.).

In addition, the fine powder of the fluororesin to be used may be used by mixing two or more types with different primary particle diameters, or two or more types with different average particle diameters of the dispersed fluororesin fine powder may be mixed. Fine powders of two or more types of fluororesin having different primary particle diameters or average particle diameters are used. By using fine powders of two or more types of fluorine-based resins with different particle sizes, it is possible to adjust the viscosity and increase the filling rate.

In addition, the fine powder of fluororesin may be subjected to various surface treatments. For example, by acid treatment, alkali treatment, ultraviolet irradiation treatment, ozone treatment, electron beam irradiation treatment, heat treatment, water washing, hot water washing, various gas treatment, etc., the surfactant or surfactant remaining on the surface of the fine powder of fluororesin can be removed. Unnecessary components such as impurities may be activated.

In the first invention, the fine powder of the fluorine-based resin preferably contains 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total amount of the non-aqueous dispersion.

When the content is less than 5% by mass, the amount of solvent is large and the viscosity is extremely reduced, so the fine powder particles of fluororesin not only become easy to settle, but also when mixed with materials such as cyanate resin and epoxy resin, , the unfavorable situation caused by a large amount of solvent, for example, the unfavorable situation that it takes time to remove the solvent sometimes occurs. In addition, if it is too large than 70% by mass, the fine powders of the fluororesin tend to aggregate with each other, and it becomes extremely difficult to maintain the state of fine particles in a stable and fluid state, which is not preferable.

The urethane microparticles used in the first invention are non-adhesive properties of PTFE, so when bonding resins or resins to metals, etc., they are contained in order to solve the problem of adhesion strength, reduction in bonding strength, etc., and The inclusion of the urethane fine particles does not impair the stability of the non-aqueous dispersion of the fluororesin.

Urethane microparticles that can be used include generally widely used microparticles made of polyurethane having a urethane bond, which are usually produced by a compound having an isocyanate group and a hydroxyl group.

In the non-aqueous solvent used, the urethane microparticles are preferably in the form of particles, but not only sufficiently cross-linked hard urethane microparticles, but also elastomeric urethane particles can be used. Ester particles. The shape of the urethane microparticles may be amorphous, spherical or true spherical.

In addition, when the urethane fine particles may contain urethane, any particles may be used. For example, inorganic substances such as urethane fine particles containing acrylic components or silicon dioxide may be used. For homopolymer or copolymer. Specifically, commercially available Daimicbeaz CM (manufactured by Dainichi Seika Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), Gran Pearl (manufactured by AICA Kogyo Co., Ltd.) and the like are mentioned.

The method of forming urethane microparticles, for example, there is a method of pulverizing a block of polyurethane to form microparticles, or a method of using suspension polymerization, emulsion polymerization, etc. to form microparticles, etc., and can use commonly used amino groups Method for producing formate microparticles. In addition, the surface of the microparticles may be coated with hydrophobic silica or silica treated with a fluorine-based compound.

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

In non-aqueous solvents, in terms of stable dispersion, the primary particle size is preferably set to 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less, so that a more uniform dispersion can be obtained.

Also, when the average particle diameter of the urethane fine particles in the non-aqueous dispersion exceeds 10 μm, sedimentation tends to occur and stable dispersion becomes difficult, which is not preferable. Preferably it is 3 μm or less, and more preferably 1 μm or less. Also, the measurement of the primary particle diameter of the urethane fine particles and the measurement of the average particle diameter of the urethane fine particles in the non-aqueous dispersion can be performed in the same manner as the respective measurement methods of the fine powder of the above-mentioned fluororesin.

In the first invention, the urethane fine particles preferably contain 0.1 to 20% by mass, more preferably 0.3 to 15% by mass, and still more preferably 0.5 to 10% by mass relative to the mass of the fine powder of the fluororesin. quality%.

When the content is less than 0.1% by mass, the addition of urethane fine particles significantly weakens the contribution to adhesion and adhesiveness, which is not preferable. On the other hand, if it is larger than 20% by mass, the electrical or physical properties of the urethane fine particles are strongly released, and the effect of the electrical properties due to the addition of PTFE becomes weak, which is unfavorable.

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 separately dispersed and then mixed.

The compound represented by the above (I) used in the first invention may be one in which the fine powder of the fluororesin is uniformly and stably dispersed in the form of fine particles in a non-aqueous solvent. Its molecular structure is a ternary polymer composed of vinyl butyral/vinyl acetate/vinyl alcohol, which reacts polyvinyl alcohol (PVA) with butyraldehyde (BA), and has butyral, acetyl, and hydroxyl groups. By changing the ratio of these three structures (the ratios of l, m, n), the solubility to non-aqueous solvents can be controlled, and the non-aqueous system with fluorine-based resin fine powder added to various resin materials Chemical reactivity in dispersion.

As the compound represented by the above (I), S-Lec B series, K(KS) series, SV series manufactured by Sekisui Chemical Co., Ltd., Mowital series manufactured by Kuraray Co., Ltd., etc. can be used as commercially available products.

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

These can be used individually or in mixture of 2 or more types.

The content of the compound represented by the above (I) is preferably 0.1 to 20% by mass relative to the fine powder of the fluororesin. When the content of this compound is less than 0.1% by mass, the dispersion stability deteriorates and the fine powder of the fluorine-based resin tends to settle. When the content exceeds 20% by mass, the viscosity becomes high, which is not preferable.

In addition, when considering the characteristics of adding a non-aqueous dispersion of fine powder of fluororesin to thermosetting resins, etc., it is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and most preferably 0.1 to 10% by mass. 0.1~5% by mass.

The non-aqueous dispersion of the fine powder of fluororesin in the first invention can also be combined with the compound represented by the above-mentioned (I) to use other surfactants or Dispersant.

For example, regardless of fluorine-based or non-fluorine-based, non-ionic, anionic, cationic, etc. surfactants or dispersants, non-ionic, anionic, cationic, etc. polymer surfactants or polymer dispersants Agents, etc., but not limited to these, can be used.

The non-aqueous solvent used in the above-mentioned non-aqueous dispersion of the first invention is, for example, selected from the group consisting of γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, Cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-amyl 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 - Ethoxypropionate, Dioxane, Methyl Lactate, Ethyl Lactate, Methyl Acetate, Ethyl Acetate, Butyl Acetate, Methyl Pyruvate, Ethyl Pyruvate, Methyl Methoxy Propionate , ethyl ethoxy propionate, anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, bibenzyl ether, phenetole, butyl phenyl ether, benzene, ethylbenzene, diethylbenzene, Amylbenzene, cumene, toluene, xylene, cumene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, Butyl Monoglycidyl Ether, Phenyl Monoglycidyl Ether, Methyl Diglycidyl Ether, Ethyl Diglycidyl Ether, Butyl Diglycidyl Ether, Phenyl Diglycidyl Ether, Cresol Monoglycidyl ether, Ethylphenol monoglycidyl ether, Butylphenol monoglycidyl ether, Mineral spirits, 2-Hydroxyethyl acrylate, Tetrahydrofurfuryl acrylate, 4-Vinylpyridine, N-methyl -2-pyrrolidone, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, epoxypropyl methacrylate, neopentyl glycol diacrylate, hexyl Glycol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropoly Ether, N,N-dimethylformamide, N,N-dimethylacetamide, dioxolane, and various silicone oils, one type of solvent or two or more of these solvents By.

Among these solvents, those that vary due to the type of resin used are preferred, and examples include methyl ethyl ketone, cyclohexanone, toluene, xylene, N-methyl-2-pyrrolidone, N,N-di Methylformamide, N,N-Dimethylacetamide, Dioxolane.

In the first invention, the above-mentioned solvents are mainly used, and other solvents may be used in combination or other solvents may be used, and the preferred one is selected according to the application (various resin materials for circuit boards) and the like.

In addition, due to the polarity of the solvent used, it is considered that the compatibility with water is higher, but when the water content is large, it will hinder the dispersibility of the fine powder of fluorine-based resin in the solvent, and sometimes cause the viscosity to increase or the particles to interact with each other. Cohesion.

In the present invention, the water content of the non-aqueous solvent and non-aqueous dispersion used by the Karl Fisher method is preferably 8000ppm or less [0≦moisture content≦8000ppm]. In the present invention (including the examples described later), the measurement of the moisture content by the Karl Fisher method is in accordance with JIS K 0068:2001, and can be measured, for example, by MCU-610 (manufactured by Kyoto Denshi Kogyo Co., Ltd.). By setting the water content in the solvent and the water content of the non-aqueous dispersion to 8000 ppm or less, it is possible to further form a non-aqueous dispersion of a fine powder of a fluorine-based resin having a fine particle size, low viscosity, and excellent storage stability. More preferably, it is at most 5000 ppm, more preferably at most 3000 ppm, and most preferably at most 2500 ppm. In addition, the adjustment of the above-mentioned water content can be carried out by dehydration of solvents such as generally used oily solvents, for example, molecular sieves can be used.

The non-aqueous dispersion of the fluorine-based resin of the first invention constituted in this way can obtain a fine dispersion due to at least containing the fine powder of the fluorine-based resin, the urethane microparticles, the compound represented by the above-mentioned formula (I) and the non-aqueous solvent. Particle size, low viscosity, excellent storage stability, suitable for mixing with various resin materials, low dielectric constant, low dielectric tangent, and non-aqueous dispersion of fluororesin that can suppress adhesion strength and reduce adhesive strength.

[The second invention: non-aqueous dispersion of fluororesin]

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

In this second invention, only a thermoplastic elastomer is used instead of the urethane fine particles of the above-mentioned first invention, which is different from the above-mentioned first invention, so the description will focus on the thermoplastic elastomer, and the fluorine-based resin used in the second invention The fine powder, the compound represented by the above-mentioned formula (I), and the non-aqueous solvent have been described in detail in the above-mentioned first invention, so the description thereof is omitted. Hereinafter, the thermoplastic elastomer used in the second invention will be described.

Due to the non-adhesiveness of PTFE, the thermoplastic elastomer system used in the second invention is contained in order to solve the problem of adhesion strength, reduction in adhesion strength, etc. when bonding resins or resins to metals, etc., and contains the heat Plastic elastomer will not impair the stability of the non-aqueous dispersion of fluororesin.

The thermoplastic elastomer of the second invention can be used as long as it can be plasticized when heated, for example, it can be selected from styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based Thermoplastic elastomers, urethane-based thermoplastic elastomers, polyamide-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 according to the use of the non-aqueous dispersion of the fluororesin.

Specifically, styrene-butadiene copolymer (SBS), hydrogenated-styrene-butadiene copolymer (SEBS), hydrogenated-styrene-isoprene copolymer (SEPS), polyester- Microdispersion in the matrix of polyether copolymer (TPEE), polyurethane-polyether/polyester copolymer (TPU), nylon-polyether/polyester copolymer (TPA), PP, etc. There are olefin-based thermoplastic elastomers (TPO) of olefin-based rubber, and the like. Commercially available products include SIS series (styrene-based thermoplastic elastomer, manufactured by JSR Corporation), TR series (styrene-butadiene thermoplastic elastomer, manufactured by JSR Corporation), RB series (polybutadiene-based Thermoplastic elastomer, manufactured by JSR Corporation), JSR EXELINK (olefin-based thermoplastic elastomer, manufactured by JSR Corporation), DYNARON series (hydrogenated thermoplastic elastomer, manufactured by JSR Corporation), Themorun (olefin-based thermoplastic elastomer , manufactured by Mitsubishi Chemical Co., Ltd.), 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.), etc.

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 soluble or insoluble in the non-aqueous solvent used.

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

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

In non-aqueous solvents, in terms of stable dispersion, the primary particle size is preferably set to 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less, so that a more uniform dispersion can be obtained.

Also, when the average particle size of the thermoplastic elastomer fine particles in the non-aqueous dispersion exceeds 10 μm, sedimentation tends to occur and stable dispersion becomes difficult, which is not preferable. Preferably it is 3 μm or less, more preferably 1 μm or less. Also, the measurement of the primary particle size of thermoplastic elastomer particles and the measurement of the average particle size of urethane particles in a non-aqueous dispersion can be performed in the same manner as the above-mentioned measurement methods of fine powders of fluorine-based resins.

In the second invention, the thermoplastic elastomer is preferably contained in an amount of 0.1 to 100% by mass, more preferably 0.3 to 80% by mass, and still more preferably 0.5 to 50% by mass, based on the mass of the fine powder of fluororesin. .

When the content is less than 0.1% by mass, the addition of the thermoplastic elastomer significantly weakens the contribution to the adhesion and adhesiveness, which is not preferable. When it exceeds 100% by mass, due to the electrical or physical properties of thermoplastic elastomers, the influence of plasticization during heating appears strongly, and the effect of electrical properties or physical properties becomes weak due to the addition of fluorine-based resins. , so it is not good.

In the second invention, the thermoplastic elastomer can be used by dissolving it in a non-aqueous solvent when dispersing the fine powder of the fluororesin, or dissolving the thermoplastic elastomer after making the fine powder dispersion of the fluororesin. elastic body to use. Also, when the thermoplastic elastomer is insoluble in a non-aqueous solvent, the fine particles of the thermoplastic elastomer and the fluorine-based resin are dispersed at the same time, or the fine particles of the thermoplastic elastomer and the fine powder of the fluorine-based resin are separately dispersed and then mixed. wait.

The non-aqueous dispersion of the fluorine-based resin of the second invention constituted in this way is because it contains at least the fine powder of the fluorine-based resin, a thermoplastic elastomer, the compound represented by the above-mentioned formula (I) and a non-aqueous solvent. Particle size, low viscosity, excellent storage stability, suitable for mixing with various resin materials, low dielectric constant, low dielectric tangent, and non-aqueous dispersion of fluorine-based resins that can suppress the decrease in adhesion strength and adhesive 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 of the first invention and the second invention is characterized by comprising at least a non-aqueous dispersion of the fluorine-based resin of the first invention or the second invention, and a cyanate resin And/or resin composition of epoxy resin.

The content of the non-aqueous dispersion of the above-mentioned fluororesin is due to the fine powder of fluororesin such as PTFE, urethane microparticles or thermoplastic elastomer contained in the dispersion, and the compound represented by the above formula (I) and non-aqueous solvents, or due to the use of cyanate resins, epoxy resins, etc. After the composition of the oxygen resin is prepared, it is removed during hardening, so the content of the fine powder of fluorine-based resin such as PTFE is finally adjusted to be preferably 1 to 100 parts by mass relative to 100 parts by mass of these resins. , more preferably 1 to 30 parts by mass, preferably a dispersion.

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

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

The resin composition used in the first invention and the second invention includes at least a thermosetting resin. Thermosetting resins include, for example, epoxy resins, polyimide resins, polyamideimide resins, triazine resins, phenol resins, melamine resins, polyester resins, cyanate resins, and modifications of these resins. These resins may be used alone or in combination of two or more. Any of these resins used as the base resin of the thermosetting resin composition is not particularly limited as long as it is suitable for users such as insulation and adhesiveness in electronic equipment.

Preferred resin compositions include at least those relative to cyanate resins and/or epoxy resins. These resins are especially good base resins for thermosetting resin compositions, and are suitable for insulation or Subsequent and so on.

The cyanate resins (cyanate ester resins) that can be used in the first invention and the second invention include, for example, at least bifunctional aliphatic cyanate, at least bifunctional aromatic cyanate, or These mixtures are, for example, selected from 1,3,5-tricyanoxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, Polymers of polyfunctional cyanate esters of at least one of naphthalene, 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, and 2,7-dicyanoxynaphthalene, bisphenol A-type cyanide Ester resins or such hydrogenated ones, bisphenol F type cyanate resins or such hydrogenated ones, 6F bisphenol A dicyanate resins, bisphenol E type dicyanate resins, tetramethylbisphenol At least one of F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, or cyanate novolak resin. Moreover, the commercial item of these cyanate resins can also be used.

Epoxy resins that can be used include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin Oxygen resin, pernaphthyl ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin Resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol epoxy resin, trimethylol epoxy resin, halogenated epoxy resin, etc.

These epoxy resins can be used 1 type or in combination of 2 or more types.

The epoxy resins that can be used in the first invention and the second invention are not limited to the above-mentioned resins as long as there are one or more epoxy groups in one molecule, and bisphenol A, hydrogenated bisphenol A, Cresol novolak series, etc.

In the present invention, the above-mentioned cyanate resin (cyanate ester resin) and epoxy resin can be used alone or in combination, and when used in combination, they can be used in combination in a mass ratio of 1:10 to 10:1.

In the first invention and the second invention, when the above-mentioned cyanate resin or epoxy resin is used, an active ester compound can be used as an additive from the viewpoint of reactivity, curability, and formability.

The usable active ester compound is generally preferably a compound having two or more active ester groups in one molecule, and examples thereof include carboxylic acid compounds, phenol compounds, and naphthol compounds. 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. Phenol compounds or naphthol compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, 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, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, phenol novolac, etc. .

These active ester compounds can be used by 1 type or in combination of 2 or more types. Examples of commercially available active ester compounds include EXB-9451, EXB-9460 (manufactured by DIC Co., Ltd.), DC808, and YLH1030 (manufactured by Japan Epoxy Resin Co., Ltd.).

The amount of these active ester compounds used is determined by the base resin of the thermosetting resin composition and the type of active ester compound used.

In addition, among the aforementioned active ester compounds, an active ester compound hardening accelerator may be used as necessary.

As the active ester compound hardening accelerator, an organic metal salt or an organic metal complex can be used, for example, an organic metal salt or an organic metal complex containing iron, copper, zinc, cobalt, nickel, manganese, tin, etc. can be used. Specifically, the aforementioned cyanate ester hardening accelerators include manganese decalinate, iron decalinate, copper decalinate, zinc decalinate, cobalt decalinate, iron octoate, copper octoate, zinc octoate, octoate Organic metal salts of cobalt, etc.; organometallic complexes of lead acetylpyruvate, cobalt acetylpyruvate, etc.

These active ester compound hardening accelerators are based on the concentration of the metal. From the viewpoint of reactivity, hardenability, and formability, they contain 0.05 to 5 parts by mass relative to 100 parts by mass of the resin used above, and preferably contain 0.1~3 parts by mass.

Also, in the first invention and the second invention, when the above-mentioned epoxy resin is used, a curing agent may be used as an additive from the viewpoint of reactivity, curability, and moldability. Hardeners that can be used include aliphatic hardeners such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine. Amines, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylene, 4,4'-diaminodiphenylene, 4,4'-diaminodiphenyl Methane, aromatic amines such as 4,4'-diaminodiphenyl ether, mercapto propionate, mercaptans such as terminal mercapto compounds of epoxy resins, polyazelaic anhydride, methyltetrahydrophthalate Dicarboxylic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2, Alicyclic acid anhydrides such as 3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2,3-dicarboxylic anhydride, and phthalic anhydride , aromatic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride, imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and their salts, the above Aliphatic amines, aromatic amines and/or amine adducts obtained by the reaction of imidazoles and epoxy resins, hydrazides such as adipic acid dihydrazide, dimethyl At least one of benzylamine, tertiary amines such as 1,8-diazabicyclo[5.4.0]undecene-7, organic phosphines such as triphenylphosphine, and dicyandiamide.

The amount of these hardeners used is determined by the type of 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, an antifoaming agent, a leveling agent, Compounds, adhesion imparting materials, etc., are generally used in thermosetting resin compositions for electronic equipment.

In the first invention and the second invention, the fine powder of fluorine-containing resin can be made It does not aggregate but exists uniformly, and has low dielectric constant and dielectric tangent, and the adhesion strength and adhesive strength will not decrease, so it can exhibit excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy.

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

The thermosetting resin compositions of the fluorine-containing resins of the first invention and the second invention can be cured by molding and curing them in the same way as conventional thermosetting resin compositions such as epoxy resin compositions. thing. The molding method and curing method can be the same as those of thermosetting resin compositions such as conventional epoxy resin compositions. The inherent methods of the thermosetting resin composition of the fluorine-containing resin of the present invention are not required and are not particularly limited. .

The cured products obtained by curing the thermosetting resin compositions of the fluorine-containing resins of the first invention and the second invention can be in the form of laminates, moldings, adhesives, coating films, and films.

The thermosetting resin compositions of the fluorine-containing resins of the first invention and the second invention, and their cured products, do not impair the adhesiveness or heat resistance of thermosetting resins such as epoxy resins, and have low dielectric properties. Constant, low dielectric tangent, excellent electrical properties, and, because it contains urethane particles, it can suppress the reduction of adhesion strength and adhesive strength, so it is suitable for electronic substrate materials, insulating materials, adhesive materials, etc., for example, it can be used as electronic Packaging materials for parts, copper-clad laminates, insulating coatings, composite materials, insulating adhesives, etc., especially suitable for the formation of insulating layers of multilayer printed wiring boards for electronic equipment, laminates for circuit boards, coating layers Films, prepregs, etc.

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

The thermosetting resin composition of fluorine-containing resin according to the third invention is characterized in that it contains at least fine powder of fluorine-containing resin, the compound represented by the above formula (I), a coloring material, and cyanate resin and/or epoxy resin. For the resin composition of resin, the fourth invention of the present invention at least includes: a fluororesin fine powder dispersion containing at least a fine powder of a fluororesin, a compound represented by the above formula (I) and a non-aqueous solvent, a coloring material, and a cyanide-containing resin composition. The resin composition of an ester resin and/or an epoxy resin is characterized by a fluororesin containing at least a fine powder of a fluororesin, a compound represented by the above-mentioned formula (I) and a non-aqueous solvent in the fifth invention. 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, the sixth invention at least includes: Fluorine resin fine powder coloring material dispersion containing at least fine powder of fluorine resin, compound represented by the above formula (I), coloring material and non-aqueous solvent, and resin composition containing cyanate resin and/or epoxy resin for the characteristic.

Hereinafter, the thermosetting resin composition of each fluorine-containing resin will be described in detail about the third invention to the sixth invention. In addition, the fine powder of fluorine-based resin used in the third invention to the sixth invention, the compound represented by the above formula (I), non-aqueous solvent, cyanate resin, epoxy resin, etc., are the same as those in the first invention above. In this case, the explanation is omitted, and when it is different, the details are as follows.

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

In the third invention, the fine powder of the fluorine-based resin used can be used as described in detail in the first invention, and its content is preferably 5 to 70% by mass relative to the total solid content of the thermosetting resin composition. , more preferably 10 to 60% by mass.

When the content is less than 5% by mass, the properties of fluorine-based resins cannot be sufficiently imparted to the final thermosetting resin, etc., and when the content exceeds 70% by mass, the mechanical strength of the final thermosetting resin, etc. Extremely weakened, etc., so it is not good.

In the third invention, the compound represented by the above-mentioned formula (I) can be used as described in the first invention, and its content is preferably 0.01-30% by mass relative to the fine powder of the fluororesin. When the content of this compound is less than 0.01% by mass, the dispersion stability deteriorates and the fluorine-based fine powder tends to settle. When the content exceeds 30% by mass, the viscosity of the thermosetting resin composition becomes high, which is not preferable.

Moreover, when the characteristics of the obtained thermosetting resin etc. are considered, it is more preferable that it is 0.01-5 mass %, and it is especially preferable that it is 0.01-2 mass %.

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

<coloring material>

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

Inorganic pigments, organic pigments, and dyes that can be used, as long as they are used to color thermosetting resin materials such as coating films and flexible printed wiring boards, to impart concealment, optical properties, light-shielding properties, or light reflection properties. When it is used for functions such as properties, it is not particularly limited, and it is preferable not to damage electrical properties such as insulation, low dielectric constant, and low dielectric tangent, and processability, so as to better exert the effects of the present invention. From the viewpoint of inorganic pigments and organic pigments, at least one selected from carbon-based black pigments, oxide-based black pigments, and white pigments can be cited.

Examples of carbon-based black pigments include carbon black such as furnace black, acetylene black, thermal black, and channel black, biotite, graphite powder, and commercially available graphite powder.

Oxide-based black pigments, for example, selected from cobalt oxide, ferric oxide, ferrous oxide, manganese oxide, titanium black, chromium oxide, bismuth oxide, tin oxide, copper oxide or copper-iron-manganese, aniline black, Perylene black, iron manganese bismuth black, cobalt iron chromium black, copper chromium manganese black, iron chrome black, manganese bismuth black, manganese yttrium black, iron manganese oxide spinel black, copper chrome spinel black, red iron ore, At least one kind of group consisting of magnetite, mica-like iron oxide, metal oxide containing titanium black and iron, composite metal oxide, etc.

Among these black pigments, carbon blacks excellent in light-shielding properties can be used as commercially available products such as #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #52, #85, #95, CF9, MA7, MA8, MA11, MA100, MA220, MA230, etc., Printex25, 35, 40, 45, 55, 150T manufactured by Evonik Industries, Printex series such as U, V, P, L6, etc., as well as perylene black pigments that improve electrical reliability, among commercial products, Lumogen black series and Paliogen black series manufactured by BASF Corporation, etc. are preferably used. In addition, aluminum flake pigments (black interference aluminum pigments) excellent in heat-shielding properties can also be used.

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

Among these white pigments, titanium oxide with high hiding power and fine powder silicon dioxide with high insulation are more preferable, and these can be used together. By using both together, insulation and reflectivity can be improved at the same time. Examples of the aforementioned titanium oxide include anatase-type titanium oxide and rutile-type titanium oxide. Among them, when used for LEDs, anatase-type titanium oxide that reflects wavelengths of near-ultraviolet LEDs and blue LEDs is more preferable. In addition, examples of the above-mentioned fine powder silica include crystalline silica, fused silica, and fumed silica.

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

Inorganic pigments and organic pigments other than the above carbon-based black pigments, oxide-based black pigments, and white pigments include, for example, azo pigments, disazo pigments, isoindolinone pigments, quinophthalone pigments, and isoindoline pigments. Pigments, anthraquinone pigments, anthrone pigments, xanthene pigments, diketopyrrolopyrrole pigments, anthraquinone (anthrone) pigments, perylene pigments, quinacridone pigments, indigo pigments, dioxazine pigments, phthalocyanine pigments And azomethine pigments, etc. Also, examples of inorganic pigments include manganese oxide. Aluminum oxide, chromium oxide. Tin oxide, iron oxide, cadmium sulfide. Red color such as selenium sulfide, cobalt oxide, zirconium dioxide. Vanadium oxide, chromium oxide. Blue series such as vanadium pentoxide, zirconium. Silicon.鐠, vanadium. Tin, chromium. titanium. Yellow series such as antimony, chromium oxide, cobalt. Chromium, Aluminum Oxide. Chromium and other green series, aluminum. manganese, iron. Silicon. Peach color of zirconium and so on.

These inorganic pigments and organic pigments containing carbon-based black pigments, oxide-based black pigments, white pigments, etc., do not impair processability and other performances, and can effectively exert concealment, optical characteristics, light-shielding properties, or light reflection. From the viewpoint of other functions such as sex and creativity, the primary particle size is preferably 1 μm or less.

Usable dyes include, for example, oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, or acid mordant dyes, which have any form of various dyes. In addition, it may be in the form of a lake of the aforementioned dye or a salt-forming compound of a dye and a nitrogen-containing compound, or the like.

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

In the first invention, among inorganic pigments, organic pigments, and dyes used as coloring materials, applications of thermosetting resin materials (insulating materials, insulating films, coating films, flexible printed wiring boards, etc.) are considered, The optimum coloring material is selected as described above from the point of view that the inclusion of the coloring material can exhibit the desired hiding properties, light-shielding properties, or reflective properties.

In the third invention, the coloring material to be used is based on the application of the thermosetting resin material (thermosetting resin film, thermosetting resin insulating film, coating layer film, flexible printed wiring board, etc.), concealment, optical characteristics, and light-shielding properties. properties, such as light reflectivity, creativity, etc., and determine a more suitable amount, never impairing the performance of insulation, low dielectric constant, low dielectric tangent, etc., electrical characteristics, processability, etc., From the point of view of containing the coloring material to exert the purpose of concealment, optical properties, light-shielding or light-reflecting properties, creativity and other functions, the lower limit is more than 0.1% by mass relative to the total solid content of the thermosetting resin composition. It is 1% by mass or more, and the upper limit is 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of not impairing properties such as mechanical strength of the final thermosetting resin.

〔Resin composition〕

In the third invention, the resin composition used includes at least cyanate resin and/or epoxy resin. These resins are used as the base resin of the thermosetting resin composition, as long as they are suitable for users such as insulation and adhesiveness in electronic equipment, there are no particular limitations.

Available cyanate ester resins (cyanate ester resins), epoxy resins, mass ratios (1:10 to 10:1) when used together, active ester compounds and their hardening accelerators, and epoxy resins For the curing agent and their respective contents, the cyanate resin, epoxy resin, active ester compound, etc. described in detail in the first invention and the second invention can be used, so the description 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, Defoaming agent, leveling agent, coupling agent, adhesion imparting material, etc., materials generally used in thermosetting resin compositions for electronic equipment.

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

Among the non-aqueous solvents used in the third invention, it is preferable to change due to the material used or the application of the thermosetting resin, and examples include acetaniline, dioxolane, o-cresol, and m-formaldehyde. Phenol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Diphenylene, gamma-butyrolactone, cyclobutane, halogenated phenols, xylene, acetone.

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

The thermosetting resin composition of the fluorine-containing resin of the third invention is characterized by comprising at least: the fine powder of the above-mentioned fluorine-containing resin, the compound represented by the above-mentioned formula (I), the above-mentioned coloring material, and the above-mentioned cyanate resin and For example, in a non-aqueous solvent, add the fine powder of the above-mentioned fluorine-based resin, the compound represented by the above-mentioned formula (I), the above-mentioned coloring material, and the above-mentioned cyanate resin and / or the resin composition of epoxy resin, for mixing, etc., in addition to stirring with a disperser or a homogenizer, etc., it can be mixed by using an ultrasonic disperser, a planetary mixer, a three-roll mill, a ball mill, or a bead mill. , jet mill and various mixers and dispersers to prepare.

In the thermosetting resin composition of the fluorine-containing resin of the third invention, by adding a predetermined amount of fine powder of the fluorine-containing resin, the compound represented by the above-mentioned formula (I), the above-mentioned coloring material, and the The resin composition of the above-mentioned cyanate resin and/or epoxy resin is mixed, and by adjusting the total resin concentration of the cyanate resin, epoxy resin, etc. necessary to become the final thermosetting resin composition, the fluorine Resin powder and coloring material can exist uniformly without agglomeration, have low dielectric constant and dielectric tangent, and can exhibit excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy.

The thermosetting resin composition of the fluorine-containing resin of the third invention includes at least: the fine powder of the above-mentioned fluorine-containing resin, the compound represented by the above-mentioned formula (I), the above-mentioned coloring material, and the above-mentioned cyanate resin and/or ring resin. The resin composition of the epoxy resin can be formed into a cured product, an insulating material, etc. by molding and curing in the same way as a thermosetting resin composition such as a conventional epoxy resin composition. The molding method and curing method can be the same as those of thermosetting resin compositions such as conventional epoxy resin compositions. The inherent method of the thermosetting resin composition of the fluorine-containing resin of the third invention is not required, and there is no special method. limited.

In addition, the thermosetting resin composition of the fluorine-containing resin of the third invention can use various additives such as surfactants, dispersants, antifoaming agents, and silica particles within the range that does not impair the effects of the present invention. Or filler materials such as acrylic particles or elastomers, etc.

In addition, in the thermosetting resin composition of fluorine-containing resin according to the third invention, the moisture content of the thermosetting resin composition according to the Karl Fisher method is preferably 5000 ppm or less [0≦moisture content≦5000 ppm]. Considering moisture incorporation from the material or in the manufacturing stage, but by keeping the moisture content of the final thermosetting resin composition at 5000ppm or less, the fine powder of fluorine-based resin or the coloring material (pigment) will not aggregate , can exist uniformly, and a thermosetting resin composition with better storage stability can be obtained.

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

The thermosetting resin composition of the fluorine-containing resin of the fourth invention is characterized in that it includes at least: a fine powder of the above-mentioned fluorine-containing resin, a compound represented by the above-mentioned formula (I) and a fine powder of the above-mentioned non-aqueous solvent. For the powder dispersion, coloring material, and resin composition containing the above-mentioned cyanate resin and/or epoxy resin, the detailed description of the above-mentioned components and the like is the same as that of the above-mentioned third invention, so the description is omitted.

In the 4th invention, compared with the above-mentioned 3rd invention, the fluororesin fine powder dispersion containing at least the fine powder of the fluororesin, the compound represented by the formula (I) and the non-aqueous solvent is prepared in advance. Adding a certain amount of coloring material and the resin composition containing the above-mentioned cyanate resin and/or epoxy resin, mixing, etc., can obtain fine powder of fluororesin and coloring material in the composition without agglomeration or Settling, uniform fine particle dispersion, etc. thermosetting resin composition.

The above-mentioned fluorine-based resin fine powder dispersion of the fourth invention can be obtained by, for example, using 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. A disperser such as a mill is used to stir, mix, and disperse to produce, but in the dispersed state, the fine powder of the fluororesin is obtained by the dynamic light scattering method or laser diffraction. The volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is preferably 10 µm or less. Usually, primary particles are aggregated into secondary particles to form a fine powder with a large particle size. By dispersing the secondary particles of the fine powder of the fluororesin to a particle size of 10 μm or less, for example, by using mixers such as dispersers and homogenizers, ultrasonic dispersers, three-roll mills, wet ball mills, Bead mill, wet jet mill, high-pressure homogenizer and other dispersing machines can be used to disperse, and stable dispersion can be obtained even in the case of long-term storage at low viscosity.

The average particle size is preferably not more than 5 μm, more preferably not more than 3 μm, still more preferably not more than 1 μm. Because it can become a more stable dispersion.

Also, in the thermosetting resin composition of the fluorine-containing resin of the fourth invention, similar to the thermosetting resin composition of the above-mentioned fluorine-containing resin of the third invention, within the range that does not impair the effect of the present invention, it can be Various additives such as surfactants, dispersants, and defoamers, fillers such as silica particles and acrylic particles, and elastomers are used.

In addition, in the thermosetting resin composition of the fluorine-containing resin of the fourth invention (including the fifth invention and the sixth invention described later), as in the thermosetting resin composition of the third invention described above, Karl Fernando is used. The moisture content of snow method is preferably below 5000ppm [0≦moisture content≦5000ppm]. Considering moisture incorporation from the material or in the manufacturing stage, but by keeping the moisture content of the final thermosetting resin composition at 5000ppm or less, the fine powder of fluorine-based resin or the coloring material (pigment) will not aggregate , can exist uniformly, and a thermosetting resin composition with better storage stability can be obtained.

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

The thermosetting resin composition of fluorine-containing resin according to the fifth invention is characterized in that it comprises at least fine powder of fluorine-containing resin and a compound represented by formula (I) dispersed in the above-mentioned non-aqueous solvent. body; 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. Inventions and the like are the same, and descriptions thereof are omitted.

Compared with the above-mentioned 3rd, 4th inventions, the 5th invention uses the fluorine-based resin fine-powder dispersion prepared in advance to contain at least the fine-powder of fluorine-based resin, the compound represented by formula (I) and the 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 mixed by adding a predetermined amount of the resin composition containing the above-mentioned cyanate resin and/or epoxy resin to the dispersion or solution etc. It is possible to obtain a thermosetting resin composition in which fine powders of fluorine-based resins and coloring materials do not aggregate or settle in the composition, and can uniformly disperse fine particles.

The above-mentioned coloring material dispersion of the fifth invention is obtained, for example, by dispersing an inorganic pigment or an organic pigment containing the above-mentioned carbon-based black pigment, oxide-based black pigment, white pigment, etc., in a non-aqueous solvent. Dispersion can be performed using a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, and the like within a range that does not impair the effects of the present invention.

The equipment used for dispersion is the same as the fine powder dispersion of the above-mentioned fluorine-based resin, for example, mixers such as dispersers and homogenizers, ultrasonic dispersers, three-roll mills, wet ball mills, bead mills, A disperser such as a wet jet mill etc. is used to stir, mix and disperse to produce.

The above-mentioned coloring material dispersion system is in the dispersed state, and the coloring material (pigment) is diffracted by dynamic light scattering or laser. The volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is preferably 3 μm or less. By dispersing the 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, Dispersion with dispersing machines such as wet jet mills and high-pressure homogenizers enables stable dispersions to be obtained even when stored at low viscosity for a long period of time.

The average particle size is preferably not more than 1 μm, more preferably not more than 0.5 μm, still more preferably not more than 0.3 μm. Because it can become a more stable dispersion.

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

The device used for dissolving, such as mixers such as dispersers and homogenizers, or ultrasonic irradiation devices, can be used for devices that can stir, mix, and dissolve. When using low-solubility coloring materials (dye) In this case, the non-aqueous solvent may be dissolved while stirring while heating.

[Sixth Invention: Thermosetting Resin Composition of Fluorine-Containing Resin]

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

Compared with the above-mentioned 3rd, 4th, 5th inventions, the 6th invention preliminarily uses the fluororesin fine powder containing at least the fine powder of fluororesin, the compound represented by formula (I), coloring agent and non-aqueous solvent for coloring Material dispersion, by adding a certain amount of the above-mentioned resin composition containing cyanate resin and/or epoxy resin to this dispersion, mixing, etc., can obtain fine powder of fluorine-based resin and coloring material in the composition It is a thermosetting resin composition that does not aggregate or settle, and can uniformly disperse fine particles.

The above-mentioned fluororesin fine powder coloring material dispersion of the sixth invention can be obtained, for example, by dispersing the fine powder of fluororesin, the compound represented by formula (I) and the coloring agent in a non-aqueous solvent. When used, within the range that does not impair the effect of the present invention, it can be dispersed using a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, or the like.

The equipment used for dispersion is the same as the fine powder dispersion or coloring material dispersion of the above-mentioned fluororesin, for example, a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, or a wet ball mill can be used , bead mill, wet jet mill and other dispersing machines, etc., to stir, mix and disperse to produce.

The above-mentioned fluororesin fine powder coloring material dispersion system contains both dispersions of fluororesin fine powder and coloring material, so it is difficult to simply adjust the average particle size, but it is better to use a filter or mesh to make the maximum particle size 10 μm or less. Because it can become a more stable dispersion.

In the 3rd invention to the 6th invention, by implementing the inventions of the 3rd invention to the 6th invention, etc., the fine powder of the fluorine-based resin and the coloring material can be obtained in the composition without aggregation or sedimentation, and can be Thermosetting resin composition with uniform fine particle dispersion.

Also, the above-mentioned 3rd invention to the 6th invention are those who use the above-mentioned non-aqueous solvent, but they can also be used in combination with other solvents or use other solvents, depending on the application of the thermosetting resin composition to be used (wiring boards containing circuit boards) , coating layer film, insulating material, etc.) choose the better one.

[Preparation of cured products, insulating materials, etc. obtained from the thermosetting resin compositions of the fluorine-containing resins of the third invention to the sixth invention]

The cured products, insulating materials, etc. obtained from the thermosetting resin compositions of the fluorine-containing resins of the third invention to the sixth invention can be obtained by the same thermosetting resin compositions as conventional epoxy resin compositions. According to the method, it can be molded and hardened to become a hardened product, an insulating material, etc. Molding method and hardening method can adopt the same method as conventional thermosetting resin composition such as epoxy resin composition, fluororesin fine powder, coloring material is dispersed by uniform fine particles, etc., colored by pigment or dye to impart concealment properties, optical properties, light-shielding properties or light reflection properties, creativity, etc., and can also be colored with excellent insulation, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc. Insulating materials such as cured products, thermosetting resin insulating films, etc.

The production method of thermosetting resin insulating film, for example, fine powder of fluorine-based resin is dispersed to produce predetermined coloring, such as black or white thermosetting resin, thermosetting resin film, thermosetting resin insulating material, in the case of thermosetting resin The thermosetting resin composition obtained above is coated on the surface of a base material and a base material for a thermosetting resin film to form a film (coating film), and the film is heat-treated to remove the solvent and then hardened. .

Usable substrates, for example, are not particularly limited in shape or material as long as they have a compact structure that does not substantially allow liquid or gas to pass through. Examples of suitable substrates include: , and the base material for film formation such as belts, molds, rollers, rollers, etc. known in itself, electronic parts or electric wires such as circuit boards whose surface is formed with a thermosetting resin film as an insulating protective film, and film formed on the surface Sliding components or products, forming a thermosetting resin film, forming a multilayer film or a film or copper foil when forming a copper-clad laminated substrate, etc.

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 The slot coating method itself is a known method.

Membranes, thin films, insulating materials, etc., made of a thermosetting resin composition coated on a substrate, for example, those that can be heated at a relatively low temperature such as room temperature or lower under reduced pressure or normal pressure method for defoaming.

A film or the like made of a thermosetting resin composition formed on a base material can be formed into a thermosetting resin, a thermosetting resin film, or a thermosetting resin insulating material by heat treatment to remove the solvent and undergo curing treatment.

Thermosetting resin, thermosetting resin film, and thermosetting resin insulating material are based on the application, and the thickness can be adjusted appropriately. For example, a thermosetting resin with a thickness of 0.1-200 μm, preferably 3-150 μm, and more preferably 5-130 μm can be used. Resin film, thin film.

Fine powder concentration of 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 , is not particularly limited, and is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and more preferably 10 to 35% by mass relative to the entire mass of the cured product obtained by curing the thermosetting resin composition of the present invention. %about. If the fine powder concentration of the fluororesin is too small, the effect of adding the fine powder of the fluororesin will not be effective, and if the concentration of the fine powder of the fluororesin is too high, the mechanical properties of the thermosetting resin will be reduced.

In addition, the concentration of the coloring material of the fluorine-based resin in the colored thermosetting resin insulating material such as the colored thermosetting resin insulating film is not particularly limited. , preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and more preferably about 5 to 20% by mass. If the concentration of the coloring material is too small, the effects of concealment, optical properties, light-shielding or light reflection, creativity, etc. cannot be exerted, and if the concentration of the coloring material is too high, the electrical properties and mechanical properties of the thermosetting resin will be reduced.

Colored thermosetting resin film obtained from the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention, 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, wherein the heat-resistant light weight white material, specifically, can be used as the base material of LED (light-emitting diode), organic EL light-emitting reflective material or metal layer white film, and can be suitably used in LED or organic EL or Flexible printed wiring substrates for mounting other light-emitting elements, etc.

In addition, black thermosetting resin materials such as black thermosetting resin films obtained from the thermosetting resin compositions of the third to sixth inventions described above are excellent in shielding properties, optical properties, and light-shielding properties in electronic parts or mounting parts to be protected. By.

<Adhesive composition for circuit boards of the third to sixth inventions>

The adhesive compositions for circuit boards of the third invention to the sixth invention are obtained by using the thermosetting resin compositions of the fluorine-containing resins of the third invention to the sixth invention, and may further contain cyanic acid dispersed in the aforementioned Rubber component in ester or epoxy resins.

The adhesive compositions for circuit boards of the third invention to the sixth invention must have sufficient flexibility (Flexible, hereinafter) in order to be used in the manufacture of flexible printed circuit boards in which wiring or substrates can be bent. Similarly), in order to complement such flexibility, it is preferable to further contain a rubber component in the above-mentioned adhesive composition for circuit boards.

The rubber components that can be used 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, denatured and modified polybutadiene rubber, etc., preferably EPDM rubber with an ethylene content of 10-40% by mass, or SBR, NBR, etc., especially EPDM rubber, which can lower the dielectric constant and dielectric loss coefficient of the resin composition, is preferable.

The content of these rubber components is preferably 1 to 80 parts by mass relative to 100 parts by mass of the aforementioned resin (cyanate resin or epoxy resin) from the viewpoint of exerting the effect of the present invention, adhesive force and heat resistance. It is 10-70 mass parts, More preferably, it is 20-60 mass parts.

The adhesive compositions for circuit boards of the third invention to the sixth invention can be composed of the above-mentioned third invention to the sixth invention. The compound represented by the formula (I), the coloring material, the resin composition made of cyanate resin or epoxy resin, etc. are produced by a usual method, preferably by dispersing the fluorine-based resin fine powder in the fourth invention In the method of adding coloring material and resin composition containing cyanate resin and/or epoxy resin and rubber components, and mixing them, in the fifth invention, the fluororesin fine powder dispersion and coloring material dispersion or coloring In the method of adding and mixing a resin composition containing cyanate resin and/or epoxy resin and rubber components to the material solution, in the fluororesin fine powder coloring material dispersion of the sixth invention, adding cyanate ester resin The resin composition of resin and/or epoxy resin and rubber component is mixed and manufactured.

Each of the adhesive compositions for circuit boards of the third invention to the sixth invention may further contain inorganic particles such as phosphorus-based flame retardants in order to supplement flame retardancy and the like. Inorganic particles such as these phosphorus-based flame retardants are 1 to 30 parts by mass, preferably 5 to 20 parts by mass, relative to 100 parts by mass of the aforementioned cyanate resin or epoxy resin.

In addition, in the adhesive compositions for circuit boards of the third invention to the sixth invention, in addition to the above-mentioned components, if necessary, an appropriate amount of a curing accelerator, an antifoaming agent, a colorant, and a phosphor other than the above-mentioned ones can be blended. , modifying agent, anti-discoloration agent, inorganic filler, silane coupling agent, light diffusing agent, thermally conductive filler and other conventionally known additives.

Hardening (reaction) accelerators other than the above, for example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)dec 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 esters, etc., zinc-based catalysts such as zinc octoate, acetylacetone such as aluminum, chromium, cobalt, and zirconium, etc. These hardening (reaction) accelerators can be used individually or in combination of 2 or more types.

The adhesive compositions for circuit boards of the third invention to the sixth invention can be molded and cured in the same way as conventional cyanate resin compositions and epoxy resin compositions to form cured products. The molding method and curing method can be the same as those of conventional cyanate resin and epoxy resin compositions. The adhesive composition for circuit boards of the present invention does not require any 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 laminates, moldings, adhesives, coating films, and thin films.

The adhesive compositions for circuit boards of the third invention to the sixth invention use fine powders of fluorine-based resins, and the coloring materials are stably and uniformly dispersed, colorless, non-uniform, and non-agglomerated, and are colored black, white, etc. The thermosetting resin composition can be used as an adhesive composition for circuit boards. Therefore, the dielectric constant and dielectric tangent are low, and it has excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy. It is suitable for circuit boards. The adhesive material can be used, for example, in the manufacture of circuit board laminates, coating films, prepregs, bonding sheets, etc. using it. The above-mentioned coating film, prepreg, adhesive film, etc. can be applied to circuit boards, such as flexible printed circuit boards (FPCB) of flexible metal foil laminates, and the adhesive for circuit boards of the present invention is used in the production of these In the case of the composition, it is possible to realize an adhesive composition for circuit boards with lower dielectric constant and dielectric tangent, and excellent properties such as adhesiveness, heat resistance, dimensional stability, and flame retardancy.

<The laminated board for circuit boards of the third invention to the sixth invention>

Each of the circuit board laminates of the third invention to the sixth invention is a circuit board laminate comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, The adhesive layer is characterized by being constituted by each of the adhesive compositions for circuit boards of the third invention to the sixth invention having the above-mentioned constitution.

Fig. 1 is a schematic cross-sectional view of a metal foil laminated board (FPCB) which will be an example of an embodiment of a laminated board for circuit boards according to the third invention to the sixth invention.

The circuit board laminate A of the present embodiment includes at least the metal foil 30 laminated on the insulating film 10, and the adhesive resin layer 20 between the insulating film 10 and the metal foil 30, the adhesive resin layer 20 It is composed (joined) of an adhesive composition for a circuit board that is colored black, white, etc. without color unevenness or aggregates of the above-mentioned structure.

Fig. 2 is a schematic cross-sectional view of a metal foil laminated board (FPCB) which will be another embodiment of the laminated board for circuit boards of the third invention to the sixth invention.

The circuit board laminate B of this embodiment replaces the single-sided structure shown in FIG. 1. As shown in FIG. For the adhesive resin layers 20, 20 between the insulating film 10 and the metal foils 30, 30, the adhesive resin layers 20, 20 are colored black, white, etc. with the above-mentioned colorless unevenness and no aggregates. The circuit board is formed (bonded) with an adhesive composition.

The insulating film 10 used in each of the circuit board laminates of the third invention to the sixth invention shown in Fig. 1 and Fig. 2 is not particularly limited as long as it has electrical insulation properties, and it can be used. Properties, mechanical strength and thermal expansion coefficient of similar metals.

The insulating film 10 that can be used is, for example, selected from polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN) , polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamide, polylactic acid, nylon, polyparabanic acid, polyether One or more types of films in which ether ketone (PEEK) is grouped are preferably polyimide (PI) films.

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

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

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

The above-mentioned metal foil 30 may be a metal foil having conductivity, for example, gold, silver, copper, stainless steel, nickel, aluminum, alloys thereof, and the like. Copper foil or stainless steel foil is suitably used from the viewpoints of conductivity, ease of handling, price, and the like. Copper foil can be used by any one manufactured by a rolling method or an electrolytic method.

The thickness of the metal foil considers the electrical conductivity, the interface adhesion with the insulating film, the flexibility of the laminate, the improvement of the bending resistance, or the viewpoint of easy formation of fine patterns during circuit processing, and the conductivity between the wiring. Depending on the point of view, etc., a better range can be set, for example, preferably within the range of 1-35 μm, more preferably within the range of 5-25 μm, and particularly preferably within the range of 8-20 μm.

In addition, for the metal foil used, the surface roughness Rz (ten-point average roughness) of the matte surface is preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and most preferably in the range of 0.2 to 2.0 in the range of μm.

The manufacture of the circuit board laminates (for example, FIG. 1 or FIG. 2 ) of the third invention to the sixth invention constituted in this way is, for example, by coating the circuit board of the invention having the above-mentioned configuration on the insulating film 10 Using the adhesive composition, after the adhesive resin layer 20 is formed, it is dried to make it in a semi-cured state, and then, the method of laminating the metal foil 30 on the adhesive resin layer 20 and performing thermocompression bonding (thermal lamination), It can produce circuit boards with low dielectric constant and dielectric tangent, and excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy, which are colorless and non-agglomerative, and can be colored black or white. laminate. At this time, by post-curing the flexible metal foil laminate, the adhesive resin layer 20 in a semi-cured state is completely cured, whereby the final flexible metal foil laminate can be obtained.

[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 the coating film has an adhesive layer formed on at least one side of the insulating film, and the adhesive layer is the third invention of the above-mentioned structure. The adhesive composition for each circuit board of the sixth invention.

Fig. 3 is a schematic cross-sectional view showing an example of an embodiment of the coating layer film of the present invention of the third invention to the sixth invention (and the seventh invention to the tenth invention described later).

The cover layer film C of this embodiment is used as a surface protection film for flexible printed wiring boards (FPC), etc., and the adhesive resin layer 50 is formed on the insulating film 40, and the adhesive resin layer 50 is bonded. There is a separator (peeling film) 60 such as paper or PET film as a protective layer. In addition, this separator (peeling film) 60 may be provided as necessary in consideration of workability, storage stability, and the like.

The insulating film 40 used is the same as the insulating film 10 used in the circuit board laminates of the 3rd invention to the 6th invention, and can be selected from polyimide (PI), liquid crystal polymer (LCP, etc.) for example. ), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE) , Polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, polyether ether ketone (PEEK) group of more than one type of film.

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

Especially when considering the heat resistance, dimensional stability, mechanical properties, etc. of the coating film, polyimide (PI) film is preferred, especially the polyimide film treated with low temperature plasma is used for the coating film better.

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

The above-mentioned adhesive resin layer 50 is formed (bonded) with the adhesive compositions for circuit boards of the third invention to the sixth invention having the above-mentioned structure, and its thickness depends on the interface adhesion with the insulating film and the adhesive strength From the viewpoint of etc., it is preferably 1 to 50 μm, more preferably 3 to 30 μm.

The covering layer films of the third invention to the sixth invention constituted in this way are used for the circuit boards of the third invention to the sixth invention in which the above-mentioned color unevenness and no aggregates are colored into black, white, etc. The adhesive composition is coated on the insulating film 40 using a comma coater, a reverse roll coater, etc. to form an adhesive layer, and it is dried to be in a semi-hardened state (the composition is dried). state or a part thereof, the state of undergoing a hardening reaction), and secondly, by laminating the separator (peeling film) 60 that becomes the above-mentioned protective layer, a low dielectric constant and a dielectric tangent can be produced, and it also has adhesiveness, heat resistance, Coating film with excellent characteristics such as dimensional stability and flame retardancy.

[The prepregs of the third invention to the sixth invention]

The prepreg according to the third invention to the sixth invention is characterized in that it is made of at least one type selected from carbon fiber, cellulose fiber, glass fiber, or aramid fiber. The structure formed by fibers is at least impregnated with each of the adhesive compositions for circuit boards of the third to sixth inventions of the third to sixth inventions, which are colorless, non-uniform, and non-agglomerated in the above-mentioned configuration and are colored black or white.

The prepregs of the third invention to the sixth invention can be used as constituent materials of multi-layer flexible printed wiring boards, etc., and are dust-free and low-fluidity prepregs, which can provide the above-mentioned adhesive composition impregnation. After the above-mentioned fibers are dried, a semi-hardened sheet or the like 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, and aramid-based fibers. 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 aramid fiber. Especially in order to minimize the dielectric constant and dielectric loss coefficient of the prepreg, use NE glass fibers with lower dielectric constant and dielectric loss coefficient (dielectric constant about 4.8) than other glass fibers. , The dielectric loss coefficient is about 0.0015) is better.

The thickness of the above-mentioned prepreg system is 15-500 μm. When used on circuit boards, a thinner thickness of 15-50 μm is better.

The prepreg system of the third invention to the sixth invention constituted in this way can provide a low dielectric constant and a low dielectric tangent by using it as an interlayer constituent material and an adhesive material of a multilayer flexible printed wiring board, etc., and It is a prepreg that has excellent characteristics such as adhesion, heat resistance, dimensional stability, and flame retardancy, and is colorless and non-uniform and has no aggregates that are colored into black, white, etc.

[The electronic equipment of the third invention to the sixth invention]

The electronic equipment of the third invention to the sixth invention is a thermosetting resin insulating material obtained by using the thermosetting resin composition of each fluorine-containing resin of the third invention to the sixth invention, and can be used, for example, in 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, TVs, home servers, thin displays, hard disks, printing Insulation materials for the main body or parts of various electronic equipment represented by watches and DVD devices.

The third to sixth inventions of the present invention are colored with pigments or dyes obtained from the thermosetting resin compositions of the fluorine-containing resins of the third to sixth inventions, even if concealment, optical properties, light-shielding properties or Functions such as light reflectivity and creativity, as well as electrical properties such as heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant, low dielectric tangent, excellent processability, colorless unevenness and no aggregation Cured products of thermosetting resin compositions colored black, white, etc., insulating materials, flexible printed wiring boards containing the above-mentioned circuit boards using adhesive compositions for circuit boards, coating films, electronic equipment, and Films and insulating materials using these thermosetting resin compositions are suitable for insulating films, interlayer insulating films for wiring boards, surface protection layers, sliding layers, release layers, fibers, filter materials, wire covering materials, bearings Various belts, tapes, hoses, etc., for coatings, heat insulation shafts, brackets, seamless belts, etc.

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

The polyimide precursor solution composition of the present invention is composed of the seventh invention to the tenth invention described below.

The seventh invention is characterized by at least comprising: fine powder of fluorine-based resin, the compound represented by the above formula (I), a coloring material, and a polyimide precursor solution, and the eighth invention is at least comprising: at least fluorine-based resin The micropowder, the compound represented by the above formula (I) and the fluororesin micropowder dispersion of the non-aqueous solvent; the coloring material; and the polyimide precursor solution; are characterized by the ninth invention. Fine powder of fluororesin, dispersion of fluororesin fine powder of compound represented by the above formula (I) and non-aqueous solvent; coloring material dispersion or coloring material solution containing at least coloring material and non-aqueous solvent; polyimide Precursor solution; as a feature, the tenth invention at least includes: a fluororesin micropowder coloring material dispersion containing at least fine powder of fluororesin, a compound represented by the above formula (I), a coloring material, and a non-aqueous solvent; And polyimide precursor solution; as the characteristic.

The composition of each polyimide precursor solution of the seventh invention to the tenth invention will be described in detail below. Also, the fine powder of fluororesin used in the seventh invention to the tenth invention, the compound represented by the above formula (I), the non-aqueous solvent, the coloring material, etc. are the same as those in the first invention or the third invention. In some cases, the description will be omitted, and in the case of different cases, they will be described in detail below.

[Seventh Invention: Polyimide Precursor Solution Composition]

The fine powder of fluorine-based resin used in the seventh invention can be used in the fine powder of fluorine-based resin described in detail in the above-mentioned first invention, and the preferred particle size of the fine powder of fluorine-based resin is the same as that of the first invention described above. Similarly, one can be appropriately selected according to the application, but in order to fully exert the stability of the polyimide precursor solution composition or the characteristics of the obtained polyimide, etc., the particle size is preferably small. The primary particle diameter of the fine powder of the fluororesin is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. In addition, the lower limit of the above-mentioned primary particle size is better, but it is preferably 0.05 μm or more and 0.3 μm or less in terms of manufacturability and cost.

The measuring method, measuring device, etc. of the primary particle diameter of the fine powder of fluororesin are the same as those of the above-mentioned first invention, so it is omitted.

Also, the fine powder of the fluororesin to be used is as described in detail in the above-mentioned first invention, and two or more kinds of different primary particle diameters may be mixed for use, or the average amount of the fine powder of the fluororesin in a dispersed state may be mixed. Two or more types of different particle diameters may be used as a mixture of fine powders of two or more types of fluorine-based resins having different primary particle diameters or average particle diameters. By using fine powders of two or more types of fluorine-based resins with different particle sizes, it is possible to adjust the viscosity, increase the filling rate, or control the surface state of polyimide, etc.

In addition, the fine powder of the fluorine-based resin may be subjected to various surface treatments as described in detail in the above-mentioned first invention.

In the seventh invention, the fine powder of the fluorine-based resin is preferably contained in an amount of 5 to 70% by mass, 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 fluorine-based resins cannot be sufficiently imparted to the final polyimide, etc., and when the content exceeds 70% by mass, the mechanical properties of the final polyimide, etc. The strength is extremely weak, etc., so it is unfavorable.

The compounds represented by the above-mentioned (I) used in the seventh invention can be those described in detail in the above-mentioned first invention, and have the structures of butyral group, acetyl group, and hydroxyl group. By changing the ratio of these three structures ( The ratios of l, m, and n) can control the solubility of non-aqueous solvents, the compatibility and chemical reactivity with polyimide precursor solutions, etc.

The content of the compound represented by the above (I) is preferably 0.01 to 30% by mass relative to the fine powder of the fluororesin. When the content of this compound is less than 0.01% by mass, the dispersion stability deteriorates and the fluorine-based fine powder tends to settle, while when it exceeds 30% by mass, the viscosity of the polyimide precursor solution becomes high, which is not preferable.

Moreover, when considering the characteristic of the obtained polyimide etc., it is more preferable that it is 0.01-5 mass %, and it is especially preferable that it is 0.01-2 mass %.

The coloring material used in the seventh invention may be at least one selected from the inorganic pigments, organic pigments, and dyes described in detail in the third invention.

Inorganic pigments, organic pigments, and dyes that can be used, as long as polyimide materials such as polyimide films, coating films, and flexible printed wiring boards have been colored in the past, and concealment, optical properties, and light-shielding properties are imparted. There are no special limitations when it is used for functions such as light reflectivity, creativity, etc., but it is preferable not to damage electrical properties such as insulation, low dielectric constant, and low dielectric tangent, and processability. From the viewpoint of more exerting the effects of the seventh invention, among the inorganic pigments and organic pigments described in detail in the third invention, at least one selected from carbon-based black pigments, oxide-based black pigments, and white pigments can be mentioned.

In the seventh invention, polyimide materials (polyimide film, polyimide insulating film, coating layer film, flexible printing film, etc.) For applications such as wiring boards), the optimum coloring material is selected as described above from the viewpoint of containing the coloring material so as to exert the desired shielding properties, light-shielding properties, or reflection characteristics.

In the seventh invention, the coloring material used is based on the application, concealment, optical Properties, light-shielding or light reflectivity, creativity, and other functions, etc., determine a more suitable amount, and never damage electrical properties such as insulation, low dielectric constant, and low dielectric tangent, processability, etc. From the viewpoint of the concealment, optical properties, light-shielding or light-reflecting properties, creativity and other functions that contain coloring materials, relative to the total solid content of the polyimide precursor solution composition, the lower limit is 0.1% by mass or more, more preferably 1% by mass or more, and the upper limit is 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of not impairing properties such as mechanical strength of the final polyimide or the like.

<Polyimide Precursor Solution>

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

Usable tetracarboxylic dianhydride and/or derivatives thereof include, for example, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2, 2'-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)pyridine dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, homo Pyrellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA ), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,6,7-naphthalene tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl ) ether dianhydride, ethylene tetracarboxylic dianhydride, ethylene glycol double dehydration trimellitate, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-two side oxygen -3-furyl)naphtho[1,2-c]furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Derivatives of acid dianhydrides include tetracarboxylic acids with the same skeleton as tetracarboxylic dianhydrides, acid chlorides of the tetracarboxylic acids, lower alcohols and esters of the tetracarboxylic acids with 1 to 4 carbon atoms, etc., which can be used separately Use or mix 2 or more types.

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

The content of the tetracarboxylic dianhydride and/or its derivatives can be changed according to the manufacturability, the use of polyimide, the required characteristics, and the like.

Diamine compounds that can be used include, for example, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyl Tetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-amine propoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine Amine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3 ,3'-diaminodiphenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 1, 5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenylenediamine, benzidine, 3,3'-dimethyl Benzidine, 3,3'-Dimethoxybenzidine, 4,4'-Diaminodiphenylphenyl, 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]pyridine, 2,4-bis(β-amino-third Butyl)toluene, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-6-aminophenyl)benzene, bis-p-(1,1- Dimethyl-5-amino-pentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, bis(p-amino Cyclohexyl)methane, 2,17-diaminoeicosane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 1, 12-diaminooctadecane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and the like can be used alone or in combination of two or more.

It is preferred to use 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 the diamine compound varies depending on the manufacturability, the use of the polyimide, the required properties, and the like.

The above-mentioned combination of tetracarboxylic dianhydride and/or its derivatives and diamine compound, preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 4,4' - Combinations of diaminodiphenyl ether (ODA), s-BPDA and p-phenylenediamine (PPD), etc.

Also, in the seventh invention, the non-aqueous solvent described in detail in the first invention can be used for the purpose of adjusting the viscosity of the polyimide precursor solution or the composition of the polyimide precursor solution.

Among the non-aqueous solvents, those that vary due to the material used or the use of polyimide are preferable, and acetaniline, dioxolane, o-cresol, m-cresol, p-cresol, etc. Cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, Gamma-butyrolactone, cyclobutane, halogenated phenols, xylene, acetone.

The content of the non-aqueous solvent used in the polyimide precursor solution used in the seventh invention is the remainder of the above-mentioned tetracarboxylic dianhydride and/or its derivatives and the above-mentioned diamine compound.

<7th Invention: Polyimide Precursor Solution Composition>

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

The polyimide precursor solution composition of the seventh invention is prepared by adding fine powder of fluororesin, the compound represented by the above formula (I) and the polyimide precursor solution of the coloring material in advance. Mixing in a certain amount can prevent the fine powder of fluororesin resin and coloring material from agglomerating or settling in the composition, and become a uniform dispersion of fine particles.

The preparation of the polyimide precursor solution used in the 7th invention can suitably adopt known methods or predetermined conditions, for example, it can be obtained by adding tetracarboxylic dicarboxylic acid in a predetermined composition ratio to a non-aqueous solvent. Anhydride and/or derivatives thereof and a diamine compound are prepared by stirring. The total concentration of tetracarboxylic dianhydride and/or its derivatives and diamine compound in the polyimide precursor solution can be set in accordance with various conditions, usually at the full amount of the reaction solution (full amount of the polyimide precursor solution ), preferably 5 to 30% by mass. The reaction conditions during such stirring are not particularly limited, but the reaction temperature is preferably set at 80°C or lower, especially 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, and when it is too high, problems such as imidization proceed. Also, the reaction time is preferably 1 to 100 hours.

Also, the composition of the polyimide precursor solution can be obtained 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, or a wet jet mill. Dispersing machines such as machines, etc., are produced by stirring, mixing, and dispersing.

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

The polyimide precursor solution composition of the seventh invention preferably has a moisture content of 5000 ppm or less [0≦moisture content≦5000 ppm] according to the Karl Fisher method. Considering the moisture incorporation of materials or in the manufacturing stage, by setting the moisture content of the final polyimide precursor solution composition to 5000ppm or less, it is possible to make fine powders of fluorine-based resins or coloring materials (pigments) It does not coagulate, can exist uniformly, and can obtain a polyimide precursor solution composition with better storage stability.

[The eighth invention: polyimide precursor solution composition]

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

The 8th invention, compared with the above-mentioned 7th invention, uses a fluorine-based resin fine-powder dispersion prepared in advance containing at least a fine powder of a fluorine-based resin, a compound represented by formula (I) and a non-aqueous solvent. Add a certain amount of coloring material to the above-mentioned polyimide precursor solution, and by mixing, etc., the fine powder of fluorine-based resin and coloring material can be obtained without aggregation or sedimentation in the composition, and uniform particle dispersion. Imide precursor solution composition.

The above-mentioned fluorine-based resin fine powder dispersion of the eighth invention can be obtained by using mixers such as dispersers, homogenizers, ultrasonic dispersers, three-roll mills, wet ball mills, bead mills, and wet jets. Dispersing machines such as mills, etc., are produced by stirring, mixing, and dispersing. In the dispersed state, the fine powder of fluororesin is obtained 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 μm or less. Usually, the primary particles aggregate to form a fine powder with a large particle size of the secondary particles. By dispersing the secondary particles of the fine powder of the fluororesin to a particle size of 10 μm or less, by using a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, or a wet ball mill , bead mill, wet jet mill, high-pressure homogenizer and other dispersing machines can be dispersed to obtain low viscosity and stable dispersions during long-term storage.

The average particle diameter is preferably at most 5 μm, more preferably at most 3 μm, and even more preferably at most 1 μm. become a more stable dispersion.

Also, in the polyimide precursor solution composition of the eighth invention, as with the polyimide precursor solution composition of the seventh invention, an interface can be used within the range that does not impair the effect of the present invention. Various additives such as active agents, dispersants, defoamers, etc., filler materials such as silica particles or acrylic particles, or elastomers, etc.

In addition, in the polyimide precursor solution composition of the eighth invention (including the ninth invention and the tenth invention described later), as in the polyimide precursor solution composition of the first invention described above, The moisture content according to the Karl Fisher method is preferably below 5000ppm [0≦moisture content≦5000ppm]. Considering the moisture incorporation of materials or in the manufacturing stage, by setting the moisture content of the final polyimide precursor solution composition to 5000ppm or less, it is possible to make fine powders of fluorine-based resins or coloring materials (pigments) It does not coagulate, can exist uniformly, and can obtain a polyimide precursor solution composition with better storage stability.

[The ninth invention: polyimide precursor solution composition]

The composition system of the polyimide precursor solution of the ninth invention at least includes: at least a fluororesin fine powder dispersion containing a fine powder of a fluororesin and a compound represented by formula (I) and the above-mentioned non-aqueous solvent; Coloring material dispersion or coloring material solution of coloring material and non-aqueous solvent; and polyimide precursor solution, the detailed description of the above-mentioned components is the same as the above-mentioned 1st invention, 7th invention, etc., so This description is omitted.

In the ninth invention, compared with the above-mentioned seventh and eighth inventions, a fluororesin fine powder dispersion containing at least fine powder of fluororesin, a compound represented by formula (I) and a non-aqueous solvent is prepared in advance; 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 a predetermined amount of the dispersion or solution to the above-mentioned polyimide precursor solution, mixing, etc., to obtain a fluorine-based resin The fine powder and coloring material will not aggregate or settle in the composition, and the polyimide precursor solution composition with uniform fine particle dispersion.

The above-mentioned coloring material dispersion of the ninth invention is obtained, for example, by dispersing an inorganic pigment or an organic pigment containing the above-mentioned carbon-based black pigment, oxide-based black pigment, white pigment, etc., in a non-aqueous solvent. Dispersion can be performed using a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, and the like within a range that does not impair the effects of the present invention.

The equipment used for dispersion is the same as the fine powder dispersion of the above-mentioned fluorine-based resin, for example, mixers such as dispersers and homogenizers, ultrasonic dispersers, three-roll mills, wet ball mills, bead mills, A disperser such as a wet jet mill etc. is used to stir, mix and disperse to produce.

The above-mentioned coloring material dispersion system is in the dispersed state, and the coloring material (pigment) is diffracted by dynamic light scattering or laser. The volume-based average particle diameter (50% volume diameter, median diameter) of the scattering method is preferably 3 μm or less. By dispersing the 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, Dispersion with dispersing machines such as wet jet mills and high-pressure homogenizers enables stable dispersions to be obtained even when stored at low viscosity for a long period of time.

The average particle size is preferably not more than 1 μm, more preferably not more than 0.5 μm, still more preferably not more than 0.3 μm. Because it can become a more stable dispersion.

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

The device used for dissolving, such as mixers such as dispersers and homogenizers, or ultrasonic irradiation devices, can be used for devices that can stir, mix, and dissolve. When using low-solubility coloring materials (dye) In this case, it is also possible to dissolve the non-aqueous solvent by heating, stirring, or the like. A precursor solution composition can be obtained.

[The tenth invention: polyimide precursor solution composition]

The polyimide precursor solution composition of the tenth invention is characterized in that it comprises at least: a fine powder containing at least a fluorine-based resin, a compound represented by formula (I), a coloring material, and a fluorine-based resin fine powder of the above-mentioned non-aqueous solvent. For the powder coloring material dispersion and the polyimide precursor solution, the detailed description of the above-mentioned components and the like is the same as that of the above-mentioned seventh invention, so the description is omitted.

When compared with the above-mentioned 7th, 8th, and 9th inventions, the 10th invention uses a fluorine-based resin micropowder containing at least a fine powder of a fluororesin, a compound represented by formula (I), a coloring agent, and a non-aqueous solvent in advance. Powder coloring material dispersion, by adding a certain amount of dispersion to the above polyimide precursor solution, mixing, etc., can obtain fine powder of fluorine-based resin and coloring material without aggregation or sedimentation in the composition , and a polyimide precursor solution composition such as uniformly dispersed fine particles.

The above-mentioned fluorine-based resin fine powder coloring material dispersion of the tenth invention is obtained, for example, by dispersing the fine powder of fluorine-based resin, the compound represented by formula (I) and the coloring agent in a non-aqueous solvent. In this case, a surfactant or dispersant, a pigment derivative (synergist), an antifoaming agent, etc. may be used for dispersion within the range that does not impair the effect of the present invention.

The equipment used for dispersion is the same as the fine powder dispersion or coloring material dispersion of the above-mentioned fluorine-based resin, for example, it can be obtained by using a mixer such as a disperser, a homogenizer, or an ultrasonic disperser, a three-roll mill, or a wet type. Dispersion machines such as ball mills, bead mills, wet jet mills, etc. are used to stir, mix, and disperse.

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

By carrying out the inventions of the seventh invention to the tenth invention, etc., it is possible to obtain a polyimide precursor in which the fine powder of the fluororesin and the coloring material do not aggregate or settle in the composition, and the fine particles are uniformly dispersed. The composition of the substance solution.

Also, the above-mentioned 7th invention to the 10th invention are those who use the above-mentioned non-aqueous solvent, but they can also be used in combination with other solvents or use other solvents, depending on the use of the polyimide used (wiring boards containing circuit boards, Covering layer film, insulating material, etc.) choose the better one.

[Preparation of polyimide, polyimide film, polyimide insulating film, etc. obtained from the polyimide precursor solution compositions of the seventh invention to the tenth invention]

The polyimide, polyimide film, polyimide insulating film, etc. of the seventh invention to the tenth invention are obtained by mixing the polyimide precursor solution of the seventh invention to the tenth invention prepared above. The polyimide precursor in the composition is imidized to disperse fluorine-based resins and coloring materials with uniform fine particles, etc., and then colored by pigments or dyes to impart concealment, optical properties, light-shielding properties or light reflection properties, Functions such as creativity, etc., can also obtain colored polyimide, polyimide film, polyimide, etc. with high insulation, heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc. Imide insulating film, coating layer film, flexible wiring board, etc.

In the 7th invention to the 10th invention, the production method of polyimide includes, for example, the preparation of a fine powder containing at least a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a non-aqueous solvent. The step of fluororesin micropowder coloring material dispersion; the step of mixing at least tetracarboxylic acid dihydrate and/or its derivatives and diamine compound to prepare polyimide precursor solution composition; mixing the fluororesin micropowder The step of making the polyimide precursor solution composition from the powder coloring material dispersion and the polyimide precursor solution composition; the polyimide is obtained by hardening the polyimide precursor solution composition The steps of the characteristic polyimide production method, and the production method of polyimide film, for example, include the same steps as the above-mentioned production method of polyimide, making polyimide precursor Solution composition, and by coating the polyimide precursor solution composition, hardening treatment, polyimide film production method characterized by the steps of obtaining a polyimide film, in addition, polyimide insulation The production method of the membrane includes, for example, the steps of preparing a polyimide precursor solution composition through the same steps as the above-mentioned polyimide production method, and by applying the polyimide precursor solution composition, A method of manufacturing a polyimide insulating film characterized by a step of performing a hardening treatment to obtain a polyimide insulating film. In addition, in each of the above-mentioned production methods, the hardening treatment (method of imidization) is not particularly limited, and a known method can be used.

For example, in the case of dispersing fluorine-based resins to produce predetermined coloring, for example, black or white polyimide, polyimide film, and polyimide insulating materials, it can be achieved by using polyimide substrates, polyimides, etc. The surface of the base material for the imide film is coated with the polyimide precursor solution composition obtained above to form a film (coating film), and the film is heat-treated to remove the solvent and perform hardening treatment ( imidization reaction).

Usable substrates, for example, are not particularly limited in shape or material as long as they have a compact structure that does not substantially allow liquid or gas to pass through. Examples of suitable substrates include: , and the film-forming base material itself is a known belt, mold, roller, roller, etc., electronic parts or wires such as a circuit board with a polyimide film as an insulating protective film formed on the surface, and a film formed on the surface Sliding parts or products, forming a thermosetting resin film, and forming a multilayer film or a film or copper foil when forming a copper laminated substrate.

In addition, as a method for applying the polyimide precursor solution 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 web coating method, etc., can be suitably used. The plate printing method, the slit coating method and the like are known methods per se.

Membranes, thin films, insulating materials, etc. formed by coating the polyimide precursor solution composition formed on the substrate, for example, can be processed under reduced pressure or normal pressure, below room temperature, etc. The method of heating at a relatively low temperature is used for defoaming.

The film formed by the polyimide precursor solution composition formed on the substrate is heat-treated to remove the solvent, and after hardening treatment (imidization), polyimide, Polyimide film, polyimide insulating material. Heat treatment Rather than heat treatment directly at high temperature, it is better to first remove the solvent at a relatively low temperature below 100~140°C, and then raise the temperature to the highest heat treatment temperature for imidization heat treatment. The maximum heat treatment temperature can be in the temperature range of 200-600°C, but it is preferably 300-500°C, more preferably 250-500°C for heat treatment. In addition, instead of the heat treatment, or in combination with the heat treatment, the imidization reaction may be performed using a catalyst such as an amine compound. In addition, carboxylic acid anhydride, etc. as a dehydrating agent for removing water generated during imidization may also be used.

Polyimide, polyimide film, and polyimide insulating material are used together, and their thickness can be adjusted appropriately. For example, the suitable thickness is 0.1~200μm, preferably 3~150μm, and more preferably 5~130μm Polyimide film and thin film. When the heating temperature is lower than 250° C., imidization does not proceed sufficiently, and when it exceeds 450° C., problems such as degradation of mechanical properties due to thermal decomposition or the like arise. Moreover, when the film thickness exceeds 200 μm, the solvent may not be sufficiently volatilized, the mechanical properties may be lowered, or problems such as foaming may occur during heat treatment.

Fluorine-based resins in colored polyimide films, colored polyimide films, colored polyimide insulating materials, etc. obtained from the polyimide precursor solution compositions of the seventh to tenth inventions above The fine powder concentration is not particularly limited, but it is preferably 5-70% by mass, more preferably 10-60% by mass, relative to the entire mass of the cured product after curing the polyimide precursor solution composition of the present invention, More preferably, it is about 10 to 35% by mass. If the concentration of fine powder of fluororesin is too small, the effect of adding the fine powder of fluororesin will not be effective, and if the concentration of fine powder of fluororesin is too high, the mechanical properties of polyimide will be reduced.

Also, the concentration of the coloring material of the fluorine-based resin in the colored polyimide insulating material such as the colored polyimide insulating film is not particularly limited, and the polyimide precursor solution composition of the present invention is hardened The overall mass of the subsequent cured product is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and more preferably about 5 to 20% by mass. If the concentration of the coloring material is too small, there will be no effects of concealment, optical properties, light-shielding or light reflection, and creativity. When the concentration of the coloring material is too high, the electrical and mechanical properties of polyimide will be reduced. .

A colored polyimide film obtained from each polyimide precursor solution composition of the seventh invention to the tenth invention, for example, a white polyimide film obtained by using a white pigment such as titanium oxide as a pigment, etc. White polyimide materials can be used as heat-resistant and lightweight white materials. Specifically, they can be used as reflective materials for LEDs (light-emitting diodes) and organic EL light, or as substrates for metal layer white films. It is suitable for assembling flexible printed wiring boards of LED or organic EL or other light-emitting elements.

In addition, the black polyimide film and other black polyimide materials obtained from the polyimide precursor solution compositions of the seventh invention to the tenth invention have shielding properties in electronic parts or mounting parts. , Optical properties, excellent light-shielding properties.

[Flexible printed wiring boards including circuit boards]

The flexible printed wiring board containing the circuit board of the seventh invention to the tenth invention uses the colored polyimide film obtained from the polyimide precursor solution composition of the seventh invention to the tenth invention. as a feature.

The flexible printed wiring board containing the circuit board of the present invention, such as a flexible printed circuit board (FPC), can be made of the above-mentioned polyimide by bonding an adhesive composition such as epoxy resin, cyanate resin, etc. The insulating polyimide film and metal foil obtained from the precursor solution composition are used to make a metal foil laminate (CCL), and a circuit is applied to the metal foil to manufacture.

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

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

The aforementioned metal foil includes a metal foil having conductivity, for example, gold, silver, copper, stainless steel, nickel, aluminum, alloys thereof, and the like. From the viewpoints of conductivity, ease of handling, price, etc., copper foil or stainless steel foil is preferably used. Copper foil can also use any one manufactured by the rolling method or the electrolytic method.

The thickness of the metal foil considers the electrical conductivity, the interface adhesion with the insulating film, the flexibility of the laminate, the improvement of the bending resistance, or the viewpoint of easy formation of fine patterns during circuit processing, and the conductivity between the wiring. Depending on the point of view, etc., a better range can be set, for example, preferably within the range of 1-35 μm, more preferably within the range of 5-25 μm, and particularly preferably within the range of 8-20 μm.

In addition, for the metal foil used, the surface roughness Rz (ten-point average roughness) of the matte surface is preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and most preferably in the range of 0.2 to 2.0 in the range of μm.

The flexible printed wiring board containing the circuit board of the 7th invention to the 10th invention thus constituted is obtained by using the polyimide precursor solution composition obtained from the above-mentioned 1st invention to the 4th invention. Imide film, as an insulating film, can be colored by pigment or dye, even if it is endowed with functions such as concealment, optical characteristics, light-shielding or light reflection, and creativity, it is also highly insulating, and has heat resistance, Flexible printed wiring boards including circuit boards with excellent electrical properties (low dielectric constant, low dielectric tangent) and processability.

〔Coating film〕

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

The adhesive layer used is an adhesive composition such as epoxy resin and cyanate resin used in the above-mentioned circuit board.

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

The thickness of the above-mentioned polyimide film can be selected within a preferable range in consideration of sufficient electrical insulation, protection, and flexibility, preferably 5-200 μm, more preferably 7-100 μm. The thickness of the aforementioned adhesive composition is preferably from 1 to 50 μm, more preferably from 3 to 30 μm, from the viewpoint of the interface adhesion with the insulating film, adhesive strength, and the like.

The covering layer film of the seventh invention to the tenth invention constituted in this way is formed on the polyimide film obtained by the polyimide precursor solution composition of the seventh invention to the tenth invention, and the two-roller is used. Coater, reverse roll coater, etc., to form an adhesive layer made of an adhesive composition by coating, and then dry it into a semi-hardened state (the state where the composition is dried or a part of it undergoes a hardening reaction), Next, by laminating the separator (peeling film) used as the above-mentioned protective layer, it is possible to manufacture a coating layer film having low dielectric constant and dielectric tangent, and excellent properties such as heat resistance, dimensional stability, and electrical characteristics.

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

The electronic equipment of the 7th invention to the 10th invention uses the polyimide insulating material obtained from the polyimide precursor solution composition of the 7th invention to the 10th invention, and can be used, for example, in applications requiring excellent performance. Various electronic devices with electrical properties (low dielectric constant, low dielectric tangent) and electrical insulation, such as thin mobile phones, game consoles, router devices, WDM devices, personal computers, TVs, home servers, thin displays, hard disks , printers, DVD devices as the main body or parts of various electronic equipment such as insulation materials.

In the present invention, the polyimide precursor solution composition obtained from the seventh invention to the tenth invention is colored with a pigment or a dye, even if it is given concealment, optical characteristics, light-shielding or light reflection, creativity, etc. The function is also heat resistance, mechanical properties, sliding properties, insulation, electrical properties such as low dielectric constant, low dielectric tangent, and polyimide or polyimide film with excellent processability. In addition to flexible printed wiring boards, coating films, and electronic equipment containing the above-mentioned circuit boards of imide insulating materials, polyimide or polyimide films and polyimide insulating materials using these can be suitable Various belts for insulating films, interlayer insulating films for wiring boards, surface protection layers, sliding layers, peeling layers, fibers, filter materials, wire covering materials, bearings, coatings, heat insulating shafts, brackets, seamless belts, etc. , adhesive tape, hose, etc.

[Example]

Hereinafter, the first invention to the tenth invention will be described in detail with reference to Examples and Comparative Examples. In addition, this 1st invention - this 10th invention are not limited to the following Examples etc.

[This first invention: Preparation of non-aqueous dispersion of fluororesin: Dispersion 1~4]

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

The average particle size of PTFE in dispersions 1 to 4 formed by the above blending numbers [1] to [4] (the average particle size analyzed by the cumulative method in the scattering intensity distribution) was measured by FPAR-1000 (Otsuka Electronics Co., Ltd. Co., Ltd.) dynamic light scattering method for measurement (refer to the following Table 2).

In addition, for dispersions 1 and 2 formed by blending numbers [1] to [4], add to blending number [5], stir and mix thoroughly to prepare dispersions 1 to 4.

Also, when the water content of the obtained dispersions 1 to 4 was measured, each water content by the Karl Fisher method was within the range of 800 to 1800 ppm, respectively.

The obtained dispersions 1 to 4 were stored in a closed container at 40°C for 1 week, and the sedimentation state of the particles was visually confirmed. There was no sedimentation, and they remained in a good state.

[Examples 1 and 2 and Comparative Examples 1 to 3: Preparation of thermosetting resin composition of fluorine-containing resin]

Using the obtained dispersions 1 to 4, a thermosetting resin composition of a fluorine-containing resin was produced with the blending recipe shown in Table 3 below. In addition, Comparative Example 3 was produced as a composition of only resin to which PTFE dispersion was not added.

After mixing with the blending ratio shown in Examples 1, 2 and Comparative Examples 1-3, use a disperser to stir and mix the PTFE dispersion and resins uniformly to obtain a thermosetting resin composition of fluorine-containing resin.

Here, the blending of any of Examples 1 and 2, and Comparative Examples 1 and 2 showed a very uniform state, and aggregates of PTFE were not observed.

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

Use an applicator to apply the thermosetting resin composition of fluorine-containing resin obtained in Examples 1, 2, and Comparative Examples 1 to 3 on the entire surface of one side of a polyimide film (thickness: 25 μm), and dry it The thickness was about 25 μm, and it became a uniform thickness, and after drying at about 120° C. for about 10 minutes, it was cured by heating at 180° C. for 60 minutes to prepare a sample for dielectric constant evaluation.

〔Evaluation of dielectric constant〕

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

〔Evaluation of Adhesion Strength〕

On the roughened surface of the copper foil (thickness 18μm) that has been roughened on one side, after covering the mesh with a thickness of 100μm as a spacer, the copper foil obtained in Examples 1, 2, and Comparative Examples 1~3 is coated. For the thermosetting resin composition of fluorine-containing resin, after drying the solvent at 50°C for 5 minutes, the roughened surface of the copper foil (thickness 18 μm) that has been roughened on one side is coated with the composition side, and then heated at 160 After lamination at 180° C., it was heated for 60 minutes to be cured, and a sample for adhesiveness evaluation was prepared.

The evaluation of the adhesion strength is to make a test piece cut into a width of 1 cm, and use a push/pull tester (Push/Pull) to perform T-peeling.

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

As shown in the above Table 4, the thermosetting resin cured products of the fluorine-containing resins of Examples 3 and 4 of the first invention show a lower dielectric constant than that of Comparative Example 6 that does not contain a fluorine-containing resin. , At the same time, compared with Comparative Examples 4 and 5 which do not contain urethane fine particles, it shows a result of higher adhesion strength.

[This second invention: Preparation of non-aqueous dispersion of fluororesin: Dispersion 5~8]

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

The average particle size of PTFE in dispersions 5-8 formed by the above-mentioned blending numbers [6]-[9] (the average particle size analyzed by the cumulative method in the scattering intensity distribution) was measured by FPAR-1000 (Otsuka Electronics Co., Ltd. Co., Ltd.) dynamic light scattering method for measurement (refer to the following Table 6).

In addition, for dispersions 5 and 6 formed by blending numbers [6] to [9], add them to blending numbers [10] and [11], stir and mix thoroughly to prepare dispersions 5 to 8.

Also, when the water content of the obtained dispersions 5 to 8 was measured, each water content by the Karl Fisher method was within the range of 800 to 1800 ppm, respectively.

The resulting dispersions 5 to 8 were stored in a closed container at 40°C for 1 week, and the sedimentation state of the particles was visually confirmed. There was no sedimentation, and they remained in a good state.

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

Using the obtained dispersions 5 to 8, a thermosetting resin composition of a fluorine-containing resin was produced with the blending recipe shown in Table 7 below. Also, Comparative Example 9 was produced as a composition of only resin to which no PTFE dispersion was added.

After mixing with the blending ratio shown in Examples 5, 6 and Comparative Examples 7-9, use a disperser to stir and mix the PTFE dispersion and resins uniformly to obtain a thermosetting resin composition of fluorine-containing resin.

Here, the blending of any one of Examples 5 and 6, and Comparative Examples 7 and 8 showed a very uniform state, and aggregates of PTFE were not observed.

[Examples 7 and 8 and Comparative Examples 10 to 12: Preparation of thermosetting resin cured product of fluorine-containing resin]

Use an applicator to apply the thermosetting resin composition of the fluorine-containing resin obtained in Examples 5, 6, and Comparative Examples 7 to 9 on the entire surface of one side of a polyimide film (thickness: 25 μm), and dry it The thickness was about 25 μm, and it became a uniform thickness, and after drying at about 120° C. for about 10 minutes, it was cured by heating at 180° C. for 60 minutes to prepare a sample for dielectric constant evaluation.

〔Evaluation of dielectric constant〕

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

〔Evaluation of Adhesion Strength〕

On the roughened surface of copper foil (thickness 18μm) that has been roughened on one side, after coating a mesh with a thickness of 100μm as a spacer, apply the fluorine-containing system obtained in Examples 5, 6, and Comparative Examples 7 to 9. The thermosetting resin composition of the resin, after drying the solvent at 50°C for 5 minutes, the roughened surface of the copper foil (thickness 18μm) that has been roughened on one side is covered with the composition side, and then carried out at 160°C After lamination, it heated and hardened at 180 degreeC for 60 minutes, and produced the sample for adhesiveness evaluation.

The evaluation of the adhesion strength is to make a test piece cut into a width of 1 cm, and use a push/pull tester (Push/Pull) to perform T-peeling.

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

As shown in the above Table 8, the thermosetting resin cured products of the fluorine-containing resins of Examples 7 and 8 of the second invention show a lower dielectric constant than that of Comparative Example 9 that does not contain a fluorine-containing resin. , and compared with Comparative Examples 7 and 8 that do not contain thermoplastic elastomers, it shows a result of higher adhesion strength.

[The third invention to the sixth invention: preparation of fluororesin fine powder dispersion, fluororesin fine powder coloring material dispersion, and coloring material dispersion]

The fluorine-based resin fine powder dispersion and the fluorine-based resin micro-powder dispersion used in the examples and comparative examples used in the third invention to the sixth invention were prepared by the preparation methods shown below. Powder coloring material dispersion, coloring material dispersion.

(Preparation of Fluorine Resin Fine Powder Dispersion)

With the blending recipe shown in the following Table 9, in the non-aqueous solvent, the compound represented by formula (I) was fully stirred and mixed and dissolved, then PTFE fine powder as fine powder of fluororesin was added, and further stirred and mixed. Then, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare fluororesin fine powder dispersion A.

(Preparation of fluororesin micropowder coloring material dispersion)

With the blending recipe shown in Table 10 below, in a non-aqueous solvent, the compound represented by formula (I) is fully stirred, mixed and dissolved, then PTFE fine powder as a fine powder of fluororesin is added, and PTFE fine powder as a coloring material is added. After black paint or white paint, further stir and mix. Then, the obtained PTFE+pigment mixed solution was dispersed with 0.3 mm diameter zirconia beads using a horizontal bead mill to prepare pigment-containing fluororesin fine powder coloring material dispersions B and C.

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

(Preparation of coloring material dispersion)

Following the blending recipe shown in Table 11, in a non-aqueous solvent, the compound represented by formula (I) was fully stirred and dissolved, and after adding a black pigment or a white pigment as a coloring material, further stirred and mixed. Then, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare coloring material dispersions D and E.

[Examples 9-18 and Comparative Examples 13-18: Preparation of Thermosetting Resin Composition]

Use the fluororesin fine powder dispersion prepared above, the fluororesin fine powder coloring material dispersion, and the coloring material dispersion to mix with the blending recipe shown in Table 12 below, and then fully stir with a disperser to obtain each heat Hardened resin composition.

For each obtained thermosetting resin composition, the settling properties and redispersibility were evaluated by the following evaluation methods.

The results are shown in Table 12 below.

(Evaluation method of sedimentation and redispersibility)

For each thermosetting resin composition, the sedimentation state of each particle (fluororesin fine powder, pigment particle) was left to stand at room temperature (25°C) for 30 minutes, then visually confirmed, and the following evaluation criteria were used, Sensory evaluation was performed on each state of sedimentation property and redispersibility.

Settling evaluation criteria:

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

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

×: The sedimentation layer can be seen in the lower part (difficult to redisperse)

Evaluation criteria for redispersibility:

○: The sediment is easy to redisperse when 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 within the scope 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 redisperse, and there is no problem with usability.

In contrast, among Comparative Examples 13 to 15, Comparative Examples 13 and 14 are ordinary thermosetting resin compositions that do not contain fluorine-based resin fine powder and coloring material (pigment), and there is no evaluation of sedimentation and redispersibility. , Comparative Examples 15-18 are thermosetting resin compositions containing coloring materials (black pigments, white pigments) that do not contain fluorine-based resin fine powder.

In addition, when the water content of each of the thermosetting resin compositions obtained in Examples 9-18 and Comparative Examples 13-18 was measured, the water content by the Karl Fisher method was respectively in the range of 800-2500 ppm.

[Examples 19-28, Comparative Examples 19-24: Evaluation of insulating material composition]

The thermosetting resin composition obtained in Examples 9-18 and Comparative Examples 13-18 was used as an insulating material composition, and was applied on one side of a polyimide film (thickness: 25 μm) with an applicator and dried. Afterwards, the thickness becomes about 25 μm, which becomes a uniform thickness. After drying at about 120° C. for about 10 minutes, it is cured by heating at 180° C. for 60 minutes, and an evaluation sample of the cured insulating material composition is produced.

(Evaluation of electrical characteristics)

According to the test specification of JIS C6481-1996, the dielectric constant of the obtained evaluation sample was measured at 1 GHz using an impedance analyzer (Impedence Analyzer). In addition, 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 the above Table 13, even if carbon black as a black pigment is contained, the evaluation samples of the insulating material compositions in Examples 19, 21, 23, 24, 26 and 28 after hardening are more stable than those without the pigment. In Examples 13 and 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 if titanium oxide is contained, the evaluation samples of the insulating material compositions in Examples 21, 23, 26, and 28 after hardening are found to have lower dielectric constants than Comparative Examples 21, 23.

[Evaluation of adhesive compositions for circuit boards]

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

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

Use an applicator to apply the adhesive compositions for circuit boards obtained in Examples 9 to 18 and Comparative Examples 13 to 18 on the entire surface of one side of a polyimide film (thickness: 25 μm), so that the thickness after drying becomes About 10μm, and become a uniform thickness, after forming the adhesive resin layer, it is dried to form a semi-hardened state. Then, the same adhesive resin layer was formed on the opposite side of the aforementioned polyimide film to produce an adhesive sheet.

Next, after laminating copper foil (thickness: about 12 μm, roughness (Rz) of matte surface: 1.6 μm) on both sides of the above-mentioned adhesive sheet, it is crimped at 170°C with a pressure of 40kgf/cm ² . After curing at 170° C. for 5 hours, a laminated board for circuit boards was manufactured.

The circuit board laminates obtained in 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)

Use an applicator to apply the adhesive compositions for circuit boards obtained in Examples 9 to 18 and Comparative Examples 13 to 18 on the entire surface of one side of a polyimide film (thickness: 25 μm), so that the thickness after drying becomes About 25 μm, and become a uniform thickness, after about 10 minutes of drying at about 120° C., a release paper with a thickness of 125 μm that has been released and coated is laminated to produce a coating layer film.

After the coating layer films of Examples 39-48 and Comparative Examples 31-36 were laminated in the order of the polyimide film of the coating layer film/the bonding surface of the coating layer film/copper foil (12 μm), this was laminated at 180 ℃, 40kgf/cm ² pressure, hot pressing for 60 minutes, and make evaluation samples.

(Evaluation of electrical characteristics)

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

(Evaluation method of heat resistance)

Adjust the sample size of 50mm×50mm, after 120°C, 0.22MPa, 12 hours of moisture absorption treatment, then treat it at 260°C for 1 minute, and observe the state of the sample with the naked eye. Evaluation criteria were "○" when there was no abnormality such as peeling, deformation, and swelling, and "×" when there was abnormality such as peeling, deformation, and swelling.

(Evaluation method of bonding strength)

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

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

〔Evaluation of prepreg〕 (Examples 49-58, Comparative Examples 37-42: Prepreg)

NE glass cloth with a thickness of about 100 μm is impregnated with the adhesive compositions for circuit boards obtained in Examples 9-18 and Comparative Examples 13-18, and then dried at about 120°C for about 10 minutes to produce an overall thickness of 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 ℃, 40kgf/cm ² pressure, hot pressing for 60 minutes, and make evaluation samples.

(Evaluation of electrical characteristics)

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

(Evaluation method of heat resistance)

Adjust the sample size of 50mm×50mm, after 120°C, 0.22MPa, 12 hours of moisture absorption treatment, then treat it at 260°C for 1 minute, and observe the state of the sample with the naked eye. Evaluation criteria were "○" when there was no abnormality such as peeling, deformation, and swelling, and "×" when there was abnormality such as peeling, deformation, and swelling.

(Evaluation method of bonding strength)

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

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

As shown in the above Tables 14 and 15, the laminates for circuit boards of Examples 29 to 38 using the thermosetting resin compositions of Examples 9 to 18 as the adhesive composition for circuit boards are the same as those of Examples 39 to 48. Although the coating layer film is colored black or white, compared with the thermosetting resin compositions of Comparative Examples 13 to 18, the circuit board laminates of Comparative Examples 25 to 30 used as the adhesive composition for circuit boards and Comparative Example 31 ~36 coating layer film, it is known that the dielectric constant is low, and the heat resistance or adhesiveness is the same.

Also, as shown in Table 16 above, the prepregs of Examples 49 to 58 using the thermosetting resin compositions of Examples 9 to 18 were colored black or white, compared to those using the thermosetting resin compositions of Comparative Examples 13 to 18. The prepregs of comparative examples 37 to 42, which were cured resin compositions, were found to have lower dielectric constants and equivalent heat resistance and adhesiveness.

[The 7th invention to the 10th invention: preparation of fluororesin fine powder dispersion, coloring material dispersion, and polyimide precursor solution]

The fluorine-based resin fine powder dispersions used in the polyimide precursor solution compositions of the examples and comparative examples used in the seventh invention to the tenth invention were prepared by the following preparation methods , Fluorine resin fine powder coloring material dispersion, coloring material dispersion, polyimide precursor solution.

(Preparation of Fluorine Resin Fine Powder Dispersion)

With the blending recipe shown in the following Table 17, in the non-aqueous solvent, the compound represented by formula (I) was fully stirred and mixed and dissolved, then PTFE fine powder as fine powder of fluororesin was added, and further stirred and mixed. Then, the obtained PTFE mixed solution was dispersed with zirconia beads with a diameter of 0.3 mm using a horizontal bead mill to prepare fluororesin fine powder dispersion A.

(Preparation of fluororesin micropowder coloring material dispersion)

According to the blending recipe shown in the following Table 18, in a non-aqueous solvent, the compound represented by formula (I) is fully stirred and mixed and dissolved, then PTFE fine powder as a fine powder of fluororesin is added, and PTFE fine powder as a coloring material is added. After black paint or white paint, further stir and mix. Then, the obtained PTFE+pigment mixed solution was dispersed with 0.3 mm diameter zirconia beads using a horizontal bead mill to prepare pigment-containing fluororesin fine powder coloring material dispersions B and C.

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

(Preparation of coloring material dispersion)

Following the blending recipe shown in Table 19, in the non-aqueous solvent, the compound represented by the formula (I) was fully stirred and dissolved, and after adding the black pigment or white pigment as the coloring material, the mixture was further stirred and mixed. Then, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare coloring material dispersions D and E.

(Preparation of Polyimide Precursor Solution)

In a glass container equipped with a stirrer and nitrogen piping, add 400 parts by mass of N,N-dimethylformamide, 27 parts by mass of p-phenylenediamine, 3,3',4,4'-biphenyl tetra After 73 parts by mass of carboxylic acid dihydrate, the mixture was sufficiently stirred to obtain a polyimide precursor solution having a solid content concentration of 18% by mass.

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

After mixing the fluororesin micropowder dispersion, fluororesin micropowder coloring material dispersion, coloring material dispersion, and polyimide precursor solution prepared above with the blending recipe shown in Table 20, fully Stir with a disperser to obtain each polyimide precursor solution composition.

For each obtained polyimide precursor solution composition, the settling properties and redispersibility were evaluated by the following evaluation methods.

These results are shown in Table 20 below.

(Evaluation method of sedimentation and redispersibility)

For each polyimide precursor solution composition, the sedimentation state of various particles (fluororesin fine powder, pigment particles) was left to stand at room temperature (25°C) for 30 minutes, then visually confirmed, and the following For each evaluation standard, a sensory evaluation was performed for each state of sedimentation property and redispersibility.

Settling evaluation criteria:

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

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

×: The sedimentation layer can be seen in the lower part (difficult to redisperse)

Evaluation criteria for redispersibility:

○: The sediment is easy to redisperse when stirring

×: The sediment is not easy to redisperse when stirring

From the results in Table 20 above, it can be seen that among Examples 59-63 in the scope of the seventh invention to the tenth invention, Examples 60 and 62 using titanium oxide, although some sediments are seen, are all easy to redisperse. There is no problem with usability, etc.

On the other hand, among Comparative Examples 43 to 45, Comparative Example 43 is a general polyimide precursor solution (composition) that does not contain fluorine-based resin fine powder and coloring material (pigment), and has no sedimentation and redispersibility In addition, Comparative Examples 44 and 45 are polyimide precursor solution compositions containing a coloring material (pigment) that does not contain fluororesin fine powder.

Also, when the moisture content of each polyimide precursor solution composition obtained in Examples 59 to 63 and Comparative Examples 43 to 45 was measured, the moisture content by the Karl Fisher method was between 800 and 3000 ppm respectively. within range.

(Preparation of polyimide film/polyimide film)

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

For each obtained polyimide film, 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 polyimide film was observed visually, and the state was sensory evaluated according to the following evaluation criteria.

Evaluation criteria:

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

×: Foreign matter such as PTFE condensation was confirmed

(Measuring method of dielectric constant of polyimide film)

According to the test specification of JIS C6481-1996, the dielectric constant of each obtained polyimide film was measured at 25° C. and 1 GHz using an impedance analyzer (Impedence Analyzer).

(Measuring method of volume resistivity of polyimide film)

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

From the results in Table 21 above, it can be seen that Examples 59-63 have the same dielectric constant as Comparative Example 43 which is made of only polyimide. On the other hand, although Comparative Examples 44 and 45 increased the dielectric constant, it was confirmed that Examples 59 to 63 were equivalent or suppressed the increase.

[Industrial availability]

The non-aqueous dispersion system of the fluorine-based resin of the first invention and the second invention has a particle size, low viscosity, excellent storage stability, and is suitable for mixing with various resin materials, and the non-aqueous dispersion of the fluorine-based resin of the present invention is used The thermosetting resin composition of the fluorine-containing resin and its cured product achieve low dielectric constant and low dielectric tangent, and can suppress the reduction of adhesion strength and bonding strength, so it can be applied to the insulating layer of multilayer printed wiring boards, Adhesives for circuit boards, laminates for circuit boards, coating films, prepregs, etc.

In the thermosetting resin composition of the fluorine-containing resin of the third invention to the sixth invention, the non-aqueous dispersion system of the fluorine-based resin is colored by a coloring material of an organic pigment, an inorganic pigment, or a dye, even if it is given concealment, Functions such as optical properties, light-shielding properties or light reflectivity, creativity, etc., can also obtain high insulation, and excellent heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc. Colored heat Curing resin compositions, etc., and thermosetting resins that can be suitably used for flexible printed wiring boards containing circuit boards, coating films, insulating films, and related insulating films for wiring boards using the thermosetting resin composition Composition insulating materials for electronic equipment, surface protection layers, sliding layers, peeling layers, fibers, filter materials, wire covering materials, bearings, coatings, heat insulating shafts, Various belts, tapes, hoses, etc. for brackets, seamless belts, etc.

In the polyimide precursor solution composition of the seventh invention to the tenth invention, the non-aqueous dispersion system of the fluorine-based resin is colored by an organic pigment, an inorganic pigment, or a coloring material of a dye, even if it is given concealment, optical Properties, light-shielding or light reflectivity, creativity, etc., can also obtain high insulation, and excellent heat resistance, electrical properties (low dielectric constant, low dielectric tangent), processability, etc. Colored polyamide imide, polyimide film, etc., and flexible printed wiring boards containing circuit boards, coating films, or insulating films and wiring boards using the polyimide or polyimide film Electronic equipment using polyimide insulating materials such as related insulating films, and polyimide, polyimide film, surface protection layer, sliding layer, peeling layer, fiber of polyimide insulating materials using the same Various belts, tapes, hoses, filter materials, wire covering materials, bearings, coatings, heat insulation shafts, brackets, seamless belts, etc.

10‧‧‧Insulating film

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

30‧‧‧Metal foil

Claims (10)

A non-aqueous dispersion of fluorine-based resin, which contains at least: 5-70% by mass of fine powder of fluorine-based resin relative to the total amount of the non-aqueous dispersion, and 0.1 The urethane fine particles of ~20% by mass contain 0.1-20% by mass of a compound represented by the following formula (I) and a non-aqueous solvent relative to the mass of the fine powder of the aforementioned fluorine-based resin. The moisture content of Xuefa is less than 8000ppm, and the average particle size of the aforementioned urethane particles is less than 10μm.

[In the above formula (I), l, m, and n are positive integers]. A non-aqueous dispersion of fluorine-based resin, which contains at least: 5-70% by mass of fine powder of fluorine-based resin relative to the total amount of the non-aqueous dispersion, and 0.1 ~100% by mass of thermoplastic elastomer, relative to the mass of the fine powder of the aforementioned fluorine-based resin, containing 0.1-20% by mass of a compound represented by the following formula (I) and a non-aqueous solvent, by the Karl Fisher method The moisture content is below 8000ppm,

[In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition of a fluorine-containing resin, which comprises at least: a fine powder of a fluorine-based resin containing 5 to 70% by mass relative to the total solid content, and, relative to the mass of the fine powder of the aforementioned fluorine-based resin, 0.01~30% by mass of a compound represented by the following formula (I), a coloring material selected from inorganic pigments, organic pigments and dyes, and a resin composition containing cyanate resin and/or epoxy resin, by Carl The moisture content of the Fisher method is less than 8000ppm, and the primary particle size of the inorganic pigment and organic pigment is less than 1μm,

[In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition of a fluorine-containing resin, comprising at least: a fine powder of a fluorine-based resin containing at least 5 to 70% by mass relative to the total solid content, and a mass of the fine powder of the aforementioned fluorine-based resin , containing 0.01 to 30% by mass of a compound represented by the following formula (I) and a fluororesin fine powder dispersion of a non-aqueous solvent; a coloring material selected from inorganic pigments, organic pigments and dyes; and containing cyanate resin and /or resin composition of epoxy resin; the water content by the Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment is 1μm or less,

[In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition of a fluorine-containing resin, comprising at least: a fine powder of a fluorine-based resin containing at least 5 to 70% by mass relative to the total solid content, and a mass of the fine powder of the aforementioned fluorine-based resin , containing 0.01 to 30% by mass of a compound represented by the following formula (I) and a fluorine-based resin fine powder dispersion; containing at least a coloring material selected from inorganic pigments, organic pigments and dyes, and a non-aqueous solvent Material dispersion or coloring material solution; and resin composition containing cyanate resin and/or epoxy resin; the water content by Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment 1 μm or less,

[In the above formula (I), l, m, and n are positive integers]. A thermosetting resin composition of a fluorine-containing resin, comprising at least: a fine powder of a fluorine-based resin containing at least 5 to 70% by mass relative to the total solid content, and a mass of the fine powder of the aforementioned fluorine-based resin , containing 0.1 to 20% by mass of a compound represented by the following formula (I), a coloring material selected from inorganic pigments, organic pigments and dyes, and a fluororesin micropowder coloring material dispersion of a non-aqueous solvent; and containing cyanate Resin composition of resin and/or epoxy resin; the water content by Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment is 1μm or less,

[In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least 5-70% by mass of fine powder of fluorine-based resin relative to the total solid content, and 0.01- 30% by mass of a compound represented by the following formula (I), a coloring material selected from inorganic pigments, organic pigments and dyes, and a polyamide sub-cavity precursor solution, the moisture content by the Karl Fisher method is 8000ppm or less, and The primary particle size of the inorganic pigment and organic pigment is 1 μm or less,

[In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least: a fine powder containing at least 5 to 70% by mass of a fluorine-based resin relative to the total solid content, the mass of the fine powder of the aforementioned fluorine-based resin, A fluororesin fine powder dispersion containing 0.01 to 30% by mass of a compound represented by the following formula (I) and a non-aqueous solvent; a coloring material selected from inorganic pigments, organic pigments, and dyes; and a polyimide precursor solution , the water content by the Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment is 1μm or less,

[In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least: a fine powder containing at least 5 to 70% by mass of a fluorine-based resin relative to the total solid content, the mass of the fine powder of the aforementioned fluorine-based resin, A fluororesin fine powder dispersion containing 0.01 to 30% by mass of a compound represented by the following formula (I) and a non-aqueous solvent; a coloring material containing at least a coloring material selected from inorganic pigments, organic pigments, and dyes, and a non-aqueous solvent Dispersion or coloring material solution; and polyimide precursor solution; the water content by Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment is 1 μm or less,

[In the above formula (I), l, m, and n are positive integers]. A polyimide precursor solution composition comprising at least: a fine powder containing at least 5 to 70% by mass of a fluorine-based resin relative to the total solid content, the mass of the fine powder of the aforementioned fluorine-based resin, A fluororesin micropowder coloring material dispersion containing 0.01 to 30% by mass of a compound represented by the following formula (I), a coloring material selected from inorganic pigments, organic pigments, and dyes, and a non-aqueous solvent; and a polyimide precursor solution; the water content by the Karl Fisher method is 8000ppm or less, and the primary particle size of the inorganic pigment and organic pigment is 1μm or less,

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

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