JP6835497B2 - Thermosetting resin composition, insulating material composition using it - Google Patents

Description

The present invention relates to a thermostable resin composition and an insulating material composition using the same, and more specifically, it is colored with a pigment or a dye and has functions such as hiding property, optical property, light shielding property, light reflectivity, and design property. A colored thermocurable resin composition that has high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric adjunct), workability, etc., and an insulating material composition using the same. The present invention relates to an adhesive composition for a circuit board, a heat-curable resin composition suitable for a laminated board for a circuit board, a coverlay film, a prepreg, a flexible wiring board, and the like, and an insulating material composition using the same.

In recent years, as electronic devices have become faster and more sophisticated, there is a demand for higher communication speeds. Under these circumstances, low dielectric constants and low dielectric loss tangents of various electronic device materials are required, and in particular, low dielectric constants and low dielectric loss tangents of insulating materials and substrate materials are required.

Thermosetting resin compositions using epoxy resins, cyanate ester resins, and the like have been widely used in electrical and electronic applications because they are excellent in heat resistance, electrical insulation, adhesiveness, and the like.
Usually, a thermocurable resin composition using an epoxy resin, a cyanate ester resin, or the like, a cured product thereof, etc. are suitably used for an electronic substrate material, an insulating material, an adhesive material, and the like, and are used, for example, for electronic parts. As a material for encapsulants, copper-clad laminates, insulating paints, composite materials, insulating adhesives, etc., an adhesive composition for circuit boards used in the manufacture of circuit boards, and laminations for circuit boards using the same. It is used as an insulating layer for boards, coverlay films, prepregs, and multilayer printed wiring boards for electronic devices.

These thermosetting resin compositions and insulating materials using them are white, black, or other colored materials in order to impart other functions such as concealing property, optical property, light shielding property, light reflecting property, and design property. There is a need to be colored and used in.
For example, component parts used for installation locations of high-voltage electrical and electronic parts and multi-layer printed wiring boards used for applications such as semiconductor mounting packages are mainly based on black, so they are based on black. A thermosetting resin composition is used. Further, the white thermocurable resin composition or the like is used as a base material for a printed wiring board on which a light emitting element such as an LED (light emitting diode) is mounted, a reflector for the light emitting element, a reflector for organic EL light emission, or a metal layer white film. It is used and the demand is increasing year by year.

Examples of these thermosetting resin compositions colored in white, black, etc., and insulating material compositions using the same include, for example.
1) An acid anhydride-curable epoxy resin composition containing an acid anhydride containing an inorganic filler and a curing accelerator as an agent A and an epoxy resin as an agent B, and the agent B is colored with a quinacridone structure. An epoxy resin composition characterized by blending an agent and a diazo dye, a high-pressure electrical and electronic component obtained by curing the epoxy resin composition (see, for example, Patent Document 1).
2) A step of dissolving and / or dispersing (B) a colorant in a dispersion liquid in which (A) an inorganic filler is dispersed in a solvent in order to provide a prepreg without color unevenness or agglomerates or an insulating resin sheet (A). A method for producing a resin composition (see, for example, Patent Document 2), which comprises 1) followed by (C) a step (2) of dissolving a novolak type epoxy resin.
3) A white curable resin composition having high reflectance and suppressed deterioration of reflectance due to aging and coloring due to deterioration, and a printed wiring board on which a light emitting element such as an LED is mounted, and reflection for a light emitting element. In order to provide a white curable resin composition capable of efficiently utilizing light from an LED or the like when used for a plate, it contains (A) rutile type titanium oxide and (B) a thermosetting resin. White thermosetting resin composition (see, for example, Patent Document 3),
4) A thermosetting resin composition for light reflection having sufficient light reflectance and molding processability and excellent heat-resistant coloring, a substrate for mounting an optical semiconductor device using the same, a method for manufacturing the same, and light. A thermosetting resin composition for light reflection (see, for example, Patent Document 4), which comprises an epoxy resin having specific physical properties, a curing agent, and a white pigment in order to provide a semiconductor device.
5) Excellent insulation and heat resistance, surface flatness, adhesion, and curability can be achieved at a high level in a well-balanced manner, and both high-temperature insulation resistance and solvent resistance required during the manufacturing process are excellent. In order to provide a thermosetting resin composition, a cured product thereof, and a display member using the same, (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, and (c) A thermosetting resin composition comprising a black colorant such as carbon black and (d) at least one selected from the group consisting of barium sulfate, silica and talc (see, for example, Patent Document 5). Etc. are known.

However, when the thermosetting resin compositions described in Patent Documents 1 to 5 are colored with a coloring material such as an organic pigment or an inorganic pigment, the cured product, an insulating material, a coverlay film or a flexible printed wiring board There is a problem in affecting the electrical characteristics (relative permittivity, dielectric loss tangent) and insulating properties of.
In particular, if carbon black is used to color black, not only the insulating property is lowered, but also the relative permittivity and dielectric loss tangent are deteriorated, which makes it unsuitable for applications such as high-speed communication and high-speed processing. There are challenges.
Therefore, colored thermosetting resin compositions and the like still have technical problems and limitations in electrical properties (low dielectric constant, low dielectric adjunct) and insulating properties, such as hiding properties, optical properties, and light-shielding properties. Thermosetting resin composition with functions such as light reflectivity and designability, and further improved electrical characteristics (low dielectric constant, low dielectric adjunct) and insulating properties, insulating material composition using it, for circuit boards At present, there is a demand for adhesive compositions, laminated boards for circuit boards, coverlay films, prepregs, flexible wiring boards, and the like.

Japanese Unexamined Patent Publication No. 2001-294728 (Claims, Examples, etc.) JP-A-2009-114377 (Claims, Examples, etc.) JP-A-2010-275561 (Claims, Examples, etc.) Japanese Unexamined Patent Publication No. 2013-155344 (Claims, Examples, etc.) JP-A-2015-78290 (Claims, Examples, etc.)

The present invention is intended to solve the above-mentioned conventional problems and the current situation, and is colored by a pigment or dye to have other properties such as hiding property, optical property, light shielding property, light reflecting property, and design property. A colored thermocurable resin composition that has high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric adjunct), workability, etc., even if it is provided with functions, and an insulating material composition using the same. An object of the present invention is to provide a thermostable resin composition suitable for a product, an adhesive composition for a circuit board, a laminated board for a circuit board, a coverlay film, a prepreg, a flexible wiring board, etc., and an insulating material composition using the same. And.

As a result of diligent studies on the above-mentioned conventional problems and the like, the present inventor can obtain the above-mentioned thermosetting resin composition, an insulating material composition using the same, and the like according to the following first to fifteenth inventions. He found out and completed the present invention.

That is, the present first invention contains at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based group, a coloring material, a cyanate ester resin and / or an epoxy resin. A thermosetting resin composition comprising a resin composition.

The second invention relates to a fluororesin micropowder dispersion containing at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oleophobic group, and a non-aqueous solvent, a coloring material, and cyanide. A thermosetting resin composition comprising at least an acid ester resin and / or a resin composition containing an epoxy resin.

The third invention comprises a fluororesin micropowder, a fluororesin micropowder dispersion containing at least a fluororesin micropowder containing at least a fluororesin-containing group and an oleophobic group, and a non-aqueous solvent, and a coloring material and a non-aqueous solvent. A thermosetting resin composition comprising at least a colored material dispersion or a colored material solution containing at least a solvent, and a resin composition containing a cyanate ester resin and / or an epoxy resin.

The fourth invention comprises a fluororesin micropowder, a fluororesin micropowder coloring material dispersion containing at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based group, a coloring material, and a non-aqueous solvent. It is a thermosetting resin composition characterized by containing at least a resin composition containing a cyanate ester resin and / or an epoxy resin.

In the fifth invention, the micropowder of the fluororesin is polytetrafluoroethylene, fluoroethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene co-weight. The first to fourth inventions, which are micropowder of one or more kinds of fluororesins selected from the group consisting of coalescence, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene. The heat-curable resin composition according to any one.

The heat curing according to any one of the first invention to the fifth invention, wherein the coloring material is at least one selected from an inorganic pigment, an organic pigment, and a dye. It is a resin composition.

The seventh invention is any one of the first invention to the fifth invention, wherein the coloring material is at least one selected from a carbon-based black pigment, an oxide-based black pigment, and a white pigment. The thermocurable resin composition according to.

The eighth invention is characterized in that, in the fluorine-based resin micropowder dispersion, the average particle size of the dispersed fluorine-based resin micropowder is 10 μm or less. The thermosetting resin composition according to any one.

The ninth invention is an insulating material composition obtained by using the thermosetting resin composition according to any one of the first invention to the eighth invention.

The tenth invention is an adhesive composition for a circuit board, which is obtained by using the thermosetting resin composition according to any one of the first invention to the eighth invention.

The eleventh invention is a laminated board for a circuit board including at least a structure of an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, and the adhesive layer. Is a laminated board for a circuit board, characterized in that is the adhesive composition for a circuit board according to the tenth invention.

In the twelfth invention, the insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene. The eleventh invention, which is one or more kinds of films selected from the group consisting of ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK). The circuit board laminate according to the above.

The thirteenth invention is an insulating film and a coverlay film in which an adhesive layer is formed on at least one surface of the insulating film, and the adhesive layer is for a circuit board according to the tenth invention. It is a coverlay film characterized by being an adhesive composition.

In the 14th invention, the insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene. The thirteenth invention characterized by being one or more kinds of films selected from the group consisting of ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK). It is a coverlay film described in.

The fifteenth invention is a structure formed of one or more kinds of fibers selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, or aramid-based fibers, at least the first invention to the eighth. The prepreg is impregnated with the thermocurable resin composition according to any one of the inventions.

According to the present invention, even if it is colored with a pigment or a dye and has functions such as hiding property, optical property, light shielding property, light reflection property, and design property, it has high insulation property, heat resistance, and electrical property ( Colored thermocurable resin composition with excellent workability, low dielectric constant, low dielectric constant), insulating material composition using it, adhesive composition for circuit board, laminated board for circuit board, coverlay film, Provided is a thermocurable resin composition suitable for prepregs, flexible printed wiring boards and the like.
Further, the insulating material composition using the thermosetting resin composition of the present invention, the adhesive composition for a circuit board, the laminated board for a circuit board, the coverlay film, the prepreg, the flexible printed wiring board and the like are organic pigments and inorganic pigments. , High insulation, heat resistance, electrical properties (low dielectric constant, even if it is colored with a dye coloring material and has functions such as concealment, optical properties, light-shielding properties, light reflectivity, and design properties. A colored insulating material composition having excellent workability (low dielectric normal contact), an adhesive composition for a circuit board, a laminated board for a circuit board, a coverlay film, a prepreg, a flexible printed wiring board, and the like can be obtained.

It is the schematic which shows an example of embodiment of the laminated board for a circuit board of this invention in the cross-sectional aspect. It is the schematic which shows another example of embodiment of the laminated board for a circuit board of this invention in the cross-sectional aspect. It is the schematic which shows an example of embodiment of the coverlay film of this invention in the cross-sectional aspect.

Hereinafter, embodiments of the present invention will be described in detail.
The thermosetting resin composition of the present invention is composed of the following first to fourth inventions, respectively.
The first invention has a resin composition containing at least a fluororesin micropowder, a fluorocarbon additive containing at least a fluororesin-containing group and an oil-based group, a coloring material, and a cyanate ester resin and / or an epoxy resin. The second invention is characterized by containing a substance, and the second invention is a fluorine containing at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based group, and a non-aqueous solvent. It is characterized by containing at least a based resin micropowder dispersion, a coloring material, and a resin composition containing a cyanate ester resin and / or an epoxy resin, and the third invention is a fluororesin micro. A fluororesin micropowder dispersion containing at least a powder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based solvent, and a non-aqueous solvent, and a coloring material dispersion containing at least a coloring material and a non-aqueous solvent. It is characterized by containing at least a coloring material solution and a resin composition containing a cyanate ester resin and / or an epoxy resin, and the fourth invention comprises micropowder of a fluororesin and at least a fluorine-containing group. At least a fluororesin micropowder coloring material dispersion containing at least a fluorine-based additive containing an oil-based group, a coloring material, and a non-aqueous solvent, and a resin composition containing a cyanate ester resin and / or an epoxy resin. It is characterized by including.
Hereinafter, each thermosetting resin composition will be described in detail for each of the first to fourth inventions. The components common to each invention will be described in detail in the first invention and the like, and the fact that they are common in the second and subsequent inventions will be described, and the details will be omitted.

[First Invention: Thermosetting Resin Composition]
<Fluorine resin micro powder>
Examples of the fluororesin micropowder used in the first invention include polytetrafluoroethylene (PTFE), ethylene fluoride-propylene copolymer (FEP), perfluoroalkoxypolymer (PFA), and chlorotrifluoroethylene. (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polychlorotrifluoroethylene (PCTFE), at least one selected from the group. Examples include micropowder of seed fluororesins.
Among the above-mentioned fluororesin micropowder, in particular, as a material having a low relative permittivity and a low dielectric loss tangent, polytetrafluoroethylene (PTFE, relative permittivity 2.1) having the best characteristics among resin materials. Desirable to use.
Such fluororesin micropowder is obtained by an emulsification polymerization method, a pulverization method, or the like, and is generally used, for example, the method described in the Fluororesin Handbook (edited by Takaomi Satokawa, Nikkan Kogyo Shimbun). It can be obtained by the method used in. In the case of the fluororesin micropowder obtained by the emulsion polymerization, the fine powder as secondary particles in which the primary particles are aggregated is recovered by agglomeration and drying.

The preferable particle size of the fluororesin micropowder is appropriately selected depending on the application, but the particle size is small in order to fully exhibit the stability of the thermosetting resin composition and the characteristics of the obtained epoxy resin and the like. Is preferable. The primary particle size of the fluororesin micropowder is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower the lower limit of the primary particle size, the better, but from the viewpoint of manufacturability, cost and the like, 0.05 μm or more and 0.3 μm or less is preferable.
As a method for measuring the primary particle size of the fluororesin micropowder, a volume-based average particle size (50% volume diameter, median diameter) measured by a laser diffraction / scattering method, a dynamic light scattering method, an image imaging method, etc. ) Is used, but by selecting a measurement method that matches the expected primary particle size, it is possible to obtain a measurement value that matches the actual particle size.
In the case of a fluororesin micropowder having a primary particle size of 1 μm or less, it indicates a value obtained by a laser diffraction / scattering method, a dynamic light scattering method, or the like at the micropowder manufacturing stage. However, in the case of micropowder that has been dried and powdered, the cohesive force between the primary particles is strong, and it is difficult to easily measure the primary particle size by laser diffraction / scattering method or dynamic light scattering method. Therefore, it may indicate a value obtained by an image imaging method. Examples of the measuring device include a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction / scattering method using Microtrac (manufactured by Nikkiso Co., Ltd.), and MacView (manufactured by Mountech Co., Ltd.). An image imaging method based on the above can be mentioned.

The fluororesin micropowder can be used by mixing two or more types having different primary particle sizes, or mixing two or more types of dispersed fluororesin micropowder having different average particle sizes. It is also possible to use a mixture of two or more types of fluororesin micropowder having different primary particle diameters and average particle diameters. By using two or more types of fluororesin micropowder having different particle sizes, it becomes possible to adjust the viscosity, increase the filling rate, and control the surface condition of the epoxy resin or the like.

Further, the fluororesin micropowder may be subjected to various surface treatments. For example, surfactants and impurities remaining on the surface of micropowder of fluororesin due to acid treatment, alkali treatment, ultraviolet irradiation treatment, ozone treatment, electron beam irradiation treatment, heat treatment, water washing, hot water washing, various gas treatments, etc. It is possible to remove or activate unnecessary components of.

In the first invention, the fluororesin micropowder is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total solid content of the thermosetting resin composition. It is desirable to be done.
If this content is less than 5% by mass, the characteristics of the fluororesin cannot be sufficiently imparted to the final thermosetting resin or the like, and if the content exceeds 70% by mass. , It is not preferable because the mechanical strength of the final thermosetting resin or the like becomes extremely weak.

<Fluorine-based additive>
The fluorine-based additive used in the first invention needs to have at least a fluorine-containing group and a lipophilic group, and is particularly limited as long as it has at least a fluorine-containing group and a lipophilic group. In addition to this, a hydrophilic group may be contained.
By using a fluorine-based additive having at least a fluorine-containing group and a lipophilic group, the surface tension of a non-aqueous solvent such as an oil-based solvent as a dispersion medium is reduced, and the wettability to the surface of polytetrafluoroethylene is improved to make poly. While improving the dispersibility of tetrafluoroethylene, the fluorine-containing group is adsorbed on the surface of polytetrafluoroethylene, and the lipophilic group extends into a non-aqueous solvent such as an oil solvent as a dispersion medium, and the three-dimensional of this lipophilic group. Due to the obstacle, the aggregation of the micropowder of the fluororesin such as polytetrafluoroethylene is prevented to further improve the dispersion stability, and the micropowder of the fluororesin and the coloring material described later are combined with the polyimide precursor solution composition. Fine particles can be uniformly and stably dispersed in the object.

Examples of the fluorine-containing group include a perfluoroalkyl group and a perfluoroalkenyl group, and examples of the lipophilic group include one or more types such as an alkyl group, a phenyl group and a siloxane group. Examples of the hydrophilic group include one or more of ethylene oxide, amide group, ketone group, carboxyl group, sulfone group and the like.
Specific examples of the fluorine-based additive that can be used include surflon series (manufactured by AGC Seimi Chemical Co., Ltd.) such as surflon S-611 containing a perfluoroalkyl group, megafuck F-555, megafuck F-558, and megafuck. Mega Fvck series such as F-563 (manufactured by DIC), Unidyne series such as Unidyne DS-403N (manufactured by Daikin Industries, Ltd.), and Fluorient series such as Futagient 610FM (manufactured by Neos) can be used.
The optimum fluorine-based additive is appropriately selected depending on the type of polytetrafluoroethylene to be used, the type of non-aqueous solvent such as an oil-based solvent, and the coloring material, but one type or a combination of two or more types is appropriately selected. It is also possible to use it.

The content of the fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is preferably 0.1 to 20% by mass with respect to the micropowder of the fluorine-based resin. If the content of this compound is less than 0.1% by mass, the dispersion stability is deteriorated and the fluororesin micropowder tends to settle, and if it exceeds 20% by mass, the viscosity becomes high, which is not preferable.
Further, considering the characteristics when a non-aqueous dispersion of a fluororesin micropowder is added to a thermosetting resin or the like, 0.1 to 10% by mass is desirable, and further 0.1 to 7% by mass is desirable. In particular, 0.1 to 5% by mass is most preferable.

In the first invention, other surfactants and dispersants may be used in appropriate amounts in combination with a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group as long as the effects of the present invention are not impaired. It is possible.
For example, nonionic, anionic, and cationic surfactants and dispersants, nonionic, anionic, and cationic surfactants and butyral (PVB) resins, regardless of whether they are fluorine-based or non-fluorine-based. Examples thereof include polymer dispersants such as, but the present invention can be used without limitation.
Examples of the butyral (PVB) resin include a ternary polymer composed of vinyl butyral / vinyl acetate / vinyl alcohol obtained by reacting polyvinyl alcohol (PVA) with butylaldehyde (BA), and examples thereof include a butyral group, an acetyl group, and the like. It has a structure with hydroxyl groups, and by changing the ratio of these three types of structures, various butyral (PVB) resins with different amounts of hydroxyl groups and degree of butyralization can be used. Eslek B series such as Eslek BM-1 (hydroxyl group amount: 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 40,000), KS-10 (hydroxyl group amount: 25 mol%, acetalization degree 65 ± 3) K (KS) series such as mol%, molecular weight: 17,000), SV series, Mobital B145 manufactured by Kuraray Co., Ltd. (hydroxyl amount: 21 to 26.5 mol%, acetalization degree 67.5 to 75.2 mol) %), B16H (hydroxyl group amount: 26.2 to 30.2 mol%, acetalization degree 66.9 to 73.1 mol%, molecular weight: 10,000 to 20,000) and the like can be used. ..

<Coloring material>
Examples of the coloring material used in the first invention include at least one selected from inorganic pigments, organic pigments, and dyes.
As inorganic pigments, organic pigments, and dyes that can be used, conventionally, heat-curable resin materials such as coverlay films and flexible printed wiring boards are colored to have concealing properties, optical properties, light-shielding properties, light reflection properties, and design properties. As long as it is used to perform such functions, it is not particularly limited, but preferably, it impairs performance such as insulation, low dielectric constant, low dielectric constant contact, electrical characteristics, and workability. However, from the viewpoint of further exerting the effect of the present invention, examples of the inorganic pigment and the organic pigment include at least one selected from carbon-based black pigment, oxide-based black pigment, and white pigment.

Examples of the carbon-based black pigment include carbon blacks such as furnace black, acetylene black, thermal black, and channel black, black mica, graphite powder, and those commercially available as graphite powder.
Examples of the oxide-based black pigment include cobalt oxide, ferrous tetraoxide, ferrous oxide, manganese oxide, titanium black, chromium oxide, bismuth oxide, stannous oxide, cupric oxide or copper-iron-manganese. , Aniline Black, Perylene Black, Iron Manganese Bismus Black, Cobalt Iron Chrome Black, Copper Chrome Manganese Black, Iron Chrome Black, Manganese Bismus Black, Manganese Ittrium Black, Iron Manganese Oxide Spinel Black, Copper Chromite Spinel Black, Hematite, Magnetite, At least one selected from the group consisting of mica-like iron oxide, titanium black, metal oxides containing iron, composite metal oxides, and the like can be mentioned.
Among these black pigments, carbon black, which has excellent light-shielding properties, and commercially available products, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44 manufactured by Mitsubishi Chemical Co., Ltd. , # 45, # 47, # 52, # 85, # 95, CF9, MA7, MA8, MA11, MA100, MA220, MA230, etc., Printex 25, 35, 40, 45, 55, 150T, U, manufactured by Ebonic Industries. It is preferable to use the Printex series such as V, P, and L6, and perylene black pigments that improve electrical reliability. For commercial products, BASF's Lumogen Black series and Paliogen Black series may be used. preferable. Further, an aluminum flake pigment (black interference aluminum pigment) having excellent heat shielding properties can also be used.

White pigments include titanium oxide, alumina, barium sulfate, magnesia, aluminum titrated, boron titrated (hexagonal cubic), barium titanate, zirconium oxide, calcium oxide, zinc oxide, zinc sulfide, calcium sulfate, basic Zinc molybdate, basic calcium molybdate zinc, molybdate white, kaolin, silica, talc, powdered mica, powdered glass, powdered aluminum, powdered nickel, calcium carbonate and the like can be used.
Among these white pigments, titanium oxide having a large shielding power and fine powder silica having a high insulating property are more preferable, and these can be used in combination, and by using both in combination, both the insulating property and the reflectivity are improved. can do. Examples of the titanium oxide include anatase-type titanium oxide and rutile-type titanium oxide. Among these, when used for LEDs, anatase-type titanium oxide that reflects the wavelengths of near-ultraviolet LEDs and blue LEDs is more preferable. Examples of the fine powder silica include crystalline silica, meltable silica, and fuzzy silica.
Since the surface of titanium oxide can be treated with alumina, silica, etc., or with a silane-based coupling agent or titanate-based coupling agent, the oxidative decomposition reaction of organic substances due to the combination of titanium oxide and a photocatalyst can be suppressed. The life of the insulating material and the coverlay film using the thermocurable resin composition can be further extended.

Examples of carbon-based black pigments, oxide-based black pigments, inorganic pigments other than white pigments, and organic pigments include azo pigments, disazo pigments, isoindolinone pigments, quinophthalone pigments, isoindolin pigments, anthraquinone pigments, and antron pigments. Examples thereof include xanthene pigments, diketopyrrolopyrrole pigments, anthraquinone (anthron) pigments, perinone pigments, quinacridone pigments, indigotin pigments, dioxazine pigments, phthalocyanine pigments, and azomethine pigments. Examples of the inorganic pigment include reddish substances such as manganese oxide / alumina, chromium / tin oxide, iron oxide, cadmium / selenium sulfide, cobalt oxide, zirconia / vanadium oxide, chromium oxide / divanadium pentoxide, and the like. Blue, zirconium / silicon / placeodium, vanadium / tin, yellow such as chromium / titanium / antimon, green such as chromium oxide, cobalt / chromium, alumina / chromium, pink such as aluminum / manganese, iron / silicon / zirconium. The system etc. can be mentioned.

Inorganic pigments and organic pigments containing these carbon-based black pigments, oxide-based black pigments, white pigments, etc., have hiding properties, optical properties, light-shielding properties, light reflectivity, and design properties without impairing performance such as processability. It is preferable that the primary particle size is 1 μm or less from the viewpoint of effectively exerting other functions such as.

Examples of dyes that can be used include those having any form of various dyes such as oil-soluble dyes, acidic dyes, direct dyes, basic dyes, mordant dyes, and acidic mordant dyes. Further, the dye may be raked and used, or may be in the form of a salt-forming compound of the dye and a nitrogen-containing compound.
As the dye to be used, a dye having a substituent that is reactive with a diamine compound such as an aromatic diamine used in the thermosetting resin composition is desirable, and a dye having a sulfonic acid group or a carboxylic acid group in the molecule is preferable. is there. For example, acid dyes (since diamine is a basic substance, acid dyes that are sensitive to bases are excluded) and the like can be preferably used. Normally, the dye is simply dissolved and dispersed in the molecules of the thermosetting resin, whereas when there is a diamine compound such as aromatic diamine, the dye is partly and a polymer matrix that has been thermoset by heat treatment. Due to the binding, the dye becomes difficult to move in the thermosetting resin, and the solvent resistance and the like can be further improved.
In the first invention, among the coloring materials used, inorganic pigments, organic pigments, and dyes, heat-curable resin materials (insulating materials, insulating films, coverlay films, flexible printed wiring boards, etc.) are used as coloring materials. As described above, the optimum preferable coloring material is selected in consideration of the point that the desired shielding property, light-shielding property and reflection property can be exhibited by the content.

In the first invention, the coloring material used is the use of the heat-curable resin material (heat-curable resin film, heat-curable resin insulating film, coverlay film, flexible printed wiring board, etc.), hiding property, optical property, light-shielding property, and the like. A suitable amount is determined in consideration of other functions such as light reflectivity and designability, and impairs performance such as insulation, low dielectric constant, low dielectric loss tangent, electrical characteristics, and workability. However, the lower limit is the total solid content of the heat-curable resin composition, because the inclusion of the coloring material allows other functions such as the desired hiding property, optical properties, light-shielding property, light reflectivity, and design property to be exhibited. It is 0.1% by mass or more, more preferably 1% by mass or more, and on the other hand, the upper limit is 30% by mass or less, more preferably 30% by mass or less from the viewpoint of not impairing the characteristics such as the mechanical strength of the final thermosetting resin or the like. , 20% by mass or less is preferable.

[Resin composition]
Examples of the resin composition used in the first invention include at least a cyanate ester resin and / or an epoxy resin. These resins serve as the base resin for the thermosetting resin composition, and can be used without particular limitation as long as they are suitable for use, such as insulating properties and adhesiveness in electronic devices.
Examples of the cyanate ester resin (cyanate ester resin) that can be used include at least a bifunctional aliphatic cyanate ester, at least a bifunctional aromatic cyanate ester, or a mixture thereof. 1,3,5-trisianatobenzene, 1,3-disianatonaphthalene, 1,4-disianatonaphthalene, 1,6-disianatonaphthalene, 1,8-disianatonaphthalene, 2,6-disianatonaphthalene, And a polymer of at least one polyfunctional cyanate ester selected from 2,7-disianatonaphthalene, bisphenol A type cyanate ester resin or those obtained by adding hydrogen, bisphenol F type cyanate ester resin or these. 6F bisphenol A dicyanic acid ester resin, bisphenol E type dicyanic acid ester resin, tetramethylbisphenol F dicyanic acid ester resin, bisphenol M dicyanic acid ester resin, dicyclopentadiene bisphenol disyanic acid ester resin, or At least one such as novolak citrate resin can be mentioned. Commercially available products of these cyanate ester resins can also be used.

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

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

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

Further, in the first invention, a non-aqueous solvent can be used for adjusting the viscosity of the thermosetting resin composition.
For example, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentylketone, methylisobutylketone, methylisopentylketone, ethyleneglycol, diethyleneglycol. , Propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol monoacetate, propylene glycol diacetate, Propropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyruvate Ethyl acid, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Xylene, Simene, Mesitylene, Methanol, Ethanol, Isopropanol, Butanol, Methylmonoglycidyl ether, Ethylmonoglycidyl ether, Butylmonoglycidyl ether, Phenylmonoglycidyl ether, Methyldiglycidyl ether, Ethyldiglycidyl ether, Butyldiglycidyl ether, phenyl Diglycidyl ether, methylphenol monoglycidyl ether, ethylphenol monoglycidyl ether, butylphenol monoglycidyl ether, mineral spirit, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate , Hydroxypropyl methacrylate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, Trimethylolpropan triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N -Selected from the group consisting of diethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, γ-butyrolactone, sulfolane, halogenated phenols, various silicone oils 1 Types of solvents, or those containing two or more of these solvents can be mentioned.
Among these non-aqueous solvents, preferably, it varies depending on the material used, the use of the thermosetting resin, etc., but acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2. Examples thereof include -pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane, halogenated phenols, xylene and acetone.
The content of these non-aqueous solvents is adjusted so as to be a suitable content for adjusting the viscosity of the thermosetting resin composition and the like.

<First invention: thermosetting resin composition>
The thermocurable resin composition of the first invention comprises at least the above-mentioned fluororesin micropowder, the above-mentioned fluorine-based additive containing at least a fluorine-containing group and an oil-based group, the above coloring material, and the above cyanate ester. It is characterized by containing a resin and / or a resin composition containing an epoxy resin. For example, the micropowder of the fluorine-based resin and at least the fluorine-containing group and the lipophilic group are contained in a non-aqueous solvent. A predetermined amount of the fluorine-based additive contained, the coloring material, and the resin composition containing the cyanate ester resin and / or the epoxy resin is added and mixed, and the mixture is stirred with a disper or a homogenizer, or super It can be prepared by using various stirrers and dispersers such as a sound disperser, a planetary mixer, a three-roll mill, a ball mill, a bead mill, and a jet mill.
In the thermocurable resin composition of the first invention, the fluororesin micropowder, the fluorine-based additive containing at least the fluorine-containing group and the lipophilic group, the coloring material, the cyanate ester resin and / Alternatively, by adding and mixing a predetermined amount of a resin composition containing an epoxy resin to a non-aqueous solvent, the total resin concentration of the cyanate ester resin, epoxy resin, etc. required in the final thermocurable resin composition can be obtained. By adjusting so that, the fluororesin powder and the coloring material can be uniformly present without agglomeration, the specific dielectric constant and the dielectric tangent are low, and the adhesiveness, heat resistance, dimensional stability, and flame retardancy are low. It will be possible to exhibit excellent characteristics such as sex.
The thermocurable resin composition of the first invention comprises at least the above-mentioned fluororesin micropowder, the above-mentioned fluorine-based additive containing at least a fluorine-containing group and an oil-based group, the above coloring material, and the above cyanate ester. It contains a resin and / or a resin composition containing an epoxy resin, and is molded and cured by the same method as a heat-curable resin composition such as a known epoxy resin composition to form a cured product, an insulating material, and the like. can do. The molding method and the curing method can be the same as those of a thermosetting resin composition such as a known epoxy resin composition, and the method peculiar to the thermosetting resin composition of the first invention is unnecessary and particularly limited. Not a thing.
Further, the thermosetting resin composition of the first invention can be used for various additives such as surfactants, dispersants and antifoaming agents, filler materials such as silica particles and acrylic particles, as long as the effects of the present invention are not impaired. Elastomers and the like can be used.
Further, in the thermosetting resin composition of the first invention, it is preferable that the thermosetting resin composition has a water content of 5000 ppm or less [0 ≦ water content ≦ 5000 ppm] by the Karl Fischer method. It is conceivable that water may be mixed in from the material or in the manufacturing stage, but when the water content of the thermosetting resin composition is finally reduced to 5000 ppm or less, the fluororesin micropowder and the coloring material (pigment) are aggregated. It is possible to make it exist uniformly without any problem, and it is possible to obtain a thermosetting resin composition having more excellent storage stability.

[Second Invention: Thermosetting Resin Composition]
The thermosetting resin composition of the second invention contains at least the above-mentioned micropowder of a fluororesin, the above-mentioned fluorine-based additive containing at least a fluorine-containing group and an oleophobic group, and the above-mentioned non-aqueous solvent. It is characterized by containing at least a powder dispersion, a coloring material, and a resin composition containing the cyanate ester resin and / or the epoxy resin, and details of each of the above components and the like are described in the first invention. Since it is the same, the description thereof will be omitted.
In the second invention, as compared with the first invention, the fluororesin micropowder contains at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oleophobic group, and a non-aqueous solvent. A dispersion prepared is used, and a fluororesin is obtained by adding and mixing a predetermined amount of a coloring material and a resin composition containing the cyanate ester resin and / or an epoxy resin to the dispersion. The micropowder and the thermocurable resin composition in which the coloring material is uniformly dispersed in the composition without agglomeration or precipitation can be obtained.

The fluororesin micropowder dispersion of the second invention includes, for example, mixers such as a diffr and a homomixer, an ultrasonic disperser, a three-roll, a wet ball mill, a bead mill, a disperser such as a wet jet mill, and the like. It can be produced by stirring, mixing, and dispersing using it, but in the dispersed state, the average particle size based on the volume by the dynamic light scattering method or the laser diffraction / scattering method of the fluororesin micropowder ( The 50% volume diameter and median diameter) are preferably 10 μm or less. Usually, the primary particles are aggregated to form micropowder having a large particle size as secondary particles. By dispersing the secondary particles of the fluororesin micropowder so as to have a particle size of 10 μm or less, for example, mixers such as a disper and a homomixer, an ultrasonic disperser, three rolls, a wet ball mill, and the like. By dispersing using a disperser such as a bead mill, a wet jet mill, or a high-pressure homogenizer, a stable dispersion can be obtained even when stored for a long period of time with low viscosity.
The average particle size is preferably 5 μm or less, more preferably 3 μm or less, and more preferably 1 μm or less. This is because it becomes a more stable dispersion.

Further, also in the thermosetting resin composition of the second invention, like the above-mentioned thermosetting resin composition of the first invention, a surfactant, a dispersant, and a defoaming agent are used as long as the effects of the present invention are not impaired. Various additives such as agents, filler materials such as silica particles and acrylic particles, and elastomers can be used.
Further, also in the thermosetting resin composition of the second invention, similarly to the thermosetting resin composition of the first invention described above, the water content by the Karl Fischer method is 5000 ppm or less [0 ≤ water content ≤ 5000 ppm]. It is preferable to have. It is conceivable that water may be mixed in from the material or in the manufacturing stage, but when the water content of the thermosetting resin composition is finally reduced to 5000 ppm or less, the fluororesin micropowder and the coloring material (pigment) are aggregated. It is possible to make it exist uniformly without any problem, and it is possible to obtain a thermosetting resin composition having more excellent storage stability.

[Third Invention: Thermosetting Resin Composition]
The thermosetting resin composition of the third invention is a fluororesin micropowder dispersion containing at least a fluororesin micropowder, a fluorine-based additive containing at least a fluororesin-containing group and an oil-based group, and the above-mentioned non-aqueous solvent. It is characterized by containing at least 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 cyanate ester resin and / or the epoxy resin. Since the details of each of the above components are the same as those of the first invention and the like, the description thereof will be omitted.
In the third invention, as compared with the first and second inventions, a fluororesin micropowder containing at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous solvent are contained in advance. A resin micropowder dispersion and a color material dispersion or a color material solution containing at least a coloring material and a non-aqueous solvent are used. In this dispersion or solution, the cyanate ester resin and / or the above-mentioned cyanate ester resin and / or By adding and mixing a predetermined amount of a resin composition containing an epoxy resin, a fluororesin micropowder and a thermocurable resin composition in which the coloring material is uniformly dispersed in fine particles without agglomeration or sedimentation in the composition. Is obtained.

The colored material dispersion of the third invention is obtained by, for example, dispersing an inorganic pigment or an organic pigment containing the above-mentioned carbon-based black pigment, oxide-based black pigment, white pigment or the like in a non-aqueous solvent. However, it can be dispersed by using a surfactant, a dispersant, a pigment derivative (synagist), an antifoaming agent, or the like, if necessary and within a range that does not impair the effects of the present invention.
As the device used for dispersion, as in the case of the above-mentioned fluororesin micropowder dispersion, for example, mixers such as a disper and a homomixer, an ultrasonic disperser, a 3-roll, a wet ball mill, a bead mill, and a wet jet mill. It can be produced by stirring, mixing, and dispersing using a disperser such as.
The colored material dispersion has a volume-based average particle size (50% volume diameter, median diameter) of 3 μm or less by a dynamic light scattering method or a laser diffraction / scattering method of a colored material (pigment) in a dispersed state. Is preferable. By dispersing this coloring material (pigment) so as to have a particle size of 3 μm or less, for example, mixers such as a disper and a homomixer, an ultrasonic disperser, a 3-roll, a wet ball mill, a bead mill, and a wet jet mill. By dispersing using a disperser such as a high-pressure homogenizer, a stable dispersion can be obtained even when stored for a long period of time with low viscosity.
The average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, and more preferably 0.3 μm or less. This is because it becomes a more stable dispersion.

The coloring material solution of the third invention can be obtained by dissolving various dyes such as the above-mentioned oil-soluble dye, acidic dye, direct dye, basic dye, mordant dye, or acidic mordant dye in a non-aqueous solvent. Is something that can be done.
As the device used for dissolution, any mixer such as a disper or homomixer, or any device capable of stirring, mixing, and dissolving such as an ultrasonic irradiation device can be used, and a coloring material having low solubility can be used. When (dye) is used, it can be dissolved by stirring a non-aqueous solvent while heating it.

[Fourth Invention: Thermosetting Resin Composition]
The thermosetting resin composition of the fourth invention contains at least a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based group, a coloring material, and the above-mentioned non-aqueous solvent. It is characterized by containing at least the powder coloring material dispersion and the resin composition containing the cyanate ester resin and / or the epoxy resin, and the details of each of the above components and the like are the same as those of the first invention and the like. Therefore, the description thereof will be omitted.
In the fourth invention, as compared with the first, second, and third inventions, a fluororesin micropowder, a fluorine-based additive containing at least a fluorine-containing group and an oil-based group, a colorant, and a non-aqueous solvent are used. A fluorine-based resin micropowder coloring material dispersion containing at least is used, and a predetermined amount of a resin composition containing the cyanate ester resin and / or an epoxy resin is added to and mixed with the dispersion to obtain a fluorine-based resin. A heat-curable resin composition in which the resin micropowder and the coloring material are uniformly dispersed in fine particles without agglomeration or precipitation in the composition can be obtained.

The fluorine-based resin micropowder coloring material dispersion of the fourth invention is, for example, a non-aqueous mixture of a fluorine-based resin micropowder, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and a colorant. It is obtained by dispersing in a solvent, but it is dispersed by using a surfactant, a dispersant, a pigment derivative (synagist), an antifoaming agent, etc., if necessary and within a range that does not impair the effect of the present invention. Is something that can be done.
Examples of the device used for dispersion include mixers such as a disper and a homomixer, an ultrasonic disperser, three rolls, and a wet ball mill, as in the case of the above-mentioned fluororesin micropowder dispersion and colored material dispersion. It can be produced by stirring, mixing, and dispersing using a disperser such as a bead mill or a wet jet mill.

Since the fluorine-based resin micropowder coloring material dispersion is a dispersion containing both the fluorine-based resin micropowder and the coloring material, it is simply like the fluorine-based resin micropowder dispersion and the coloring material dispersion. Although it is difficult to obtain the average particle size, it is preferable to use a filter, a mesh, or the like so that the maximum particle size is 10 μm or less. This is because it becomes a more stable dispersion.

In the present invention, by carrying out each of the above inventions 1 to 4, the micropowder of the fluororesin and the coloring material are thermally cured by uniformly dispersing fine particles in the composition without agglomeration or precipitation. A resin composition can be obtained.
Further, in the first to fourth inventions, the non-aqueous solvent is used, but it can be used in combination with another solvent or another solvent can be used, and the thermosetting resin composition to be used. A suitable material is selected according to the application of the product (wiring plate including circuit board, coverlay film, insulating material, etc.).

[Preparation of cured product, insulating material, etc. obtained from each thermosetting resin composition of the first to fourth inventions]
The cured product, insulating material, etc. obtained from the thermosetting resin composition of the present invention are molded and cured by the same method as the thermosetting resin composition such as a known epoxy resin composition, and the cured product, insulating material, etc. Can be. The molding method and the curing method can be the same as those of a heat-curing resin composition such as a known epoxy resin composition. Micropowder of a fluororesin and a coloring material are uniformly dispersed in fine particles, and a pigment or dye is used. Even if it is colored and has functions such as concealment, optical properties, light-shielding properties, light reflectivity, and design properties, it has high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric adjunct), and processing. A colored cured product having excellent properties, an insulating material such as a heat-curable resin insulating film, and the like can be obtained.
As a method for producing a thermosetting resin insulating film, for example, micropowder of a fluororesin is dispersed to produce a predetermined coloring, for example, a black or white thermocurable resin, a thermocurable resin film, or a thermocurable resin insulating material. In this case, the heat-curable resin composition obtained above is applied to the surfaces of the heat-curable resin base material and the heat-curable resin film base material to form a film-like material (coating film), and the film-like material is heated. It can be obtained by treating, removing the solvent, and performing a curing treatment.
The substrate that can be used is not particularly limited in shape and material as long as it has a dense structure that does not substantially allow liquid or gas to permeate, and is not particularly limited in shape or material, and is used when producing an ordinary film. Film-forming substrates such as belts, molds, rolls, and drums that are known in themselves, electronic components such as circuit boards that form a thermosetting resin film as an insulating protective film on the surface, electric wires, and coatings on the surface. Preferable examples thereof include sliding parts and products to be formed, one film and copper foil for forming a multilayer film and a copper-clad laminate by forming a thermosetting resin film.
Further, as a method of applying the thermosetting resin composition to these substrates, for example, a spray method, a roll coating method, a rotary coating method, a bar coating method, an inkjet method, a screen printing method, a slit coating method and the like itself. A known method can be appropriately adopted.
A film, a film, an insulating material, etc. made of a thermosetting resin composition applied to this base material is defoamed by a method of heating at a relatively low temperature such as room temperature or lower under reduced pressure or normal pressure, for example. It doesn't matter.

A film-like material composed of a thermosetting resin composition formed on a base material is heat-treated to remove a solvent and then cured to be a thermosetting resin, a thermosetting resin film, or a thermosetting resin insulating material. Is formed.
The thickness of the thermosetting resin, the thermosetting resin film, and the thermosetting resin insulating material is appropriately adjusted according to the application. For example, the thickness is 0.1 to 200 μm, preferably 3 to 150 μm, and more preferably 5 to 130 μm. The thermosetting resin film and film of the above are preferably used.

The micropowder concentration of the fluororesin in the colored thermosetting resin film, the colored thermosetting resin film, the colored thermosetting resin insulating material, etc. obtained from the thermosetting resin compositions of the first to fourth inventions is particularly limited. Although not, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, still more preferably, based on the total mass of the cured product obtained by curing the thermosetting resin composition of the present invention. , 10 to 35% by mass is preferable. If the micropowder concentration of the fluororesin is too small, there is no effect of adding the micropowder of the fluororesin, and if the micropowder concentration of the fluororesin is too high, the mechanical properties of the thermosetting resin are deteriorated.
Further, the concentration of the colored material of the fluororesin in the colored thermosetting resin insulating material such as the colored thermosetting resin insulating film is not particularly limited, but the thermosetting resin composition of the present invention is cured. It is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, still more preferably about 5 to 20% by mass, based on the total mass of the cured product. If the concentration of the coloring material is too small, there is no effect of exhibiting concealment, optical properties, light-shielding property, light reflectivity, design, etc., and if the concentration of the coloring material is too high, the electrical properties of the thermosetting resin, Mechanical characteristics and the like will deteriorate.

A colored thermocurable resin film obtained from each of the thermocurable resin compositions of the first to fourth inventions, for example, a white thermocurable resin such as a white film obtained by using a white pigment such as titanium oxide as a pigment. As a material, it can be used as a heat-resistant and lightweight white material, specifically, an LED (light emitting diode), a reflective material for organic EL light emission, or a base material for a metal layer white film, and also an LED, an organic EL, or another light emitting element. It can be suitably used for a flexible printed wiring board or the like on which the above is mounted.
Further, in a black thermosetting resin material such as a black thermosetting resin film obtained from each of the thermosetting resin compositions of the first to fourth inventions, the shielding property, optical property, and light shielding property of the electronic component or mounting component to be protected. Will be excellent.

<Adhesive composition for circuit boards>
The adhesive composition for a circuit board of the present invention is obtained by using each of the thermosetting resin compositions of the first to fourth inventions described above, and is a rubber component dispersed in the cyanate ester resin or the epoxy resin. May be further contained.
The adhesive composition for a circuit board of the present invention has sufficient flexibility (Flexible, the same applies hereinafter) for use in manufacturing a flexible printed circuit board that can bend wiring and a substrate. Although it must be possessed, it is preferable that the adhesive composition for a circuit board further contains a rubber component in order to supplement such flexibility.

Examples of the rubber component that can be used include natural rubber (NR) and synthetic rubber, preferably styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), and ethylene propylene diene monomer (EPDM). ) Rubber, polybutadiene rubber, modified and modified polybutadiene rubber and the like, preferably EPDM rubber having an ethylene content of 10 to 40% by mass, SBR, NBR and the like can be used, and in particular, EPDM rubber, which can reduce the relative dielectric constant and the dielectric loss coefficient value of the resin composition, is preferable.
The content of these rubber components is 1 to 80 parts by mass with respect to 100 parts by mass of the resin (cyanic acid ester resin or epoxy resin) from the viewpoint of further exerting the effect of the present invention, adhesive strength and heat resistance. , It is preferably 10 to 70 parts by mass, and more preferably 20 to 60 parts by mass.

The circuit board adhesive composition of the present invention contains the above-mentioned configurations of the first to fourth inventions, for example, in the first invention, the above-mentioned fluororesin micropowder, and the above-mentioned at least a fluorine-containing group and an epoxy group. It can be produced by a usual method of mixing the contained fluorine-based additive, the coloring material, a resin composition composed of a cyanate ester resin or an epoxy resin, and the like, preferably the fluorine-based resin micropowder of the second invention. A method of adding and mixing a coloring material, a cyanate ester resin and / or an epoxy resin, and a resin composition containing a rubber component to the dispersion, a fluororesin micropowder dispersion and a coloring material dispersion of the third invention. Alternatively, a method of adding and mixing a cyanate ester resin and / or an epoxy resin and a resin composition containing a rubber component to a coloring material solution, and a cyanate ester in the fluororesin micropowder coloring material dispersion of the fourth invention. It can be produced by a method of adding and mixing a resin and / or an epoxy resin and a resin composition containing a rubber component.

The adhesive composition for a circuit board of the present invention may further contain inorganic particles such as a phosphorus-based flame retardant in order to supplement flame retardancy and the like. The inorganic particles such as these phosphorus-based flame retardants are preferably 1 to 30 parts by mass, preferably 5 to 20 parts by mass with respect to 100 parts by mass of the cyanate ester resin or epoxy resin.
In addition to the above components, the adhesive composition for circuit boards of the present invention contains curing accelerators, defoamers, colorants, phosphors, modifiers, discoloration inhibitors, inorganic fillers other than the above, if necessary. Conventionally known additives such as a silane coupling agent, a light diffusing agent, and a heat conductive filler can be blended in an appropriate amount.
Examples of the curing (reaction) accelerator other than the above include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and the first such as 1,8-diazabicyclo (5,4,0) undecene-7. Tertiary amines and their salts, phosphines such as triphenylphosphine, phosphonium salts such as triphenylphosphonium bromide, aminotriazoles, tin octylate, tin dilaurate and the like, zinc octylate and the like, aluminum , Metal catalysts such as acetylacetonate such as chromium, cobalt and zirconium are used. These curing (reaction) accelerators may be used alone or in combination of two or more.

The adhesive composition for a circuit board of the present invention can be molded and cured by the same method as the known cyanate ester resin composition and epoxy resin composition to obtain a cured product. The molding method and the curing method can be the same as those of the known cyanate ester resin and epoxy resin compositions, and the method specific to the circuit board adhesive composition of the present invention is unnecessary and particularly limited. Not.
The adhesive composition for a circuit board of the present invention can be further formed into various forms such as a laminate, a molded product, an adhesive, a coating film, and a film.
The adhesive composition for a circuit board of the present invention is a heat-curable resin composition colored in black, white, etc., in which micropowder of a fluororesin and a coloring material are stably and uniformly dispersed without color unevenness or agglomerates. Since an adhesive composition for a circuit board can be obtained using the above, it has low specific dielectric constant and dielectric tangent, and has excellent properties such as adhesiveness, heat resistance, dimensional stability, and flame retardancy, so that it can be used for a circuit board. It is suitable as an adhesive material, and can be used, for example, in the production of laminated boards for circuit boards, coverlay films, prepregs, bonding sheets, and the like using the same. The coverlay film, prepreg, bonding sheet, etc. can be applied to a circuit board, for example, a flexible printed circuit board (FPCB) such as a flexible metal foil laminated board, and the circuit of the present invention is used for manufacturing these. When an adhesive composition for a substrate is used, the adhesive composition for a circuit board has properties such as low relative permittivity and dielectric tangent, and excellent adhesiveness, heat resistance, dimensional stability, and flame retardancy. It will be feasible.

<Laminated board for circuit board>
The laminated board for a circuit board of the present invention is a laminated board for a circuit board including at least a structure of 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 composed of an adhesive composition for a circuit board having the above structure.

FIG. 1 is a schematic view showing a metal foil laminated board (FPCB) as an example of an embodiment of the laminated board for a circuit board of the present invention in a cross-sectional manner.
The laminated board A for a circuit board of the present embodiment is one in which a metal foil 30 is laminated on an insulating film 10 and at least includes an adhesive resin layer 20 interposed between the insulating film 10 and the metal foil 30. The adhesive resin layer 20 is composed (bonded) of an adhesive composition for a circuit board colored in black, white, or the like without color unevenness or agglomerates having the above-mentioned structure.
FIG. 2 is a schematic view showing a metal foil laminated board (FPCB), which is another example of the embodiment of the laminated board for a circuit board of the present invention, in a cross-sectional manner.
The laminated board B for a circuit board of the present embodiment adopts a double-sided structure as shown in FIG. 2 instead of the single-sided structure of FIG. 1, and metal foils 30 and 30 are laminated on both sides of the insulating film 10. The adhesive resin layers 20 and 20 interposed between the insulating film 10 and the metal foils 30 and 30, respectively, are included, and the adhesive resin layers 20 and 20 also have color unevenness having the above configuration. It is composed (bonded) of an adhesive composition for a circuit board colored in black or white without agglomerates.

The insulating film 10 used in the laminated board for a circuit board according to the present invention shown in FIGS. 1 and 2 is not particularly limited as long as it has electrical insulation, but has heat resistance, flexibility, mechanical strength, and the like. Those having a coefficient of thermal expansion similar to that of metal can be used.
Examples of the insulating film 10 that can be used include polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), and polyetherimide (PEI). Examples thereof include one or more films selected from the group consisting of polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK), and polyimide (PI) is preferable. ) It is a film.
Further, the film formed from these materials is preferably provided with a film whose surface is further surface-treated with low-temperature plasma or the like from the viewpoint of further improving the interfacial adhesion with the adhesive resin layer 20. Can be used.
The thickness of the insulating film 10 can be selected in a suitable range in consideration of sufficient electrical insulation, the thickness of the metal foil laminated plate, flexibility, and the like, and is preferably 5 to 50 μm. Preferably, it is 7 to 45 μm.

The adhesive resin layer 20 is composed (bonded) of the adhesive composition for a circuit board having the above structure, and the thickness thereof is the interfacial adhesion with the insulating film, the flexibility of the laminated board, and the adhesion. From the viewpoint of strength and the like, it is preferably 1 to 50 μm, more preferably 3 to 30 μm.

Examples of the metal foil 30 include those having a conductive metal foil, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and alloys thereof. Copper foil or stainless steel foil is preferably used from the viewpoints of conductivity, ease of handling, price and the like. As the copper foil, any one produced by a rolling method or an electrolytic method can be used.
The thickness of the metal leaf is such that it has electrical conductivity, interfacial adhesion with an insulating film, flexibility of laminated plates, improvement of bending resistance, easy formation of fine patterns in circuit processing, and conductivity between wirings. A suitable range can be set in consideration of the above points, for example, in the range of 1 to 35 μm, more preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.
Further, in the metal foil to be 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. In particular, it is preferably in the range of 0.2 to 2.0 μm.

In the production of the circuit board laminate (for example, FIG. 1 or FIG. 2) having such a structure, for example, the circuit board adhesive composition of the present invention having the above structure is formed on the insulating film 10. After coating to form an adhesive resin layer 20, it is dried to a semi-cured state, and then a metal foil 30 is laminated on the adhesive resin layer 20 and heat-bonded (heat-laminated). Manufactures laminated boards for circuit boards colored in black, white, etc. with low rate and dielectric adjacency and excellent properties such as adhesiveness, heat resistance, dimensional stability, and flame retardancy without color unevenness or agglomerates. can do. At this time, the final flexible metal leaf laminate can be obtained by completely curing the semi-cured adhesive resin layer 20 by post-curing the flexible metal leaf laminate.

[Coverlay film]
Next, the coverlay film of the present invention is a coverlay film in which an insulating film and an adhesive layer are formed on at least one surface of the insulating film, and the adhesive layer is a circuit board having the above configuration. It is characterized by being an adhesive composition for use.
FIG. 3 is a schematic view showing an example of an embodiment of the coverlay film of the present invention in a cross-sectional manner.
The coverlay film C of the present embodiment is used as a surface protective film or the like for a flexible printed wiring board (FPC), and has an adhesive resin layer 50 formed on an insulating film 40. A separator (release film) 60 such as paper or PET film serving as a protective layer is bonded onto the adhesive resin layer 50. The separator (release film) 60 is provided as needed 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 above-mentioned laminated board for circuit boards, and is, for example, polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (). Select from the group consisting of PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK). One or more types of films can be mentioned.
Further, the film formed from these materials is preferably provided with a film whose surface is further surface-treated with low-temperature plasma or the like from the viewpoint of further improving the interfacial adhesion with the adhesive resin layer 50. Can be used.
In particular, considering the heat resistance, dimensional stability, mechanical properties, etc. of the coverlay film, a polyimide (PI) film is preferable, and a polyimide film treated with low temperature plasma is particularly preferable to be used as the coverlay film.
The thickness of the insulating film 40 can be selected in a suitable range in consideration of sufficient electrical insulation, protection, flexibility, etc., preferably 5 to 200 μm, more preferably 7 to 7. 100 μm is desirable.

The adhesive resin layer 50 is composed (bonded) of the adhesive composition for a circuit board having the above configuration, and its thickness is determined from the viewpoint of interfacial adhesion to an insulating film, adhesive strength, and the like. It is preferably 1 to 50 μm, more preferably 3 to 30 μm.

The coverlay film of the present invention having the above-mentioned structure is obtained by using a comma roll coater or a reverse coating of the adhesive composition for a circuit board of the present invention, which is colored black, white, etc. without color unevenness or agglomerates. It is applied onto the insulating film 40 using a roll coater or the like to form an adhesive layer, and dried to a semi-cured state (a state in which the curing reaction is progressing in a dry state or a part thereof). Next, by laminating the separator (release film) 60 which is the protective layer described above, the relative dielectric constant and the dielectric tangent are low, and excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy are obtained. Coverlay film having can be manufactured.

[Prepreg]
The prepreg of the present invention aggregates at least the color unevenness having the above-mentioned structure on a structure formed by one or more kinds of fibers selected from the group consisting of carbon fibers, cellulose fibers, glass fibers, or aramid fibers. It is characterized in that it is impregnated with the adhesive composition for a circuit board of the present invention, which is colored in black, white or the like.
In the present invention, the prepreg can be used as a constituent material for a multilayer flexible printed wiring board or the like, and is a dust-free, low-flow prepreg. The fibers are impregnated with the above-mentioned adhesive composition and then dried. It can be provided as a semi-cured sheet or the like.

Examples of the fiber used for this prepreg include one or more kinds of fibers selected from the group consisting of carbon-based fiber, cellulose-based fiber, glass-based fiber, and aramid-based fiber, and specifically, E glass fiber and D glass. Examples thereof include one or more fibers selected from the group consisting of fibers, NE glass fibers, H glass fibers, T glass fibers, and aramid fibers. In particular, in order to reduce the relative permittivity and dielectric loss coefficient of prepreg to the maximum, NE glass fiber (relative permittivity about 4.8, dielectric loss coefficient) having a lower relative permittivity and dielectric loss coefficient than other glass fibers It is preferable to use about 0.0015).

The prepreg is configured to have a thickness of 15 to 500 μm, and is preferably thinner, about 15 to 50 μm, for use in a circuit board.
The prepreg of the present invention configured in this way has low relative permittivity and dielectric loss tangent, and has adhesiveness, heat resistance, and dimensional stability when used as a material that also adheres to interlayer constituent materials such as multilayer flexible printed wiring boards. Provided is a prepreg colored in black, white, etc., which has excellent properties such as property and flame retardancy and has no color unevenness or agglomerates.

〔Electronics〕
In the present invention, the electronic device uses the heat-curable resin insulating material obtained from the heat-curable resin compositions of the first to fourth inventions, for example, excellent electrical characteristics (low specific dielectric constant, Various electronic devices that require low dielectric normal contact) and electrical insulation, such as thin mobile phones, game machines, router devices, WDM devices, personal computers, televisions, home servers, thin displays, hard disks, printers, DVD devices, etc. , Can be used as an insulating material for the main body and parts of various electronic devices.

In the present invention, the heat-curable resin compositions of the first to fourth inventions described above are colored with pigments and dyes to provide functions such as hiding property, optical properties, light-shielding property, light reflectivity, and design property. Even if it is, it is colored in black, white, etc., which has excellent electrical characteristics such as heat resistance, mechanical properties, slidability, insulation, low dielectric constant, low dielectric adjacency, and excellent workability, without color unevenness or agglomerates. A cured product of a heat-curable resin composition, an insulating material, a flexible printed wiring board including the above circuit board using an adhesive composition for a circuit board, a coverlay film, an electronic device, and further, a heat-curable resin composition thereof. Using films and insulating materials, insulating films, interlayer insulating films for wiring boards, surface protection layers, sliding layers, release layers, fibers, filter materials, wire coating materials, bearings, paints, heat insulating shafts, trays, seamless belts, etc. It can be suitably used for various belts, tapes, tubes and the like.

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

[Preparation of Fluorine Resin Micropowder Dispersion, Fluorine Resin Micropowder Coloring Material Dispersion, Coloring Material Dispersion]
The fluororesin micropowder dispersion, the fluororesin micropowder coloring material dispersion, and the coloring material dispersion used in each of the thermosetting resin compositions of Examples and Comparative Examples were prepared by each of the preparation methods shown below.

(Preparation of fluororesin micropowder dispersion)
In the formulation shown in Table 1 below, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is sufficiently stirred and mixed and dissolved in a non-aqueous solvent, and then PTFE micropowder is used as a fluororesin micropowder. Was added, and further stirring and mixing was performed. 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 a fluororesin micropowder dispersion A.

(Preparation of fluororesin micropowder colored material dispersion)
In the formulation shown in Table 2 below, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is sufficiently stirred and mixed and dissolved in a non-aqueous solvent, and then PTFE micropowder is used as a fluororesin micropowder. A black pigment or a white pigment was added as a coloring material, and the mixture was further stirred and mixed. Then, the obtained PTFE + pigment mixed solution was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare pigment-containing fluororesin micropowder coloring material dispersions B and C.

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

(Preparation of colored material dispersion)
In the formulation shown in Table 3 below, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group is sufficiently stirred and mixed and dissolved in a non-aqueous solvent, and then a black pigment or a white pigment is added as a coloring material. Then, further stirring and mixing was performed. Then, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to prepare colored material dispersions D and E.

[Examples 1 to 10 and Comparative Examples 1 to 6: Preparation of thermosetting resin composition]
Using the fluororesin micropowder dispersion, the fluororesin micropowder coloring material dispersion, and the coloring material dispersion prepared above, they are mixed according to the formulation shown in Table 4 below, and then sufficiently stirred with a disper. A thermosetting resin composition was obtained.
Each of the obtained thermosetting resin compositions was evaluated for sedimentability and redispersibility by the following evaluation method.
These results are shown in Table 4 below.

(Evaluation method of sedimentation and redispersibility)
For each thermosetting resin composition, the settling state of various particles (fluorine-based resin micropowder, pigment particles) was allowed to stand at room temperature (25 ° C.) for 30 minutes, and then visually confirmed. Each state of redispersibility was sensorimetrically evaluated.
Evaluation criteria for sedimentation:
◯: No settling layer at the bottom △: No settling layer at the bottom (easy redispersion)
×: A subsidence layer can be seen at the bottom (difficult to redisperse)
Evaluation criteria for redispersibility:
◯: Easily redispersed when the sediment was agitated ×: Difficult to redisperse when the sediment was agitated

As is clear from the results in Table 4 above, in Examples 1 to 10 which are the scope of the present invention, some precipitates were observed in Examples 2, 4, 7, and 9 using titanium oxide, but any of them It was easily redistributed and was at the level of problems in terms of usability.
On the other hand, in Comparative Examples 1 to 3, Comparative Examples 1 and 2 are ordinary thermosetting resin compositions containing no fluororesin micropowder and coloring material (pigment), and evaluation of sedimentability and redispersibility. On the other hand, Comparative Examples 3 to 6 are thermosetting resin compositions containing a coloring material (black pigment, white pigment) that does not contain fluororesin micropowder.
Moreover, when the water content of each of the obtained thermosetting resin compositions of Examples 1 to 10 and Comparative Examples 1 to 6 was measured, each water content by the Karl Fischer method was in the range of 800 to 2500 ppm, respectively. It was.

[Examples 11 to 20, Comparative Examples 7 to 12: Evaluation of Insulating Material Composition]
Using the thermosetting resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 6 as the insulating material composition, the entire surface of one side of the polyimide film (thickness: 25 μm) has a thickness of about 25 μm after drying. The insulating material composition was evaluated as having been cured by applying it to a uniform thickness using a coater, drying it at about 120 ° C. for about 10 minutes, and then heating it at 180 ° C. for 60 minutes to cure it. A sample was prepared.

(Evaluation of electrical characteristics)
The relative permittivity of the obtained evaluation sample was measured at 1 GHz using an impedance analyzer (Impedence Analyzer) according to the test standard of JIS C6481-1996. Moreover, the volume resistivity was measured according to the test standard of JIS C2151. The results are shown in Table 5 below.

As shown in Table 5 above, even if carbon black is contained as the black pigment, the evaluation samples obtained by curing the insulating material compositions in Examples 11, 13, 15, 16, 18 and 20 do not contain the pigment. It was found that the relative permittivity was low and the volume resistance was high as compared with Comparative Examples 7 and 8 and Comparative Examples 9 and 11 containing carbon black as a black pigment. Further, it was found that the evaluation samples in which the insulating material compositions in Examples 12, 14, 17 and 19 were cured had a lower relative permittivity than those in Comparative Examples 10 and 12, even if titanium oxide was contained.

[Evaluation of Adhesive Composition for Circuit Boards]
The thermosetting resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were used as the adhesive composition for a circuit board.

(Examples 21 to 30, Comparative Examples 13 to 18: Laminated boards for circuit boards)
The adhesive compositions for circuit boards obtained in Examples 1 to 10 and Comparative Examples 1 to 6 were applied to the entire surface of one side of the polyimide film (thickness: 25 μm) so that the thickness after drying was about 10 μm. After applying to a uniform thickness using a coater to form an adhesive resin layer, this was dried to a semi-cured state. Then, a similar adhesive resin layer was formed on the opposite surface of the polyimide film to prepare an adhesive sheet.
Next, copper foil (thickness: about 12 μm, matte surface roughness (Rz): 1.6 μm) was laminated on both sides of the adhesive sheet, and then crimped at 170 ° C. at a pressure of ^{40 kgf / cm 2.} After 5 hours at 170 ° C., it was cured to produce a laminated board for a circuit board.
The obtained laminated boards for circuit boards of Examples 21 to 30 and Comparative Examples 13 to 18 were used as evaluation samples.

(Examples 31-40, Comparative Examples 19-24: Coverlay film)
The adhesive composition for each circuit board obtained in Examples 1 to 10 and Comparative Examples 1 to 6 was applied to the entire surface of one side of the polyimide film (thickness: 25 μm) so that the thickness after drying was about 25 μm. A coverlay film was produced by applying a uniform thickness using a coater, drying at about 120 ° C. for about 10 minutes, and then laminating a release-coated release paper having a thickness of 125 μm.
The coverlay films of Examples 31 to 40 and Comparative Examples 19 to 24 were laminated in the order of the polyimide film of the coverlay film / the adhesive surface of the coverlay film / copper foil (12 μm), and then this was laminated at 180 ° C. and 40 kgf / cm. ^An evaluation sample was prepared by hot pressing at pressure 2 for 60 minutes.

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

(Evaluation method of heat resistance)
A sample having a size of 50 mm × 50 mm was prepared, subjected to moisture absorption treatment at 120 ° C., 0.22 MPa for 12 hours, and then treated at 260 ° C. for 1 minute, and the state of the sample was observed with the naked eye. As the evaluation criteria, "○" was given if there were no abnormalities such as peeling, deformation, or swelling, and "x" was given if there were any abnormalities such as peeling, deformation, or swelling.

(Evaluation method of adhesive strength)
A sample cut into 100 mm × 10 mm was prepared, and the adhesive strength of the adhesive layer formed using Tensilon was measured.

The evaluation results of the laminated board for circuit boards are shown in Table 6 below, and the evaluation results of the coverlay film are shown in Table 7 below.

[Evaluation of prepreg]
(Examples 41 to 50, Comparative Examples 25 to 30: prepreg)
A NE glass cloth having a thickness of about 100 μm was impregnated with the adhesive compositions for circuit boards obtained in Examples 1 to 10 and Comparative Examples 1 to 6, and then dried at about 120 ° C. for about 10 minutes. A thermosetting prepreg having an overall thickness of about 125 μm was produced.
After laminating the prepregs of Examples 41 to 50 and Comparative Examples 25 to 30 in the order of polyimide film (12.5 μm) / prepreg / polyimide (12.5 μm), this is 60 at 180 ° C. and a pressure of 40 ^{kgf / cm 2.} Hot press for minutes to prepare evaluation samples.

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

(Evaluation method of heat resistance)
A sample having a size of 50 mm × 50 mm was prepared, subjected to moisture absorption treatment at 120 ° C., 0.22 MPa for 12 hours, and then treated at 260 ° C. for 1 minute, and the state of the sample was observed with the naked eye. As the evaluation criteria, "○" was given if there were no abnormalities such as peeling, deformation, or swelling, and "x" was given if there were any abnormalities such as peeling, deformation, or swelling.

(Evaluation method of adhesive strength)
A sample cut into 100 mm × 10 mm was prepared, and the adhesive strength of the adhesive layer formed using Tensilon was measured.

The evaluation results of the prepreg are shown in Table 8 below.

As shown in Tables 6 and 7, the laminated boards for circuit boards of Examples 21 to 30 and the laminated boards for circuit boards using the thermosetting resin compositions of Examples 1 to 10 as the adhesive composition for circuit boards and Examples 31 to 31 Although the coverlay film of 40 is colored black or white, the circuit boards of Comparative Examples 13 to 18 using the thermosetting resin compositions of Comparative Examples 1 to 6 as the adhesive composition for the circuit board. It was found that the dielectric constant was lower than that of the coverlay film of Comparative Examples 19 to 24 and that the same heat resistance and adhesiveness could be obtained.
Further, as shown in Table 8 above, the prepregs of Examples 41 to 50 using the thermosetting resin compositions of Examples 1 to 10 are comparative examples even though they are colored black or white. It was found that the prepregs of Comparative Examples 25 to 30 using the thermosetting resin compositions 1 to 6 had a lower dielectric constant and the same heat resistance and adhesiveness could be obtained.

It is colored with organic pigments, inorganic pigments, and dye coloring materials, and has high insulation, heat resistance, and electrical properties, even if it has functions such as hiding properties, optical properties, light-shielding properties, light reflectivity, and design properties. A colored thermocurable resin composition having excellent workability (low dielectric constant, low dielectric normal contact) can be obtained, and a flexible printed wiring board including a circuit board using the thermocurable resin composition, a coverlay, etc. Electronic devices using insulating materials made of heat-curable resin compositions such as films, insulating films, and correlated insulating films for wiring boards, and surface protective layers and sliding layers using these heat-curable resin composition insulating materials. , Peeling layer, fiber, filter material, wire coating material, bearing, paint, heat insulating shaft, tray, various belts such as seamless belt, tape, tube and the like.

10 Insulating film 20 Adhesive resin layer (adhesive composition layer for circuit boards)
30 metal leaf

Claims (15)

At least, the amount of the fluororesin micropowder is 5 to 70% by mass based on the total solid content, and the amount of the fluororesin additive containing at least a fluorine-containing group and an oleophobic group is 0.1 based on the fluororesin micropowder. A thermosetting resin composition comprising ~ 20% by mass , a coloring material, and a resin composition containing a cyanate ester resin and / or an epoxy resin. The amount of the fluororesin micropowder is 5 to 70% by mass based on the total solid content, and the amount of the fluororesin additive containing at least a fluorine-containing group and an oleophobic group is 0.1 to 20% by mass based on the fluororesin micropowder. A thermosetting resin composition containing at least a fluororesin micropowder dispersion containing at least% and a non-aqueous solvent, a coloring material, and a resin composition containing a cyanate ester resin and / or an epoxy resin. Stuff. The amount of the fluororesin micropowder is 5 to 70% by mass based on the total solid content, and the amount of the fluororesin additive containing at least a fluorine-containing group and an oleophobic group is 0.1 to 20% by mass based on the fluororesin micropowder. % And a fluororesin micropowder dispersion containing at least 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 resin containing a cyanate ester resin and / or an epoxy resin. A thermocurable resin composition comprising, and at least, a composition. The amount of the fluororesin micropowder is 5 to 70% by mass based on the total solid content, and the amount of the fluororesin additive containing at least a fluorine-containing group and an oleophobic group is 0.1 to 20% by mass based on the fluororesin micropowder. A thermosetting resin containing at least a fluororesin micropowder coloring material dispersion containing at least%, a coloring material, and a non-aqueous solvent, and a resin composition containing a cyanate ester resin and / or an epoxy resin. Composition. The micropowder of the fluororesin is polytetrafluoroethylene, fluoroethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotri. The thermocurable resin according to any one of claims 1 to 4, which is a micropowder of one or more kinds of fluororesins selected from the group consisting of a fluoroethylene copolymer and polychlorotrifluoroethylene. Composition. The thermosetting resin composition according to any one of claims 1 to 5, wherein the coloring material is at least one selected from an inorganic pigment, an organic pigment, and a dye. The thermosetting resin composition according to any one of claims 1 to 5, wherein the coloring material is at least one selected from a carbon-based black pigment, an oxide-based black pigment, and a white pigment. In the fluorine-based resin micropowder dispersion or the fluorine-based resin micropowder coloring material dispersion , the average particle size based on the volume by the dynamic scattering method or the laser diffraction / scattering method of the dispersed fluorine-based resin micropowder is The thermocurable resin composition according to any one of claims 2 to 4, wherein the size is 10 μm or less. An insulating material composition obtained by using the thermosetting resin composition according to any one of claims 1 to 8. An adhesive composition for a circuit board, which is obtained by using the thermosetting resin composition according to any one of claims 1 to 8. The laminated board for a circuit board including at least a structure of an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is described in claim 10. A laminated board for a circuit board, which is an adhesive composition for a circuit board. The insulating film includes polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), and the like. The laminate for a circuit board according to claim 11, wherein the film is one or more selected from the group consisting of polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK). Board. An insulating film and a coverlay film in which an adhesive layer is formed on at least one surface of the insulating film, and the adhesive layer is the adhesive composition for a circuit board according to claim 10. Coverlay film featuring. The insulating film includes polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), and the like. The coverlay film according to claim 13, wherein the film is one or more selected from the group consisting of polyester, para-aramid, polylactic acid, nylon, polyparavanic acid, and polyetheretherketone (PEEK). The heat according to at least one of claims 1 to 8 on a structure formed of one or more kinds of fibers selected from the group consisting of carbon fibers, cellulosic fibers, glass fibers, or aramid fibers. A prepreg characterized by being impregnated with a cured resin composition.

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