CN112852257A

CN112852257A - Nonaqueous dispersion of fluorine-containing resin, heat-curable resin composition of fluorine-containing resin using same, and cured product thereof

Info

Publication number: CN112852257A
Application number: CN202110012272.3A
Authority: CN
Inventors: 佐藤厚志; 阿部寛史; 阪上正史; 铃木孝典
Original assignee: Mitsubishi Pencil Co Ltd
Current assignee: Mitsubishi Pencil Co Ltd
Priority date: 2016-05-25
Filing date: 2017-05-25
Publication date: 2021-05-28
Anticipated expiration: 2037-05-25
Also published as: KR20170133277A; TW201835201A; TWI794172B; CN107434945B; KR102399221B1; CN112852257B; CN107434945A

Abstract

The present invention relates to a nonaqueous dispersion of a fluorine-containing resin, a thermosetting resin composition of a fluorine-containing resin using the same, and a cured product thereof. [ problem ] to]Providing: a nonaqueous dispersion of a fluorine-containing resin, a thermosetting resin composition containing the same, a polyimide precursor solution composition, and the like, which have a fine particle diameter, a low viscosity, and excellent storage stability, can be suitably mixed with a resin material such as a thermosetting resin composition, can achieve a low dielectric constant and a low dielectric loss tangent, and can suppress a decrease in adhesion strength and adhesive strength, and are suitably used for an insulating layer of a printed wiring board, an adhesive for a circuit board, a laminate for a circuit board, a cover film, a prepreg, and the like. [ solution means ] to]A nonaqueous dispersion of a fluorine-based resin, characterized by containing at least: fine powder of a fluorine-based resin, fine urethane particles, a compound represented by the following formula (I) (wherein l, m, and n are positive integers), and a nonaqueous solvent.

Description

Nonaqueous dispersion of fluorine-containing resin, heat-curable resin composition of fluorine-containing resin using same, and cured product thereof

The present application is a divisional application of a nonaqueous dispersion having an application date of 2017, 5/25/No. 201710377232.2 and an application name of a fluororesin, a thermosetting resin composition containing a fluororesin using the same, and a cured product of the same.

Technical Field

The present invention relates to a nonaqueous dispersion of a fluororesin having a fine particle diameter, a low viscosity, and excellent storage stability, a thermosetting resin composition of a fluororesin using the same, a cured product thereof, a polyimide precursor solution composition, and the like.

Background

In recent years, electronic devices have been required to have higher communication speeds, along with higher speeds and higher functions. Among these, various electronic device materials are required to have a low dielectric constant and a low dielectric loss tangent, and also insulating materials, substrate materials, and the like are required to have a low dielectric constant, a low dielectric loss tangent, and the like of thermosetting resins that can be used therein.

As a material having a low dielectric constant and a low dielectric loss tangent, polytetrafluoroethylene (PTFE, relative dielectric constant 2.1) having the most excellent characteristics among resin materials is attracting attention, and a method of melt-mixing PTFE into various resin materials, for example, a composition of: which is a composition comprising at least 50 mass% of PTFE and an effective amount of a polyarylene ether ketone necessary to impart melt processability to the composition, characterized in that at least 20 mass% of the aforementioned PTFE has at least 10⁸Pa · s melt viscosity (see, for example, patent document 1).

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

As a method for solving the problem, the present applicant has proposed a method for producing an oily solvent dispersion of PTFE and adding the oily solvent dispersion to a thermosetting resin material or the like, for example, an oily solvent dispersion of PTFE characterized by containing 5 to 70 mass% of PTFE having a primary particle diameter of 1 μm or less and 0.1 to 40 mass% of a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group with respect to the mass of polytetrafluoroethylene, and having a water content of 20000ppm or less based on the karl fischer method as a whole (for example, see patent documents 2 and 3).

The resin material to which PTFE is added as described above can exhibit an effect in terms of low dielectric constant and low dielectric loss tangent which have not been achieved so far, but has a problem in terms of slightly lowering adhesion strength and adhesive strength when resins are bonded to each other, a resin is bonded to a metal, and the like due to non-adhesiveness of PTFE, and further improvement of adhesion strength and adhesive strength is desired.

On the other hand, thermosetting resin compositions using epoxy resins, cyanate resins, and the like are widely used for electric and electronic applications because of their excellent heat resistance, electrical insulation, adhesiveness, and the like.

In general, a thermosetting resin composition using an epoxy resin, a cyanate resin, or the like, a cured product thereof, or the like is suitably used for an electronic substrate material, an insulating material, an adhesive material, or the like, and for example, as a material such as a sealing material, a copper-clad laminate, an insulating coating material, a composite material, an insulating adhesive, or the like used for an electronic component, and further, as an adhesive composition for a circuit substrate used for manufacturing a circuit substrate, a laminate for a circuit substrate using the same, a cover film, a prepreg, an insulating layer of a multilayer printed wiring board for an electronic device, or the like.

These thermosetting resin compositions and insulating materials using the same are required to be colored in white, black, other colors, and the like in order to impart other functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties.

For example, in a multilayer printed wiring board used for a component used in a place where a high-voltage electric/electronic component is installed, a semiconductor mounting package, and the like, a black-based thermosetting resin composition is mainly used because black is the main color. Further, white thermosetting resin compositions and the like are used as printed wiring boards on which light emitting elements such as LEDs (light emitting diodes) are mounted, as reflecting plates for light emitting elements, as reflecting materials for organic EL light emission, and as substrates for metal layer white films, and demand is increasing year by year.

As the thermosetting resin composition colored in white, black or the like, and the insulating material composition using the same, for example, there are known:

1) an epoxy resin composition characterized by being an acid anhydride-curable epoxy resin composition in which a composition comprising an acid anhydride and an inorganic filler and a curing accelerator is used as an agent a and an epoxy resin is used as an agent B, wherein the agent B comprises a coloring agent having a quinacridone structure and a diazo dye (see, for example, patent document 4);

2) a method for producing a resin composition, in order to provide a prepreg or an insulating resin sheet free from color unevenness and aggregates, is characterized by comprising the steps of: a step (1) of dissolving and/or dispersing the colorant (B) in a dispersion liquid in which the inorganic filler (A) is dispersed in a solvent; and, step (2), thereafter, dissolving (C) a novolac-type epoxy resin (see, for example, patent document 5);

3) to provide a white curable resin composition which has high reflectance, is suppressed in the decrease of reflectance and the coloring due to deterioration with time, and can effectively utilize light of an LED or the like when used for a printed wiring board on which a light-emitting element such as an LED is mounted and a reflector for a light-emitting element, a white thermosetting resin composition comprising: (A) rutile titanium oxide and (B) a thermosetting resin (see, for example, patent document 6);

4) in order to provide a thermosetting resin composition for light reflection having sufficient light reflectance and moldability and excellent heat-resistant coloring property, a substrate for mounting an optical semiconductor element using the same, a method for producing the same, and an optical semiconductor device, a thermosetting resin composition for light reflection contains: an epoxy resin having specific physical properties, a curing agent, and a white pigment (see, for example, patent document 7);

5) in order to provide a thermosetting resin composition which is excellent in insulation properties and heat resistance, can achieve surface flatness, adhesion properties, and curability at a high level and in a well-balanced manner, and is excellent in both high-temperature insulation resistance and solvent resistance required in a production process, a cured product thereof, and a display member using the same, a thermosetting resin composition comprising: (a) a carboxyl group-containing resin as a thermosetting component, (b) an epoxy resin, (c) a black colorant such as carbon black, and (d) at least 1 selected from the group consisting of barium sulfate, silica, and talc (for example, see patent document 8); and the like.

However, the thermosetting resin compositions and the like described in patent documents 4 to 8 have the following problems: when colored with a coloring material such as an organic pigment or an inorganic pigment, the resultant cured product, an insulating material, a cover film, and electrical characteristics (relative permittivity, dielectric loss tangent) and insulating properties of a flexible printed wiring board are affected.

In particular, when carbon black is used to color black, there is a problem that the insulation properties are deteriorated and the relative permittivity and the dielectric loss tangent are deteriorated, and thus the use of carbon black is not suitable for high-speed communication, high-speed processing, and the like.

Therefore, in colored thermosetting resin compositions and the like, there are technical problems, limitations, and the like in terms of electrical characteristics (low dielectric constant, low dielectric loss tangent), insulation properties, and the like, and the current situation is as follows: a thermosetting resin composition which provides functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties and further improves electrical properties (low dielectric constant and low dielectric loss tangent) and insulation properties, an insulating material composition using the same, an adhesive composition for a circuit board, a laminate for a circuit board, a cover film, a prepreg, a flexible wiring board, and the like are required.

On the other hand, conventionally, polyimides contained in polyimide films and the like are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation, chemical resistance, mechanical properties, and the like. For example, when polyimide is used as a film, it is used as an insulating base material for electronic circuit materials, and it is also used by processing it into an adhesive film or an adhesive tape. When used as a coating agent, the polyimide precursor solution composition may be coated, dried, and then heat-treated to be imidized, or may be used as an insulating layer of an electronic circuit (interlayer insulating material of a multilayer wiring board), a surface protective film of an organic EL element or a semiconductor element, a heat-resistant protective film, an abrasion-resistant film, or the like.

Generally, a polyimide film is used as a base film of a flexible printed multilayer circuit board by bonding the polyimide film to a copper foil using an adhesive, or processing the polyimide film into a laminate (copper-clad polyimide film) composed of a film layer and a copper foil by a vapor deposition method, a plating method, a sputtering method, a casting method, or the like.

The copper-clad laminate is used by processing a copper foil portion to form a wiring pattern or the like, and the wiring pattern is covered and protected by an insulating cover film or the like. Further, a polyimide film is mainly used as a base material of the cover film.

There is a demand for a cover film, a flexible printed wiring board, or the like using such a polyimide film or the like to be colored in white, black, other colors, or the like in order to impart other functions such as concealing properties, optical properties, light shielding properties, light reflecting properties, and design properties.

For example, white polyimide materials such as white polyimide films are used as heat-resistant lightweight white materials, as reflective materials for LEDs (light emitting diodes) and organic ELs, and as substrates for metal layer white films, and are suitably used for LEDs, organic ELs, flexible printed circuit boards on which other light emitting elements are mounted, and the like.

On the other hand, with recent reduction in film thickness and cost of colored polyimide materials such as black, requirements for shielding properties and optical properties of electronic parts and mounted parts to be protected have been increasing, and the demand for colored polyimide materials such as black having shielding properties and light-shielding properties has been increasing year by year.

As polyimide materials such as polyimide films colored in white, black, or the like, for example, there are known:

1) a white polyimide film obtained by casting and drying a liquid obtained by mixing a white pigment into a polyamic acid obtained by reacting a specific diamine component with an aromatic tetracarboxylic acid on a support to obtain a polyimide precursor film, and imidizing the polyimide precursor film (see, for example, patent document 9);

2) a multilayer polyimide film having a light-shielding property or a light-reflecting property, in which a pigment-containing polyimide layer is laminated on one surface or both surfaces of a polyimide layer, and a polyimide composed of a specific component and constituting the pigment-containing polyimide layer (for example, see patent document 10);

3) a colored light-shielding polyimide film formed from a resin composition containing a polyimide having a specific repeating unit, a colored coloring material, and a white pigment (for example, see patent document 11);

4) a black polyimide film comprising a perylene black pigment (a) having a benzimidazole skeleton and silica (B), wherein the total weight of the pigments (a) and (B) and the weight ratio of the pigment (a) to the polyimide film as a whole are set to specific ranges (see, for example, patent document 12);

5) a pigment-added polyimide film containing at least 2 or more pigments, wherein the polyimide film has a gloss and a thermal expansion coefficient within specific ranges (see, for example, patent document 13);

6) a colored base material polyimide film which is a polyimide polymer obtained by reacting a specific diamine monomer with a specific dianhydride monomer, comprising: a matting agent comprising polyimide particles and 1 or more kinds of coloring pigments (see, for example, patent document 14); and the like.

However, the colored polyimide materials such as the colored polyimide films described in patent documents 9 to 14 have the following problems: when colored with a coloring material such as an organic pigment or an inorganic pigment, the electrical characteristics (relative permittivity, dielectric loss tangent) and insulation properties of a cover film or a flexible printed wiring board are affected.

In particular, when carbon black is used to color black, there is a problem that the insulation property is lowered and the relative permittivity and dielectric loss tangent are deteriorated, and therefore, the use of carbon black is not suitable for high-speed communication, high-speed processing, and the like.

Therefore, in the colored polyimide material and the like, there are technical problems, limitations, and the like in terms of electrical characteristics (low dielectric constant, low dielectric loss tangent), insulation properties, and the like, and the current situation is as follows: a polyimide precursor solution composition which provides functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties, and further improves electrical properties (low dielectric constant and low dielectric loss tangent) and insulation properties, and a polyimide film using the same are required.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2001-49068 (claims, examples, etc.)

Patent document 2: japanese laid-open patent publication (claims, examples, etc.) No. 2015-199901

Patent document 3: japanese laid-open patent publication (claims, examples, etc.) No. 2015-199903

Patent document 4: japanese laid-open patent publication No. 2001-294728 (claims, examples, etc.)

Patent document 5: japanese laid-open patent publication No. 2009-114377 (claims, examples, etc.)

Patent document 6: japanese laid-open patent publication No. 2010-275561 (claims, examples, etc.)

Patent document 7: japanese laid-open patent publication No. 2013-155344 (claims, examples, etc.)

Patent document 8: japanese laid-open patent publication (claims, examples, etc.) No. 2015-78290

Patent document 9: japanese laid-open patent publication No. 2008-1699237 (claims, examples, etc.)

Patent document 10: international publication WO2010/126047 (claims, examples, etc.)

Patent document 11: japanese laid-open patent publication No. 2012-167169 (claims, examples, etc.)

Patent document 12: japanese laid-open patent publication No. 2013-28767 (claims, examples, etc.)

Patent document 13: japanese patent laid-open No. 2014-141575 (claims, examples, etc.)

Patent document 14: japanese laid-open patent publication (claims, examples, etc.) No. 2015-44977

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in order to solve the above conventional problems and current situations, and a1 st object thereof is to provide: a nonaqueous dispersion of a fluororesin having a fine particle diameter, a low viscosity, excellent storage stability, suitable for mixing with various resin materials, capable of achieving a low dielectric constant and a low dielectric loss tangent and capable of suppressing a decrease in adhesion strength and adhesion strength, a thermosetting resin composition of a fluororesin using the same, and a cured product thereof; the 2 nd purpose lies in, provide: a colored thermosetting resin composition suitable for thermosetting resin compositions, insulating material compositions using the same, adhesive compositions for circuit boards, thermosetting resin compositions of fluorine-containing resins for laminate plates for circuit boards, cover films, prepregs, flexible wiring boards, and the like, insulating material compositions using the same, and the like, which are excellent in high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric loss tangent), processability, and the like, even if colored with pigments or dyes to impart other functions such as concealing properties, optical properties, light shielding properties, light reflection properties, design properties, and the like; the 3 rd purpose lies in, provide: even if colored with a pigment or dye to impart other functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties, the colored polyimide precursor solution composition is suitable for a polyimide, a polyimide film, a cover film using the same, a flexible printed wiring board, and the like, and the polyimide film using the same has high insulation properties, heat resistance, electrical properties (low dielectric constant and low dielectric loss tangent), and processability.

Means for solving the problems

The present inventors have conducted intensive studies on the above conventional problems and the like, and as a result, have found that: the following inventions 1 to 10 can provide the non-aqueous dispersion of the fluorine-containing resin of the above object 1, the thermosetting resin composition of the fluorine-containing resin using the dispersion, and the cured product thereof, the thermosetting resin composition of the fluorine-containing resin of the above object 2, the insulating material composition using the thermosetting resin composition, the polyimide precursor solution composition of the above object 3, the polyimide film using the polyimide precursor solution composition, and the like, and the present invention has been completed.

That is, the present invention 1 is a non-aqueous dispersion of a fluorine-based resin, characterized by containing at least: fine powder of a fluorine-based resin, fine urethane particles, a compound represented by the following formula (I), and a nonaqueous solvent.

[ in the formula (I), I, m and n are positive integers ]

The present invention 2 is a non-aqueous dispersion of a fluorine-based resin, characterized by containing at least: a fine powder of a fluorine-based resin, a thermoplastic elastomer, a compound represented by the formula (I), and a nonaqueous solvent.

The fine powder of the fluorine-based resin is preferably fine powder of 1 or more fluorine-based resins selected from the group consisting of polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene.

The fine powder of the fluorine-based resin is preferably contained in an amount of 5 to 70% by mass, and the fine urethane particles are preferably contained in an amount of 0.1 to 20% by mass based on the mass of the fine powder of the fluorine-based resin.

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

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

The thermosetting resin composition of the fluorine-containing resin according to the invention 1 or 2 is characterized by containing at least: the non-aqueous dispersion of a fluorine-containing resin according to claim 1 or 2 and the resin composition containing a cyanate ester resin and/or an epoxy resin are characterized in that the cured product is obtained by curing a thermosetting resin composition of each of the fluorine-containing resins.

The thermosetting resin composition of the fluorine-containing resin according to claim 2 is characterized by containing at least: the non-aqueous dispersion of a fluorine-containing resin according to claim 2 and the resin composition containing a thermosetting resin are characterized in that the cured product is obtained by curing the thermosetting resin composition of each of the fluorine-containing resins.

The present invention according to claim 3 is a thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin.

The present invention according to claim 4 is a thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a nonaqueous solvent.

The present invention according to claim 5 is a thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluororesin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a resin composition containing a cyanate ester resin and/or an epoxy resin, the fluororesin fine powder dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent.

The present invention according to claim 6 is a thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluororesin fine powder coloring material dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a nonaqueous solvent.

The coloring material is preferably at least 1 selected from the group consisting of inorganic pigments, organic pigments, and dyes, and the coloring material is preferably at least 1 selected from the group consisting of carbon-based black pigments, oxide-based black pigments, and white pigments.

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

The insulating material composition and the adhesive composition for circuit boards according to the invention 3 to 6 are characterized by being obtained by using the thermosetting resin composition containing the fluorine-containing resin according to any one of the invention 3 to 6.

The circuit board laminate according to any one of the present invention 3 to 6 is characterized by comprising: an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is an adhesive composition for a circuit board obtained by using a thermosetting resin composition containing a fluorine-containing resin according to any one of the invention 3 to 6.

The insulating film is preferably 1 or more selected from the group consisting of Polyimide (PI), Liquid Crystal Polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyether imide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, poly-parabanic acid, and polyether ether ketone (PEEK).

The cover film according to any one of claims 3 to 6 is characterized by comprising an insulating film and an adhesive layer formed on at least one surface of the insulating film, wherein the adhesive layer is an adhesive composition for a circuit board obtained by using a thermosetting resin composition containing a fluorine-containing resin according to any one of claims 3 to 6.

The prepreg according to any one of claims 3 to 6 is characterized in that a structure comprising 1 or more types of fibers selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, and aramid-based fibers is impregnated with at least the thermosetting resin composition containing the fluorine-containing resin according to any one of claims 3 to 6.

The present invention 7 is a polyimide precursor solution composition characterized by containing at least: a fine powder of a fluorine-based resin, a compound represented by the formula (I), a coloring material, and a polyimide precursor solution.

The present invention according to 8 is a polyimide precursor solution composition characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a nonaqueous solvent.

The present invention according to claim 9 is a polyimide precursor solution composition containing at least: a fluorine-based resin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent.

The 10 th aspect of the present invention is a polyimide precursor solution composition containing at least: a fluorine-based resin fine powder coloring material dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a nonaqueous solvent.

The polyimide precursor solution preferably contains at least: a tetracarboxylic acid dihydrate and/or a derivative thereof, and a diamine compound.

The polyimide, the polyimide film, and the polyimide insulating film according to any one of the inventions 7 to 10 are obtained by using the polyimide precursor solution composition according to any one of the inventions 7 to 10.

The coverlay film and the flexible printed wiring board according to any one of the inventions 7 to 10 are characterized by using a polyimide film obtained by using the polyimide precursor solution composition according to any one of the inventions 7 to 10.

ADVANTAGEOUS EFFECTS OF INVENTION

The non-aqueous dispersion of a fluororesin according to claim 1 or 2 has a small particle diameter, a low viscosity, an excellent storage stability, and is suitable for mixing with various resin materials, and the thermosetting resin composition containing a fluororesin using the non-aqueous dispersion according to claim 1 or 2 and the cured product thereof can achieve a low dielectric constant and a low dielectric loss tangent and suppress a decrease in adhesion strength and adhesive strength.

According to the present invention 3 to 6, there is provided: a colored thermosetting resin composition suitable for a fluorine-containing resin, which is colored to have excellent properties such as high insulation, heat resistance, electrical properties (low dielectric constant and low dielectric loss tangent), and processability even if a pigment or a dye is used for coloring to impart functions such as concealing properties, optical properties, light-shielding properties, light reflection properties, and design properties, an insulating material composition using the same, an adhesive composition for a circuit board, a laminate for a circuit board, a cover film, a prepreg, and a flexible printed wiring board.

Further, even if the insulating material composition, the adhesive composition for circuit boards, the laminate for circuit boards, the cover film, the prepreg, the flexible printed wiring board, and the like, which are made of the thermosetting resin composition containing the fluorine-containing resin according to the present invention 3 to 6 are colored with a coloring material such as an organic pigment, an inorganic pigment, or a dye to impart functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties, the colored insulating material composition, the adhesive composition for circuit boards, the laminate for circuit boards, the cover film, the prepreg, the flexible printed wiring board, and the like, which are excellent in high insulation properties, heat resistance, electrical properties (low dielectric constant, low dielectric loss tangent), processability, and the like, can be obtained.

According to the present invention 7 to 10, even if a pigment or dye is colored to impart functions such as concealing properties, optical properties, light shielding properties, light reflecting properties, and design properties, the colored polyimide precursor solution composition is suitable for a polyimide, a polyimide film, a cover film using the same, a flexible wiring board, and the like, and has excellent insulating properties, heat resistance, electrical properties (low dielectric constant, low dielectric loss tangent), and processability.

Further, the polyimide, polyimide film, polyimide insulating film, cover film, flexible printed wiring board, and the like, which are produced using the polyimide precursor solution composition according to the present invention 7 to 10, can provide colored polyimide, polyimide film, polyimide insulating film, cover film, flexible printed wiring board, and the like, which are excellent in high insulation, heat resistance, electrical characteristics (low dielectric constant, low dielectric loss tangent), processability, and the like, even when colored with a coloring material such as an organic pigment, an inorganic pigment, or a dye to impart functions such as hiding properties, optical characteristics, light-shielding properties, light-reflecting properties, and design properties.

Drawings

Fig. 1 is a schematic diagram showing an example of an embodiment of a circuit board laminate according to the present invention 3 to 6 in a cross-sectional form.

Fig. 2 is a schematic diagram showing another example of the embodiment of the circuit board laminated board according to the 3 rd to 6 th inventions in a cross-sectional form.

Fig. 3 is a schematic view showing an example of an embodiment of the cover film according to the 3 rd to 10 th inventions in a cross-sectional form.

Description of the reference numerals

10 insulating film

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

30 metal foil

Detailed Description

Hereinafter, embodiments of the present invention 1 to 10 will be described in detail for each invention. The components common to the respective inventions are described in detail in the first invention 1 and the like, and the components common to the respective inventions are described in detail in the following description of the invention 2 and the like, and the detailed description thereof is omitted.

[ invention 1: nonaqueous dispersion of fluorine-based resin ]

The non-aqueous dispersion of a fluororesin according to claim 1 is characterized by containing at least: fine powder of a fluorine-based resin, fine urethane particles, a compound represented by the following formula (I), and a nonaqueous solvent.

[ in the formula (I), I, m and n are positive integers ]

Examples of the fine powder of the fluorine-based resin that can be used in the present invention 1 include: fine powders of at least 1 fluorine-based resin selected from the group consisting of Polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy Polymer (PFA), Chlorotrifluoroethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and Polychlorotrifluoroethylene (PCTFE), and preferably those having a primary particle diameter of 1 μm or less.

Among the fine powders of the fluorine-based resin, polytetrafluoroethylene (PTFE, relative permittivity 2.1) having the most excellent characteristics is particularly desired to be used as a material having a low relative permittivity and a low dielectric loss tangent among resin materials.

The fine powder of the fluorine-based resin can be obtained by an emulsion polymerization method, and can be obtained by a method generally used in, for example, a method described in a manual of fluororesin (edited by filial minister of black chuan, journal industry press). Further, the fine powder of the fluororesin obtained by the emulsion polymerization is aggregated and dried, and recovered as fine powder in the form of secondary particles in which the primary particles are aggregated, and various methods for producing fine powders generally used can be used.

The fine powder of the fluororesin preferably has a primary particle diameter of 1 μm or less, and in the nonaqueous dispersion, the average particle diameter is preferably 1 μm or less.

In terms of stable dispersion in a nonaqueous solvent, a more uniform dispersion is obtained by setting the primary particle diameter to preferably 0.5 μm or less, more preferably 0.3 μm or less.

Further, if the average particle diameter of the fine powder of the fluororesin in the nonaqueous dispersion exceeds 1 μm, the fine powder is liable to settle and is difficult to be stably dispersed, which is not preferable. Preferably 0.5 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05 μm or more and 0.3 μm or less.

In the present invention 1, as a method for measuring the primary particle diameter, a volume-based average particle diameter (50% volume diameter, median particle diameter) measured by a laser diffraction/scattering method, a dynamic light scattering method, an image forming method, or the like can be used, but the primary particles of the fine powder of the fluorine-based resin dried to be in a powder state have a strong cohesive force with each other, and it may be difficult to easily measure the primary particle diameter by the laser diffraction/scattering method, the dynamic light scattering method, or the like. In the above case, values obtained by the image imaging method can be expressed.

On the other hand, as a method for measuring the particle diameter of the fluororesin in the nonaqueous dispersion, a volume-based average particle diameter (50% volume diameter, median particle diameter) measured by a laser diffraction/scattering method, a dynamic light scattering method, an image forming method, or the like can be used.

Examples of the apparatus for measuring the particle diameter include: a dynamic light scattering method using FPAR-1000 (available from Otsuka electronics Co., Ltd.), a laser diffraction and scattering method using Microtrac (available from Nikkiso Co., Ltd.), an image forming method using Mac-View (available from Mountech Co., Ltd.), and the like.

The fine powder of the fluororesin to be used may be obtained by mixing 2 or more kinds of fine powders having different primary particle diameters, or may be obtained by mixing 2 or more kinds of fine powders of the fluororesin in a dispersed state having different average particle diameters, or may be obtained by mixing 2 or more kinds of fine powders of the fluororesin having different primary particle diameters and average particle diameters. By using fine powders of 2 or more kinds of fluorine-based resins having different particle diameters, the viscosity can be adjusted or the filling ratio can be increased.

Further, the fine powder of the fluorine-based resin may be subjected to various surface treatments. For example, the surface of the fine powder of the fluororesin may be treated with an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, an ozone treatment, an electron beam irradiation treatment, a heat treatment, a water washing, a hot water washing, various gas treatments, or the like to remove or activate unnecessary components such as surfactants and impurities remaining on the surface of the fine powder.

In the present invention 1, the fine powder of the fluororesin is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total amount of the nonaqueous dispersion.

When the content is less than 5% by mass, the amount of the solvent is large, and the viscosity extremely decreases, so that not only the fine particles of the fluorine-based resin are liable to settle, but also disadvantages may occur due to the large amount of the solvent when mixed with materials such as cyanate ester resin and epoxy resin, for example, it takes time to remove the solvent, which is not preferable. On the other hand, if the amount is more than 70% by mass, the fine particles of the fluororesin tend to aggregate with each other, and it becomes extremely difficult to maintain the fine particles in a stable and fluid state, which is not preferable.

The urethane fine particles used in the present invention 1 are contained to eliminate the following problems: since PTFE has non-adhesiveness, adhesion strength and adhesive strength are reduced when resins are bonded to each other or when a resin is bonded to a metal or the like, and stability and the like of a non-aqueous dispersion of a fluorine-based resin are not impaired even when the urethane fine particles are contained.

Examples of urethane fine particles that can be used include: the fine particles formed of a polyurethane having a urethane bond, which is generally widely used, are generally formed from a compound having an isocyanate group and a hydroxyl group.

The urethane fine particles are preferably present in the form of particles in the nonaqueous solvent used, and not only hard urethane fine particles that have been sufficiently crosslinked but also elastomer-like urethane fine particles can be used. The shape of the fine urethane particles may be irregular, spherical, or spherical.

As the urethane fine particles, any particles may be used as long as they contain urethane, and for example, urethane fine particles containing an acrylic component, urethane fine particles containing an inorganic substance such as silica, or the like may be used, and they may be homopolymers or copolymers. Specifically, there may be mentioned: commercially available DAIMIC BEAZ CM (manufactured by Dari chemical industries, Ltd.), Art Pearl (manufactured by Geneva industries, Ltd.), Grand Pearl (manufactured by AICA Kogyo Co., Ltd.), etc.

As a method for producing urethane fine particles, for example, the following methods can be used: a method of pulverizing and micronizing the polyurethane in a lump form; a method for producing urethane microparticles which is generally used, such as a method for carrying out microparticulation by suspension polymerization, emulsion polymerization, or the like. The surface of the fine particles may be coated with hydrophobic silica or silica treated with a fluorine-based compound.

The particle size of the fine urethane particles is preferably 10 μm or less in the primary particle size, and in the nonaqueous dispersion, the average particle size is preferably 10 μm or less.

The primary particle diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less, from the viewpoint of stable dispersion in a nonaqueous solvent, whereby a more uniform dispersion is obtained.

Further, if the average particle diameter of the urethane fine particles in the nonaqueous dispersion exceeds 10 μm, the particles are liable to settle and are difficult to be stably dispersed, which is not preferable. Preferably 3 μm or less, and more preferably 1 μm or less. The measurement of the primary particle size of the urethane fine particles and the measurement of the average particle size of the urethane fine particles in the nonaqueous dispersion can be performed in the same manner as in the above-described measurement methods of the fine powder of the fluorine-based resin.

In the present invention 1, the urethane fine particles are preferably contained in an amount of 0.1 to 20 mass%, more preferably 0.3 to 15 mass%, and still more preferably 0.5 to 10 mass% based on the mass of the fine powder of the fluororesin.

If the content is less than 0.1% by mass, the advantage of the adhesion and adhesiveness due to the addition of the fine urethane particles is remarkably reduced, which is not preferable. On the other hand, if the amount exceeds 20 mass%, the electrical and physical properties of the urethane fine particles are strongly developed, and therefore, the effect of the electrical properties by the addition of PTFE is also reduced, which is not preferable.

In the present invention 1, the fine urethane particles and the fine fluorine resin powder may be dispersed simultaneously, or the fine urethane particles and the fine fluorine resin powder may be dispersed separately and mixed.

The compound represented by the above (I) used in the present invention 1 is obtained by dispersing fine particles of a fluorine-based resin uniformly and stably in a nonaqueous solvent in the form of fine particles. The ternary polymer having a molecular structure of vinyl butyral/vinyl acetate/vinyl alcohol is obtained by reacting polyvinyl alcohol (PVA) with Butyral (BA) and has a structure of butyraldehyde group, acetyl group, and hydroxyl group, and the solubility in a nonaqueous solvent and the chemical reactivity when a nonaqueous dispersion of fine particles of a fluorine-based resin is added to various resin materials can be controlled by changing the ratio (each ratio of l, m, and n) of these 3 structures.

Commercially available compounds of the above-mentioned formula (I) include Slecbk B series, K (KS) series, SV series, KURARAY CO., and Mowital series available from LTD, all of which are available from the Water chemical industry.

Specifically, there may be mentioned: trade name manufactured by hydroprocess chemical industries; slecbk BM-1 (hydroxyl amount: 34 mol%, butyralization degree of 65. + -.3 mol%, molecular weight: 4 ten thousand), Slecbk BH-3 (hydroxyl amount: 34 mol%, butyralization degree of 65. + -.3 mol%, molecular weight: 11 ten thousand), Slecbk BH-6 (hydroxyl amount: 30 mol%, butyralization degree of 69. + -.3 mol%, molecular weight: 9.2 ten thousand), Slecbk BX-1 (hydroxyl amount: 33. + -.3 mol%, acetalization degree of 66 mol%, molecular weight: 10 ten thousand), Slecbk BX-5 (hydroxyl amount: 33. + -.3 mol%, acetalization degree of 66 mol%, molecular weight: 13 ten thousand), Slecbk BM-2 (hydroxyl amount: 31 mol%, butyralization degree of 68. + -.3 mol%, molecular weight: 5.2), Slecbk-5 (hydroxyl amount: 34 mol%, butyralization degree of 65. + -.3 mol%, Slecbk molecular weight: 1-36 mol%, and Slecbk-5.2 (hydroxyl amount: 34 mol%, butyralization degree of 65. + -.3 mol%, molecular weight: 3 mol%, Slecbk-1-36 mol%, BL 1: 36 mol%, and Slecbk-5 mol% Butyralation degree 63 ± 3 mol%, molecular weight: 1.9 ten thousand), Slecbk BL-1H (hydroxyl amount: 30 mol%, butyralation degree 69. + -.3 mol%, molecular weight: 2 ten thousand), Slecbk BL-2 (hydroxyl amount: 36 mol%, butyralation degree 63. + -.3 mol%, molecular weight: 2.7), Slecbk BL-2H (hydroxyl amount: 29 mol%, butyralation degree of 70. + -.3 mol%, molecular weight: 2.8 ten thousand), Slecbk BL-10 (hydroxyl amount: 28 mol%, butyralation degree 71. + -.3 mol%, molecular weight: 1.5 ten thousand), slecbks-10 (hydroxyl group amount: 25 mol%, acetalization degree of 65. + -.3 mol%, molecular weight: 1.7 ten thousand), KURARAY co., trade name manufactured by LTD; mowital B145 (hydroxyl content: 21 to 26.5 mol%, acetalization degree: 67.5 to 75.2 mol%), Mowital B16H (hydroxyl content: 26.2 to 30.2 mol%, acetalization degree: 66.9 to 73.1 mol%, molecular weight: 1 to 2 ten thousand), and the like.

These may be used alone or in combination of 2 or more.

The content of the compound represented by the formula (I) is preferably 0.1 to 20% by mass based on the fine powder of the fluororesin. When the content of the compound is less than 0.1% by mass, dispersion stability is deteriorated, fine powder of the fluororesin is liable to settle, and when it exceeds 20% by mass, viscosity is undesirably increased.

Furthermore, considering the properties of the non-aqueous dispersion in which fine particles of a fluorine-based resin are added to a thermosetting resin or the like, the content is preferably 0.1 to 15% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.1 to 5% by mass.

In the nonaqueous dispersion of the fine powder of the fluororesin according to the invention 1, other surfactants and dispersants may be used in combination with the compound represented by the formula (I) as long as the effects of the invention 1 are not impaired.

For example, both fluorine-based and non-fluorine-based may be mentioned: surfactants such as nonionic, anionic and cationic surfactants, dispersants, polymeric surfactants such as nonionic, anionic and cationic surfactants, polymeric dispersants, and the like, but the surfactant is not limited thereto.

Examples of the nonaqueous solvent used in the nonaqueous dispersion of the present invention 1 include 1 kind of solvent selected from the group consisting of the following solvents or a solvent containing 2 or more kinds of these solvents: gamma-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-amyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexylacetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl pyruvate, ethyl acetate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl acetate, ethyl acetate, methyl acetate, ethyl acetate, Methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethylbenzyl ether, tolylmethyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, methanol, ethanol, isopropanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether, methylene diglycidyl ether, ethylene diglycidyl ether, butylene diglycidyl ether, phenylene diglycidyl ether, methyl phenol monoglycidyl ether, ethyl phenol monoglycidyl ether, butyl phenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-vinylpyridine, N-methyl-2-pyrrolidone, methyl methacrylate, ethyl phenol monoglycidyl ether, butyl phenol monoglycidyl ether, ethyl methacrylate, methyl methacrylate, ethyl methacrylate, N-methyl-2-pyrrolidone, methyl methacrylate, ethyl methacrylate, N-butyl phenol monoglycidyl, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbons, hydrofluoroethers, hydrochlorofluorocarbons, hydrofluorocarbons, perfluoropolyethers, N-dimethylformamide, N-dimethylacetamide, dioxolane, various silicone oils.

Among these solvents, those which vary depending on the resin substance used and the like include, preferably: methyl ethyl ketone, cyclohexanone, toluene, xylene, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide and dioxolane.

In the present invention 1, the above-mentioned solvent is mainly used, but may be used in combination with other solvents, or other solvents may be used, and an appropriate solvent may be selected depending on the application (various circuit board resin materials) to be used, and the like.

It is considered that the compatibility with water is high due to the polarity of the solvent used, but when the amount of water is large, the dispersibility of the fine powder of the fluororesin in the solvent is inhibited, and the viscosity may increase or the particles may aggregate.

In the present invention, the water content of the nonaqueous solvent or the nonaqueous dispersion to be used is preferably 8000ppm or less [ 0. ltoreq. water content.ltoreq.8000 ppm ] based on Karl Fischer's method. In the present invention (including examples described later), the measurement of the water content by the karl fischer method can be performed according to JIS K0068: 2001, measured by MCU-610 (manufactured by Kyoto electronics industries, Ltd.). By setting the water content in the solvent and the water content of the nonaqueous dispersion to 8000ppm or less, a fine powder of the fluororesin having a fine particle diameter, a low viscosity, and excellent storage stability can be formed, and it is preferably set to 5000ppm or less, more preferably to 3000ppm or less, and particularly to 2500ppm or less. As the adjustment of the water content, a dehydration method using a solvent such as a commonly used oily solvent can be used, and for example, a molecular sieve can be used.

The nonaqueous dispersion of the fluororesin of the present invention 1 thus constituted contains at least fine particles of the fluororesin, urethane fine particles, the compound represented by the formula (I) and a nonaqueous solvent, and thus can obtain a nonaqueous dispersion of the fluororesin which has a fine particle diameter and a low viscosity, is excellent in storage stability, is suitable for mixing with various resin materials, and can achieve a low dielectric constant and a low dielectric loss tangent while suppressing a decrease in adhesion strength and adhesive strength.

[ invention 2: nonaqueous dispersion of fluorine-based resin ]

The non-aqueous dispersion of a fluororesin according to claim 2 is characterized by containing at least: a fine powder of a fluorine-based resin, a thermoplastic elastomer, a compound represented by the formula (I), and a nonaqueous solvent.

The present invention 2 is different from the above invention 1 only in that a thermoplastic elastomer is used instead of the urethane fine particles of the above invention 1, and therefore, a thermoplastic elastomer will be described, and fine particles of a fluororesin used in the present invention 2, a compound represented by the above formula (I), a nonaqueous solvent, and the like will be described in detail in the above invention 1, and therefore, the description thereof will be omitted. The thermoplastic elastomer used in the present invention 2 will be described below.

The thermoplastic elastomer used in the invention 2 is contained for the purpose of eliminating the decrease in adhesion strength and adhesion strength when the resins are bonded to each other or the resin is bonded to a metal or the like due to the non-adhesiveness of PTFE, and the stability of the non-aqueous dispersion of the fluorine-based resin is not impaired even when the thermoplastic elastomer is contained.

As the thermoplastic elastomer of the present invention 2, any thermoplastic elastomer can be used as long as it is an elastomer that is plasticized upon heating, and examples thereof include: at least 1 selected from the group consisting of styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polybutadiene (1,2-BR) -based thermoplastic elastomers, acrylic elastomers, and silicone elastomers can be appropriately selected depending on the use of the nonaqueous dispersion of the fluorine-based resin.

Specifically, there may be mentioned: and olefinic thermoplastic elastomers (TPOs) in which an olefinic rubber is finely dispersed in a matrix of an olefinic resin such as styrene-butadiene copolymer (SBS), hydrogenated-styrene-butadiene copolymer (SEBS), hydrogenated-styrene-isoprene copolymer (SEPS), polyester-polyether copolymer (TPEE), polyurethane-polyether/polyester copolymer (TPU), nylon-polyether/polyester copolymer (TPA), PP, and the like. Among the commercially available products, there may be mentioned: SIS series (styrene-based thermoplastic elastomer, JSR), TR series (styrene-butadiene thermoplastic elastomer, JSR), RB series (polybutadiene-based thermoplastic elastomer, JSR), JSR EXELINK (olefin-based thermoplastic elastomer, JSR), DYNARON series (hydrogenated thermoplastic elastomer, JSR), thermoren (olefin-based thermoplastic elastomer, mitsubishi chemical co), EPOX series (olefin-based thermoplastic elastomer, TPE), Septon series (hydrogenated thermoplastic elastomer, KURARAY co., LTD), and the like.

These thermoplastic elastomers can be used alone, or can be mixed with 2 or more kinds.

The thermoplastic elastomer used in the present invention 2 may be soluble in or insoluble in the nonaqueous solvent used.

When the thermoplastic elastomer is insoluble in the nonaqueous solvent to be used, the thermoplastic elastomer is preferably used in the form of fine particles.

The particle size is preferably a primary particle size of 10 μm or less, and in the nonaqueous dispersion, an average particle size of 10 μm or less is preferred.

Further, when the average particle diameter of the thermoplastic elastomer fine particles in the nonaqueous dispersion exceeds 10 μm, the particles are liable to settle and are difficult to be stably dispersed, which is not preferable. Preferably 3 μm or less, and more preferably 1 μm or less. The measurement of the primary particle diameter of the thermoplastic elastomer fine particles and the measurement of the average particle diameter of the urethane fine particles in the nonaqueous dispersion can be performed in the same manner as the above-described measurement methods of the fine powder of the fluororesin.

In the present invention 2, the thermoplastic elastomer is preferably contained in an amount of 0.1 to 100% by mass, more preferably 0.3 to 80% by mass, and still more preferably 0.5 to 50% by mass, based on the mass of the fine powder of the fluororesin.

If the content is less than 0.1% by mass, the advantage of the addition of the thermoplastic elastomer in the adhesion and adhesiveness is significantly reduced, which is not preferable. On the other hand, if the amount exceeds 100 mass%, the effect of the addition of the fluorine-based resin on the electrical properties and physical properties of the thermoplastic elastomer, the effect of plasticization during heating, and the like are strongly exerted, and therefore, it is not preferable.

In the present invention 2, the thermoplastic elastomer may be used by dissolving it in a nonaqueous solvent when the fine powder of the fluororesin is dispersed, or may be used by dissolving it after preparing a dispersion of the fine powder of the fluororesin. When the thermoplastic elastomer is insoluble in the nonaqueous solvent, the fine particles of the thermoplastic elastomer and the fluororesin may be dispersed at the same time, or the fine particles of the thermoplastic elastomer and the fine powder of the fluororesin may be dispersed separately and mixed.

The nonaqueous dispersion of a fluororesin according to claim 2 thus constituted contains at least a fine powder of a fluororesin, a thermoplastic elastomer, a compound represented by the formula (I) and a nonaqueous solvent, and thus can be obtained as a nonaqueous dispersion of a fluororesin having a fine particle diameter, a low viscosity, excellent storage stability, suitability for mixing with various resin materials, a low dielectric constant and a low dielectric loss tangent, and suppressed in the decrease in adhesion strength and adhesive strength.

[ thermosetting resin compositions of fluorine-containing resin according to the invention 1 and 2]

The thermosetting resin composition of fluorine-containing resin according to the present invention 1 and the present invention 2 is characterized by containing at least: the non-aqueous dispersion of a fluorine-based resin according to claim 1 or 2, and a resin composition containing a cyanate ester resin and/or an epoxy resin.

The content of the nonaqueous dispersion of the fluorine-based resin varies depending on the amounts of the fine powder of the fluorine-based resin such as PTFE, the urethane fine particles or the thermoplastic elastomer, the compound represented by the formula (I), and the nonaqueous solvent contained in the dispersion, and varies depending on the use of the composition such as the cyanate ester resin and the epoxy resin, and the nonaqueous solvent such as the oily solvent in the resin composition is removed at the time of curing or after the composition including the cyanate ester resin and the epoxy resin is prepared, and therefore, the content of the fine powder of the fluorine-based resin such as PTFE is preferably adjusted to 1 to 100 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the resin.

When the content of the fine powder of the fluororesin such as PTFE is 1 part by mass or more per 100 parts by mass of the resin, the electric characteristics such as a low relative permittivity and a low dielectric loss tangent can be exhibited, and on the other hand, when the content is 100 parts by mass or less, the effect of the present invention can be exhibited without impairing the adhesiveness and heat resistance of the cyanate resin and the epoxy resin.

In the present invention 1, the content of the fine urethane particles and the content of the compound represented by the formula (I) are in the range of 0.1 to 20% by mass relative to the fine powder of the fluororesin, as described above. The content of the thermoplastic elastomer of the invention 2 is in the range of 0.1 to 100% by mass relative to the mass of the fine powder of the fluororesin, and the content of the compound represented by the formula (I) is in the range of 0.1 to 20% by mass relative to the fine powder of the fluororesin as described above.

The resin composition used in the present invention 1 and the present invention 2 includes a resin composition containing at least a thermosetting resin. Examples of the thermosetting resin include: epoxy resin, polyimide resin, polyamide-imide resin, triazine resin, phenol resin, melamine resin, polyester resin, cyanate resin, modified resins thereof, and the like, and these resins may be used alone in 1 kind or in combination of 2 or more kinds. These resins are base resins of the thermosetting resin composition, and may be used without particular limitation as long as they are suitable for use in electronic devices, such as insulation properties and adhesion properties.

Preferred resin compositions include: the resin composition contains at least a cyanate ester resin and/or an epoxy resin, and these resins are suitable as a base resin for thermosetting resin compositions, and are suitable for insulation, adhesion, and the like in electronic devices.

Examples of the cyanate ester resin (cyanate ester resin) that can be used in the present invention 1 and the present invention 2 include: aliphatic cyanate ester having at least 2 functionalities, aromatic cyanate ester having at least 2 functionalities or a mixture thereof, for example, there may be mentioned: a polymer of at least 1 polyfunctional cyanate ester selected from the group consisting of 1,3, 5-tricyclohexylene, 1, 3-dicyanatonaphthalene, 1, 4-dicyanatonaphthalene, 1, 6-dicyanatonaphthalene, 1, 8-dicyanatonaphthalene, 2, 6-dicyanatonaphthalene, and 2, 7-dicyanatonaphthalene; at least 1 of bisphenol A cyanate resin or a substance obtained by adding hydrogen to the bisphenol A cyanate resin, bisphenol F cyanate resin or a substance obtained by adding hydrogen to the bisphenol F cyanate resin, 6F bisphenol A dicyanate resin, bisphenol E dicyanate resin, tetramethyl bisphenol F dicyanate resin, bisphenol M dicyanate resin, dicyclopentadiene bisphenol dicyanate resin, cyanate novolac resin, and the like. Further, 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-o-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthylene ether-type epoxy resin, glycidyl amine-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, cyclohexane dimethanol-type epoxy resin, trimethylol-type epoxy resin, halogenated epoxy resin, and the like.

These epoxy resins may be used in 1 kind or in combination of 2 or more kinds.

The epoxy resin that can be used in the present invention 1 and the present invention 2 is not limited to the above resin as long as 1 molecule has 1 or more epoxy groups, and bisphenol a, hydrogenated bisphenol a, cresol novolac-based resins, and the like are suitable.

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

In the case of using the cyanate ester resin or the epoxy resin in the present invention 1 and the present invention 2, an active ester compound may be used as an additive in view of reactivity, curability, and moldability.

As the active ester compound that can be used, a compound having 2 or more active ester groups in 1 molecule is generally preferable, and examples thereof include: carboxylic acid compounds, phenol compounds, naphthol compounds, and the like. Examples of the carboxylic acid compound include: acetic acid, benzoic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound and the naphthol compound include: hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, and the like.

These active ester compounds may be used in 1 kind or in combination of 2 or more kinds. Examples of commercially available active ester compounds include: EXB-9451, EXB-9460 (available from DIC corporation), DC808, YLH1030 (available from Nippon epoxy Co., Ltd.), and the like.

The amount of these active ester compounds to be used is determined depending on the kind of the base resin of the heat-curable resin composition to be used and the active ester compound to be used.

Further, the active ester compound may be used as a curing accelerator as needed.

As the active ester compound curing accelerator, an organic metal salt or an organic metal complex is used, and for example, there are used: contains an organometallic salt or an organometallic complex of iron, copper, zinc, cobalt, nickel, manganese, tin, or the like. Specifically, examples of the curing accelerator for the active ester compound include: organic metal salts such as manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octylate, copper octylate, zinc octylate, and cobalt octylate; and organic metal complexes such as lead acetylacetonate and cobalt acetylacetonate.

The curing accelerator for these active ester compounds may be contained in an amount of 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on the concentration of the metal, based on 100 parts by mass of the resin used, from the viewpoints of reactivity, curability and moldability.

When the epoxy resin is used in the present invention 1 and the present invention 2, a curing agent can be used as an additive in view 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, isophoronediamine, aromatic amines such as m-phenylenediamine, p-phenylenediamine, 3 ' -diaminodiphenylsulfone, 4 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylether, mercaptopropionate, thiols such as terminal mercapto compounds of epoxy resins, polyazelaic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2, 3-dicarboxylic anhydride, norbornane-2, 3-dicarboxylic anhydride, methyl-5-norbornene-2, 3-dicarboxylic anhydride, mixtures thereof, and mixtures thereof, At least 1 kind of the alicyclic acid anhydride such as methyl-norbornane-2, 3-dicarboxylic anhydride, aromatic acid anhydride such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, imidazole such as 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole and salts thereof, amine adduct obtained by reaction of imidazole and epoxy resin, hydrazine such as dihydrazide adipate, dimethylbenzylamine, tertiary amine such as 1, 8-diazabicyclo [5.4.0] undec-7-ene, organic phosphine such as triphenylphosphine, dicyandiamide and the like.

The amount of these curing agents to be used is determined depending on the kind of the epoxy resin to be used and the curing agent to be used.

The resin compositions according to the present invention 1 and the present invention 2 may be used in combination with materials generally used in thermosetting resin compositions for electronic devices, such as inorganic fillers, thermoplastic resin components, rubber components, flame retardants, colorants, thickeners, defoaming agents, leveling agents, coupling agents, and adhesion imparting materials.

In the present invention 1 and the present invention 2, by adjusting the total resin concentration of the cyanate ester resin, the epoxy resin, and the like, which is necessary for the final fluorine-containing resin thermosetting resin composition, the fine fluorine-containing resin powder can be uniformly present without aggregation, and the composition can exhibit excellent properties such as low relative permittivity and dielectric loss tangent, no adhesion strength, and no decrease in adhesion strength, and thus, excellent adhesiveness, heat resistance, dimensional stability, and flame retardancy.

[ thermosetting resin cured products of fluorine-containing resins according to invention 1 and 2]

The thermosetting resin compositions of the fluorine-containing resin according to the present invention 1 and the present invention 2 can be molded and cured by the same method as the known thermosetting resin compositions such as epoxy resin compositions to form cured products. The molding method and the curing method may be the same as those of known thermosetting resin compositions such as epoxy resin compositions, and there is no need for a method specific to the thermosetting resin composition of the fluorine-containing resin of the present invention, and there is no particular limitation.

The cured product obtained by curing the thermosetting resin composition of the fluorine-containing resin according to the invention 1 and the invention 2 may be in the form of a laminate, a molded product, an adhesive, a coating film, a film, or the like.

The fluorine-containing resin thermosetting resin composition according to the present invention 1 and the present invention 2, and cured products thereof, are excellent in electrical characteristics such as low relative permittivity and low dielectric loss tangent without impairing the adhesiveness and heat resistance of a thermosetting resin such as an epoxy resin and the like, and further, contain urethane fine particles to suppress the decrease in adhesion strength and adhesive strength, and are therefore suitable for electronic substrate materials, insulating materials, adhesive materials and the like, and are useful as materials such as sealing materials, copper-clad laminates, insulating paints, composite materials, insulating adhesives and the like used for electronic components, and particularly suitable for the formation of insulating layers of multilayer printed wiring boards for electronic devices, laminates for circuit boards, covering films, prepregs and the like.

(invention 3 to 6: heat-curable resin composition containing fluorine-based resin ]

The thermosetting resin composition of fluorine-containing resin according to claim 3 is characterized by containing at least: the present invention is a fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin, the present invention according to claim 4, comprising at least: a fluorine-based resin fine powder dispersion, a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin, wherein the fluorine-based resin fine powder dispersion contains at least: the invention of claim 5 is a fluororesin fine powder, a compound represented by the formula (I) and a nonaqueous solvent, and is characterized by containing at least: a fluororesin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a resin composition containing a cyanate ester resin and/or an epoxy resin, the fluororesin fine powder dispersion containing at least: the present invention is a fluororesin fine powder, a compound represented by the formula (I) above, and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent, and the present invention is characterized by containing at least: a fluororesin fine powder coloring material dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), a coloring material, and a nonaqueous solvent.

Hereinafter, the thermosetting resin compositions of the respective fluorine-containing resins will be described in detail with respect to the present invention 3 to 6. The fine powder of the fluororesin used in the invention 3 to the invention 6, the compound represented by the formula (I), the nonaqueous solvent, the cyanate ester resin, the epoxy resin, and the like are the same as those in the invention 1, and the description thereof will be omitted, and the details thereof will be described later.

(invention 3: heat-curable resin composition containing fluorine-based resin ]

In the present invention 3, the fine powder of the fluororesin described in detail in the above invention 1 can be used as the fine powder of the fluororesin, and the content thereof is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total solid content of the thermosetting resin composition.

When the content is less than 5% by mass, the properties of the fluorine-based resin cannot be sufficiently imparted to the final thermosetting resin or the like, and when the content exceeds 70% by mass, the mechanical strength of the final thermosetting resin or the like is extremely weakened, which is not preferable.

In the present invention 3, the compound represented by the formula (I) used may be the compound described in detail in the above invention 1, and the content thereof is preferably 0.01 to 30% by mass based on the fine powder of the fluororesin. When the content of the compound is less than 0.01% by mass, dispersion stability is deteriorated, and the fluorine-based fine powder is liable to settle, and when it exceeds 30% by mass, the viscosity of the thermosetting resin composition is increased, which is not preferable.

Further, in consideration of the properties of the obtained thermosetting resin, the content is more preferably 0.01 to 5% by mass, particularly preferably 0.01 to 2% by mass.

In the present invention 3 (the present invention 10), as described in detail in the above invention 1, other surfactants and dispersants may be used in combination with the compound represented by the above formula (I).

Coloring material

Examples of the coloring material used in the present invention 3 include: at least 1 selected from inorganic pigment, organic pigment and dye.

The inorganic pigments, organic pigments and dyes that can be used are not particularly limited as long as they are conventionally used for imparting functions such as concealing properties, optical properties, light shielding properties, light reflecting properties, design properties and the like to thermosetting resin materials such as cover films and flexible printed wiring boards, and from the viewpoint that the effects of the present invention can be further exerted without impairing the properties such as insulating properties, low dielectric constant, low dielectric loss tangent and the like, and processability, preferred examples of the inorganic pigments and organic pigments include: at least 1 selected from carbon black pigment, oxide black pigment and white pigment.

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

Examples of the oxide-based black pigment include: at least 1 selected from the group consisting of cobalt oxide, ferroferric oxide, ferrous oxide, manganese oxide, titanium black, chromium oxide, bismuth oxide, stannous oxide, copper oxide or copper-iron-manganese, aniline black, perylene black, iron-manganese-bismuth black, cobalt-iron-chromium black, copper-chromium-manganese black, iron-chromium black, manganese-bismuth black, manganese-yttrium black, iron-manganese oxide spinel black, copper-chromite spinel black, hematite, magnetite, micaceous iron oxide, metal oxides containing titanium black and iron, composite metal oxides, and the like.

Among these Black pigments, carbon Black having excellent light-shielding properties is preferably used, and commercially available products such as #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #52, #85, #95, CF9, MA7, MA8, MA11, MA100, MA220, MA230, and the like, produced by Mitsubishi chemical corporation, Printex series such as Printex25, 35, 40, 45, 55, 150T, U, V, P, L6 produced by Evonik Industries, and the like, are preferably used, and perylene Black pigments having improved electrical reliability are preferably used, and commercially available perylene Black pigments such as Lumogen Black series and Paliogen series produced by BASF corporation, are preferably used. In addition, an aluminum flake pigment (black interference aluminum pigment) having excellent heat insulating properties may also be used.

As white pigments, it is possible to use: titanium oxide, aluminum oxide, barium sulfate, magnesium oxide, aluminum nitride, boron nitride (hexagonal cubic), barium titanate, zirconium oxide, calcium oxide, zinc sulfide, calcium sulfate, basic zinc molybdate, basic calcium zinc molybdate, molybdenum white, kaolin, silica, talc, powdered mica, powdered glass, powdered aluminum, powdered nickel, calcium carbonate, and the like.

Among these white pigments, titanium oxide having a large shielding force and fine powder silica having a high insulating property are more preferable, and these can be used in combination, and by using both of them in combination, the insulating property and the reflectivity can be improved together. Examples of the titanium oxide include anatase type titanium oxide and rutile type titanium oxide. Among these, anatase-type titanium oxide which reflects the wavelengths of a near-ultraviolet LED and a blue LED is more preferable for use in an LED. Examples of the fine powder silica include crystalline silica, fused silica, and fumed silica.

The surface of titanium oxide is treated with alumina, silica, or the like, and further treated with a silane coupling agent or a titanate coupling agent, whereby the oxidative decomposition reaction of organic substances caused by the combination of titanium oxide and a photocatalyst can be suppressed, and therefore, the life of an insulating material, a coating film, or the like using the thermosetting resin composition can be further extended.

Examples of the inorganic pigments and organic pigments other than the carbon-based black pigment, oxide-based black pigment, and white pigment include: azo pigments, disazo pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, anthraquinone pigments, anthrone pigments, xanthene pigments, diketopyrrolopyrrole pigments, anthraquinone (anthrone) pigments, perinone pigments, quinacridone pigments, indigo pigments, dioxazine pigments, phthalocyanine pigments, azomethine pigments, and the like. Examples of the inorganic pigment include: red color systems such as manganese oxide-aluminum oxide, chromium oxide-tin oxide, iron oxide, cadmium sulfide and selenium sulfide, blue color systems such as cobalt oxide, zirconium oxide-vanadium oxide and chromium oxide-vanadium pentoxide, yellow color systems such as zirconium-silicon-praseodymium, vanadium-tin, chromium-titanium-antimony, green color systems such as chromium oxide, cobalt-chromium and aluminum-chromium oxide, and peach color systems such as aluminum-manganese, iron-silicon-zirconium.

Inorganic pigments and organic pigments including these carbon-based black pigments, oxide-based black pigments, white pigments, and the like preferably have a primary particle size of 1 μm or less, from the viewpoint that they can effectively exert other functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties without impairing the properties such as workability.

Examples of dyes that can be used include: the dye may be any of various dyes such as oil-soluble dyes, acid dyes, direct dyes, basic dyes, mordant dyes, and acid mordant dyes. When the dye is used by being laked, it 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 reactive to a diamine compound such as an aromatic diamine used in the thermosetting resin composition is preferably used, and a dye having a sulfonic acid group or a carboxylic acid group in the molecule is preferably used. For example, an acid dye (a diamine is a basic substance, and therefore a dye which is weak to a base even if it is an acid dye) or the like can be suitably used. In general, the dye is simply dissolved and dispersed in the molecule of the thermosetting resin, and in the case of a diamine compound such as an aromatic diamine, since a part of the dye is bonded to the polymer matrix thermally cured by heat treatment, the dye is less likely to move in the thermosetting resin, and the solvent resistance and the like can be further improved.

In the present invention 1, from among inorganic pigments, organic pigments, and dyes as coloring materials to be used, the most preferable coloring material is selected as described above, in consideration of the use of a thermosetting resin material (insulating material, insulating film, cover film, flexible printed wiring board, etc.) and the content of the coloring material, in view of the fact that the desired shielding property, light shielding property, and reflection property can be exhibited.

In the invention 3, the coloring material to be used is determined in an appropriate amount in consideration of the use, concealing property, optical property, light-shielding property, light-reflecting property, design property and other functions of the thermosetting resin material (thermosetting resin film, thermosetting resin insulating film, cover film, flexible printed wiring board and the like), and the lower limit is 0.1 mass% or more, more preferably 1 mass% or more, based on the total solid content of the thermosetting resin composition, from the viewpoint that the other functions such as insulating property, low dielectric constant, low dielectric loss tangent and the like, processability and the like can be exhibited without impairing the properties such as insulating property, low dielectric constant, low dielectric loss tangent and the like by containing the coloring material, and the upper limit is preferably 30 mass% or less, from the viewpoint that the mechanical strength and the like of the final thermosetting resin and the like are not impaired, More preferably 20% by mass or less.

[ resin composition ]

The resin composition used in the present invention 3 includes at least: cyanate ester resins and/or epoxy resins. These resins are base resins of the thermosetting resin composition, and may be used without particular limitation as long as the resins are suitable for use in electronic devices, such as insulation properties and adhesion properties.

The cyanate ester resin (cyanate ester resin), the epoxy resin, the mass ratio thereof when used in combination (in the range of 1: 10 to 10: 1), the active ester compound and the curing accelerator thereof, the curing agent for the epoxy resin, the contents thereof, and the like, which are described in detail in the above-mentioned invention 1 and invention 2, can be used, and therefore, the description thereof will be omitted.

As described in detail in the above inventions 1 and 2, the resin composition of the present invention 3 may be used in combination with a material generally used in thermosetting resin compositions for electronic devices, such as an inorganic filler, a thermoplastic resin component, a rubber component, a flame retardant, a coloring agent, a thickener, an antifoaming agent, a leveling agent, a coupling agent, and an adhesion imparting material.

In the present invention 3, the nonaqueous solvent described in detail in the present invention 1 can be used for adjusting the viscosity of the thermosetting resin composition.

In the nonaqueous solvent used in the present invention 3, it is preferable that the solvent varies depending on the material used, the use of the thermosetting resin, and the like, and examples thereof include: acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, gamma-butyrolactone, sulfolane, halogenated phenols, xylene and acetone.

The content of these nonaqueous solvents is adjusted so as to be a content suitable for adjusting the viscosity of the thermosetting resin composition and the like.

The thermosetting resin composition of fluorine-containing resin according to claim 3 is characterized by containing at least: the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the resin composition containing the cyanate ester resin and/or the epoxy resin may be prepared, for example, by adding a predetermined amount of the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the resin composition containing the cyanate ester resin and/or the epoxy resin to a nonaqueous solvent, mixing them, and the like, and using various mixers and dispersers such as an ultrasonic disperser, a planetary mixer, a triple roll mill, a ball mill, a bead mill, and a jet mill, in addition to stirring by a disperser, a homogenizer, and the like.

In the fluorine-containing resin thermosetting resin composition according to claim 3, by adding and mixing a predetermined amount of fine powder of a fluorine-containing resin, the compound represented by the formula (I), the coloring material, and the resin composition containing a cyanate ester resin and/or an epoxy resin to a nonaqueous solvent, the total resin concentration of the cyanate ester resin, the epoxy resin, and the like required for the final thermosetting resin composition is adjusted, whereby the fluorine-containing resin powder and the coloring material can be uniformly present without aggregation, and excellent characteristics such as low relative permittivity and dielectric loss tangent, adhesiveness, heat resistance, dimensional stability, and flame retardancy can be exhibited.

The thermosetting resin composition of fluorine-containing resin according to claim 3 contains at least: the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the resin composition containing the cyanate ester resin and/or the epoxy resin are molded and cured by the same method as in the case of a thermosetting resin composition such as a known epoxy resin composition to obtain a cured product, an insulating material, and the like. The molding method and the curing method may be the same as those of known thermosetting resin compositions such as epoxy resin compositions, and there is no need for a method specific to the thermosetting resin composition of the fluorine-containing resin of the present invention 3, and there is no particular limitation.

The thermosetting resin composition of the fluorine-containing resin of the present invention 3 can use various additives such as a surfactant, a dispersant, and an antifoaming agent, a filler material such as silica particles and acrylic particles, an elastomer, and the like, as long as the effects of the present invention are not impaired.

Further, in the thermosetting resin composition of the fluorine-containing resin according to claim 3, the water content of the thermosetting resin composition by Karl Fischer's method is preferably 5000ppm or less (0. ltoreq. water content. ltoreq.5000 ppm). By setting the water content of the thermosetting resin composition to 5000ppm or less in consideration of the mixing of water from the material, the mixing of water in the production stage, and the like, the fine powder of the fluororesin and the coloring material (pigment) can be uniformly present without aggregation, and the thermosetting resin composition having more excellent storage stability can be obtained.

[ the present invention 4: heat-curable resin composition containing fluorine-based resin ]

The thermosetting resin composition of fluorine-containing resin according to claim 4 is characterized by containing at least: a fluorine-based resin fine powder dispersion containing at least: the fine powder of the fluorine-based resin, the compound represented by the formula (I), the nonaqueous solvent, the components, and the like are described in detail in the same manner as in the above-mentioned invention 3 and the like, and therefore, the description thereof is omitted.

In the present invention according to claim 4, compared with the above invention 3, a fluororesin fine powder dispersion prepared in advance is used, the fluororesin fine powder dispersion containing at least: the fine powder of a fluorine-based resin, the compound represented by formula (I), and the nonaqueous solvent are added to the dispersion in a predetermined amount, and the resin composition containing the cyanate ester resin and/or the epoxy resin is mixed, and the like, whereby a thermosetting resin composition having the fine powder of a fluorine-based resin and the coloring material uniformly dispersed in fine particles and the like in the composition without aggregation and sedimentation can be obtained.

The fluorine-based resin fine powder dispersion according to the invention of claim 4 can be produced, for example, as follows: the fluorine-based resin fine powder is obtained by stirring, mixing, and dispersing using a mixer such as a disperser or a homomixer, a disperser such as an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet mill, and the like, and the volume-based average particle diameter (50% volume diameter, median diameter) of the fluorine-based resin fine powder in a dispersed state by a dynamic light scattering method or a laser diffraction/scattering method is preferably 10 μm or less. Generally, the particles are fine particles having large particle diameters in the form of secondary particles, in which primary particles are aggregated. The secondary particles of the fine powder of the fluororesin are dispersed so as to have a particle diameter of 10 μm or less, and for example, the dispersion is carried out by using a disperser such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, a high-pressure homogenizer, or the like, whereby a dispersion having a low viscosity and being stable even when stored for a long period of time can be obtained.

The average particle diameter is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. This is because a more stable dispersion is obtained.

In the thermosetting resin composition containing a fluorine-containing resin according to claim 4, as in the thermosetting resin composition containing a fluorine-containing resin according to claim 3, various additives such as a surfactant, a dispersant, and an antifoaming agent, a filler material such as silica particles and acrylic particles, an elastomer, and the like can be used within a range not to impair the effects of the present invention.

Further, in the thermosetting resin composition of the fluorine-containing resin according to the invention 4 (including the invention 5 and the invention 6 described later), the water content by Karl Fischer's method is preferably 5000ppm or less [ 0. ltoreq. water content. ltoreq.5000 ppm ] as in the case of the thermosetting resin composition according to the invention 3. The moisture content of the thermosetting resin composition is finally set to 5000ppm or less in consideration of the mixing of moisture from the material, the mixing of moisture in the production stage, and the like, and the fine powder of the fluororesin and the coloring material (pigment) can be uniformly present without aggregation, and the thermosetting resin composition having more excellent storage stability can be obtained.

[ invention 5: heat-curable resin composition containing fluorine-based resin ]

The thermosetting resin composition of fluorine-containing resin according to claim 5 is characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material dispersion or a coloring material solution, and the resin composition containing a cyanate ester resin and/or an epoxy resin, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by formula (I), and the non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent, and the detailed description of each component and the like is the same as in the above-mentioned invention 3 and the like, and therefore, the description thereof is omitted.

In the present invention according to claim 5, compared with the above inventions 3 and 4, a fluorine-based resin fine powder dispersion and a coloring material dispersion or a coloring material solution prepared in advance are used, the fluorine-based resin fine powder dispersion containing at least: a thermosetting resin composition which comprises a fine powder of a fluorine-based resin such as a fine particle dispersed in a composition and a coloring material without aggregation or sedimentation can be obtained by adding a predetermined amount of the resin composition comprising a cyanate ester resin and/or an epoxy resin to the dispersion or solution containing at least a coloring material and a non-aqueous solvent and mixing the resultant.

The coloring material dispersion according to the invention of claim 5 can be obtained by, for example, dispersing an inorganic pigment or an organic pigment containing the carbon-based black pigment, the oxide-based black pigment, the white pigment, or the like in a nonaqueous solvent, and if necessary, may be dispersed using a surfactant, a dispersant, a pigment derivative (synergist), an antifoaming agent, or the like, as long as the effects of the invention are not impaired.

The device used for dispersion can be prepared by stirring, mixing, and dispersing with a mixer such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, or the like, as in the case of the fine powder dispersion of the fluororesin.

In the above-mentioned coloring material dispersion, the volume-based average particle diameter (50% volume diameter, median particle diameter) of the coloring material (pigment) by the dynamic light scattering method or the laser diffraction/scattering method is preferably 3 μm or less in a dispersed state. By dispersing the coloring material (pigment) so as to have a particle diameter of 3 μm or less, for example, by using a disperser such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, a high-pressure homogenizer, or the like, a dispersion having a low viscosity and being stable even when stored for a long period of time can be obtained.

The average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. This is because a more stable dispersion is obtained.

The coloring material solution according to claim 5 is obtained by dissolving various dyes such as the oil-soluble dye, the acid dye, the direct dye, the basic dye, the mordant dye, or the acid mordant dye in a nonaqueous solvent.

The device used for dissolution may be any device capable of stirring, mixing, and dissolution, such as a disperser and a homomixer, or an ultrasonic irradiation device, and when a coloring material (dye) having low solubility is used, the coloring material may be dissolved by stirring while heating the nonaqueous solvent.

[ invention 6: heat-curable resin composition containing fluorine-based resin ]

The thermosetting resin composition of fluorine-containing resin according to claim 6 is characterized by containing at least: a fluororesin fine powder coloring material dispersion containing at least: the fine powder of a fluorine-based resin, the compound represented by the formula (I), the coloring material, and the nonaqueous solvent are the same as those in the above invention 1 and the like, and therefore, the detailed description thereof is omitted.

In the present invention according to claim 6, compared with the above inventions 3,4 and 5, a fluororesin fine powder coloring material dispersion containing at least: the fine powder of a fluorine-based resin, the compound represented by formula (I), the colorant and the nonaqueous solvent are added to the dispersion in a predetermined amount and mixed, whereby a thermosetting resin composition can be obtained which contains the fine powder of a fluorine-based resin such as a fine particle dispersed uniformly in the composition and a coloring material without aggregation or sedimentation.

The fluororesin fine powder coloring material dispersion according to claim 6 can be obtained by dispersing fine powder of a fluororesin, a compound represented by the formula (I), and a colorant in a nonaqueous solvent, for example, and if necessary, the fine powder can be dispersed using a surfactant, a dispersant, a pigment derivative (synergist), an antifoaming agent, or the like, as far as the effects of the present invention are not impaired.

The device used for dispersion can be prepared by stirring, mixing, and dispersing using, for example, a disperser such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, or the like, as in the fine powder dispersion and the coloring material dispersion of the fluororesin.

Since the above-mentioned fluororesin fine powder coloring material dispersion is a dispersion containing both a fluororesin fine powder and a coloring material, it is difficult to simply obtain the average particle diameter thereof, as in the case of the fluororesin fine powder dispersion and the coloring material dispersion, and it is preferable to use a filter, a sieve or the like so that the maximum particle diameter becomes 10 μm or less. This is because a more stable dispersion is obtained.

In the present invention 3 to the present invention 6, by carrying out the respective inventions of the above-mentioned invention 3 to 6, it is possible to obtain a thermosetting resin composition in which fine particles of a fluororesin or a coloring material are uniformly dispersed in fine particles or the like in the composition without aggregation or sedimentation.

In the above-mentioned 3 rd to 6 th inventions, the above-mentioned nonaqueous solvent is used, but it may be used in combination with other solvents or other solvents, and an appropriate nonaqueous solvent may be selected depending on the application of the thermosetting resin composition to be used (including a wiring board of a circuit board, a cover film, an insulating material, and the like).

[ preparation of cured product, insulating Material, etc. obtained from thermosetting resin composition of fluorine-containing resin according to any of the inventions 3 to 6]

The cured product, insulating material, and the like obtained from the thermosetting resin composition of each fluorine-containing resin according to the present invention 3 to 6 can be molded and cured by the same method as the known thermosetting resin composition such as an epoxy resin composition to form a cured product, insulating material, and the like. The molding method and the curing method can be the same as those of known thermosetting resin compositions such as epoxy resin compositions, etc., fine particles of fluorine-based resin and coloring materials are uniformly dispersed in fine particles, etc., and functions such as hiding properties, optical properties, light-shielding properties, light-reflecting properties, design properties, etc. are imparted by coloring with pigments and dyes, and colored cured products having high insulation properties, excellent heat resistance, electrical properties (low dielectric constant, low dielectric loss tangent), processability, etc., and insulating materials such as thermosetting resin insulating films, etc. can be obtained.

As a method for producing a thermosetting resin insulating film, for example, when a fine powder of a fluorine-based resin is dispersed and subjected to predetermined coloring, for example, when a black or white thermosetting resin, a thermosetting resin film, or a thermosetting resin insulating material is produced, a film-like material (coating film) is formed by applying the thermosetting resin composition obtained above to the surface of a thermosetting resin base material or a thermosetting resin film base material, and the film-like material is subjected to heat treatment to remove a solvent and to curing treatment, thereby obtaining the thermosetting resin insulating film.

The substrate that can be used is not particularly limited in shape and material as long as it has a dense structure to the extent that it is substantially impermeable to liquid and gas, and suitable examples thereof include: a film-forming substrate such as a tape, a die, a roll, or a drum, an electronic component such as a circuit board having a thermosetting resin film as an insulating protective film formed on the surface thereof, an electric wire, a sliding component having a coating film formed on the surface thereof, a product, a multilayered film formed by forming a thermosetting resin film, a single film in the case of a copper-clad laminated board, a copper foil, and the like, which are known per se, used for producing a general film.

As a method for coating the thermosetting resin composition on these substrates, for example, the following methods can be suitably employed: known methods per se include spray coating, roll coating, spin coating, bar coating, ink jet coating, screen printing, and slit coating.

The film, insulating material, and the like formed from the thermosetting resin composition applied to the substrate can be defoamed by heating at a relatively low temperature, such as room temperature or lower, under reduced pressure or normal pressure.

The film-like material formed of the thermosetting resin composition on the base material is subjected to heat treatment to remove the solvent, and is subjected to curing treatment to form a thermosetting resin, a thermosetting resin film, and a thermosetting resin insulating material.

The thickness of the thermosetting resin, thermosetting resin film, thermosetting resin insulating material is appropriately adjusted depending on the application, and for example: a thermosetting resin film or film having a thickness of 0.1 to 200 μm, preferably 3 to 150 μm, more preferably 5 to 130 μm.

The concentration of the fine powder of the fluorine-containing resin in the colored thermosetting resin film, the colored thermosetting resin insulating material, and the like obtained from the thermosetting resin composition of each fluorine-containing resin according to the above-described 3 rd to 6 th aspects is not particularly limited, and is preferably 5 to 70 mass%, more preferably 10 to 60 mass%, and further preferably about 10 to 35 mass% with respect to the total mass of the cured product obtained by curing the thermosetting resin composition of the present invention. When the concentration of the fine powder of the fluororesin is too small, the effect of adding the fine powder of the fluororesin is not obtained, and when the concentration of the fine powder of the fluororesin is too large, the mechanical properties and the like of the thermosetting resin are deteriorated.

The concentration of the coloring material of the fluorine-based resin in the colored thermosetting resin insulating material such as the colored thermosetting resin insulating film is not particularly limited, and is preferably about 0.1 to 30% by mass, more preferably about 1 to 20% by mass, and further preferably about 5 to 20% by mass, relative to the entire mass of the cured product obtained by curing the thermosetting resin composition of the present invention. When the concentration of the coloring material is too small, the effects of hiding property, optical properties, light-shielding property, light-reflecting property, design property, and the like are not exhibited, and when the concentration of the coloring material is too large, the electrical properties, mechanical properties, and the like of the thermosetting resin are deteriorated.

The colored thermosetting resin film obtained from the thermosetting resin composition of fluorine-containing resin according to each of the above 3 rd to 6 th aspects, for example, a white thermosetting resin material such as a white film obtained by using a white pigment such as titanium oxide as a pigment, can be used as a heat-resistant lightweight white material, specifically, as a material for an LED (light emitting diode), a reflective material for organic EL light emission, or a base material for a metal layer white film, and can be suitably used for an LED, an organic EL, a flexible printed wiring board on which other light emitting elements are mounted, and the like.

The black thermosetting resin material such as a black thermosetting resin film obtained from each of the thermosetting resin compositions of the above-described inventions 3 to 6 is excellent in shielding properties, optical properties and light shielding properties in electronic components and mounted components to be protected.

Adhesive composition for circuit boards according to any of claims 3 to 6

The adhesive composition for circuit boards according to the invention 3 to 6 is obtained by using the thermosetting resin composition of the fluorine-containing resin according to the invention 3 to 6, and may further contain a rubber component dispersed in the cyanate resin or the epoxy resin.

The adhesive composition for circuit boards according to the present invention 3 to 6 is required to have sufficient flexibility (hereinafter, the same applies) even in the composition itself in order to be used for manufacturing a Flexible printed circuit board or the like capable of bending a wiring or a substrate, and preferably further contains a rubber component in order to compensate for such flexibility.

Examples of the rubber component that can be used include: the Natural Rubber (NR) or the synthetic rubber preferably includes: styrene-butadiene rubber (SBR), Isoprene Rubber (IR), acrylonitrile butadiene rubber (NBR), Ethylene Propylene Diene Monomer (EPDM) rubber, polybutadiene rubber, modified and modified polybutadiene rubber, and the like, EPDM rubber having an ethylene content of 10 to 40 mass% or SBR, NBR, and the like can be preferably used, and EPDM rubber capable of reducing the relative dielectric constant and the dielectric loss coefficient value of the resin composition is particularly preferable.

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

The adhesive composition for circuit boards according to the 3 rd to 6 th aspects of the present invention can be produced by a usual method of mixing fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and a resin composition formed of a cyanate ester resin or an epoxy resin in the 3 rd to 6 th aspects of the present invention, for example, and is preferably produced by the following method: a method of adding and mixing a resin composition containing a coloring material, a cyanate ester resin and/or an epoxy resin, and further a rubber component to the fluorine-based resin fine powder dispersion of the invention 4; a method of adding and mixing a resin composition containing a cyanate ester resin and/or an epoxy resin and further a rubber component to the fluorine-based resin fine powder dispersion and the coloring material dispersion or the coloring material solution according to claim 5; a method of adding and mixing a resin composition containing a cyanate ester resin and/or an epoxy resin and further a rubber component to the fluorine-based resin fine powder coloring material dispersion of the invention 6.

The adhesive composition for circuit boards according to the 3 rd to 6 th aspects of the present invention may further contain inorganic particles such as a phosphorus flame retardant in order to further compensate for flame retardancy and the like. The inorganic particles such as these phosphorus flame retardants are desirably 1 to 30 parts by mass, preferably 5 to 20 parts by mass, based on 100 parts by mass of the cyanate ester resin or the epoxy resin.

The adhesive composition for circuit boards according to the 3 rd to 6 th aspects of the present invention may further contain, in addition to the above components, a curing accelerator, a defoaming agent, a coloring agent, a fluorescent material, a modifier, an antitarnish agent, an inorganic filler, a silane coupling agent, a light diffusing agent, a heat conductive filler, and other conventionally known additives in an appropriate amount as needed.

As curing (reaction) accelerators other than the above, for example, there can be used: imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, tertiary amines and salts thereof such as 1, 8-diazabicyclo (5,4,0) undec-7-ene, phosphines such as triphenylphosphine, phosphonium salts such as triphenylphosphonium bromide, tin-based catalysts such as aminotriazoles, tin octylate and dibutyltin dilaurate, zinc-based catalysts such as zinc octylate, and acetylacetone salts such as aluminum, chromium, cobalt and zirconium. These curing (reaction) accelerators may be used alone or in combination of 2 or more.

The adhesive composition for circuit boards according to the present invention 3 to 6 can be molded and cured by the same method as that for known cyanate resin compositions and epoxy resin compositions to form a cured product. The molding method and the curing method may be the same as those of known cyanate ester resin and epoxy resin compositions, and are not particularly limited, and there is no need for a method specific to the adhesive composition for circuit boards of the present invention.

The adhesive composition for circuit boards of the present invention can further be formed into various forms such as laminates, molded articles, adhesives, coating films, and films.

The adhesive composition for circuit boards according to each of the inventions 3 to 6 can be obtained by using a thermosetting resin composition in which fine particles of a fluororesin or a coloring material is stably and uniformly dispersed, and the coloring material is colored black, white or the like without color unevenness or aggregates, and therefore, the adhesive composition for circuit boards has characteristics of low relative permittivity and dielectric loss tangent, and excellent adhesiveness, heat resistance, dimensional stability, flame retardancy and the like, and is therefore suitable for an adhesive material for circuit boards, and can be used for producing, for example, a laminate for circuit boards, a cover film, a prepreg, a bonding sheet and the like using the adhesive material. The cover film, prepreg, bonding sheet and the like can be used for a circuit board, for example, a Flexible Printed Circuit Board (FPCB) such as a flexible metal foil laminate, and when the adhesive composition for a circuit board of the present invention is used for production thereof, an adhesive composition for a circuit board having characteristics such as a lower relative permittivity and a lower dielectric loss tangent, and excellent adhesiveness, heat resistance, dimensional stability, flame retardancy and the like can be realized.

Laminated board for circuit board according to any one of claims 3 to 6

The circuit board laminate according to any one of the inventions 3 to 6 is characterized by comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is composed of the circuit board adhesive composition according to any one of the inventions 3 to 6 having the above-described configuration.

Fig. 1 is a schematic view of a metal foil laminate (FPCB) showing one example of the embodiment of the circuit board laminate according to the 3 rd to 6 th inventions in a cross-sectional form.

In the circuit board laminate a of the present embodiment, the metal foil 30 is laminated on the insulating film 10, and the adhesive resin layer 20 is at least interposed between the insulating film 10 and the metal foil 30, and the adhesive resin layer 20 is formed (joined) of the circuit board adhesive composition which is free from color unevenness and aggregates and is colored black, white, or the like.

Fig. 2 is a schematic view of a metal foil laminate (FPCB) showing another example of the embodiments of the circuit board laminate according to the 3 rd to 6 th inventions in cross section.

In the circuit board laminate B of the present embodiment, instead of the one-sided structure of fig. 1, as shown in fig. 2, a two-sided structure is adopted, in which metal foils 30, 30 are laminated on both sides of an insulating film 10, and at least adhesive resin layers 20, 20 are interposed between the insulating film 10 and the metal foils 30, respectively, and the adhesive resin layers 20, 20 are formed (joined) from the circuit board adhesive composition which is free from color unevenness and aggregates and is colored black, white, or the like.

The insulating film 10 used in the circuit board laminates of the 3 rd to 6 th inventions such as fig. 1 and 2 is not particularly limited as long as it has electrical insulation, and a film having heat resistance, flexibility, mechanical strength, and a coefficient of thermal expansion similar to that of metal can be used.

Examples of the insulating film 10 that can be used include: the film is preferably a Polyimide (PI) film, which is selected from the group consisting of Polyimide (PI), Liquid Crystal Polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyether imide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyoxamide, and polyether ether ketone (PEEK).

In addition, in the film formed of these materials, it is preferable to use a film whose surface is further surface-treated with low-temperature plasma or the like on the surface of the film in order to further improve the interface adhesion force with the adhesive resin layer 20.

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

The adhesive resin layer 20 is formed (bonded) from the adhesive composition for circuit boards having the above-described configuration, and is desirably 1 to 50 μm, more preferably 3 to 30 μm in thickness from the viewpoint of interface adhesion with the insulating film, flexibility of the laminate, adhesive strength, and the like.

Examples of the metal foil 30 include metal foils having conductivity, and examples thereof include: gold, silver, copper, stainless steel, nickel, aluminum, alloys thereof, and the like. From the viewpoint of conductivity, ease of handling, price, and the like, copper foil and stainless steel foil are preferably used. As the copper foil, any copper foil produced by a rolling method or an electrolytic method can be used.

The thickness of the metal foil is set to an appropriate range in consideration of conductivity between the wirings, and the like, and is preferably 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, from the viewpoints of conductivity, interface adhesiveness with the insulating film, flexibility of the laminate, and bending resistance, and easiness of forming a fine pattern in circuit processing.

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

The laminate for circuit boards according to the respective inventions 3 to 6 (for example, fig. 1 or fig. 2) thus constituted can be produced, for example, by a method of coating the adhesive composition for circuit boards of the present invention constituted as described above on the insulating film 10 to form the adhesive resin layer 20, then drying the adhesive resin layer to form a semi-cured state, and then laminating the metal foil 30 on the adhesive resin layer 20 and performing thermocompression bonding (thermal lamination), and a laminate for circuit boards colored black, white, or the like, which has excellent properties such as low relative permittivity and dielectric loss tangent, and excellent adhesiveness, heat resistance, dimensional stability, flame retardancy, and the like, and which is free from color unevenness and aggregates can be produced. In this case, post-curing the flexible metal foil laminate allows the semi-cured adhesive resin layer 20 to be completely cured, and a final flexible metal foil laminate can be obtained.

[ covering films according to the 3 rd to 6 th aspects of the present invention ]

Next, the cover film according to the 3 rd to 6 th aspects of the present invention is characterized in that an insulating film and an adhesive layer on at least one surface of the insulating film are formed, and the adhesive layer is the adhesive composition for circuit boards according to the 3 rd to 6 th aspects of the present invention having the above-described configuration.

Fig. 3 is a schematic diagram showing an example of an embodiment of the cover film of the present invention according to the 3 rd to 6 th inventions (and the 7 th to 10 th inventions described later) in a cross-sectional form.

The cover film C of the present embodiment is used as a surface protection film for a flexible printed circuit board (FPC) or the like, and the adhesive resin layer 50 is formed on the insulating film 40, and a separator (release film) 60 such as paper or a PET film as a protection layer is bonded to the adhesive resin layer 50. The separator (release film) 60 may be provided as needed in consideration of workability, storage stability, and the like.

As the insulating film 40 to be used, similarly to the insulating film 10 to be used for the circuit board laminate according to the invention of the 3 rd to 6 th aspects, for example, there are mentioned: and (b) 1 or more films selected from the group consisting of Polyimide (PI), Liquid Crystal Polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyether imide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyoxamide, and polyether ether ketone (PEEK).

In addition, for the film formed of these materials, a film obtained by further performing surface treatment on the surface of the film with low-temperature plasma or the like is preferably used in order to further improve the interface adhesion force with the adhesive resin layer 50.

In view of heat resistance, dimensional stability, mechanical properties, and the like of the cover film, a Polyimide (PI) film is particularly preferable, and a polyimide film subjected to low-temperature plasma treatment is particularly preferable for the cover film.

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

The adhesive resin layer 50 is formed (bonded) from the adhesive composition for circuit boards of the invention 3 to 6 having the above-described structure, and is desirably 1 to 50 μm, more desirably 3 to 30 μm, in thickness from the viewpoint of interface adhesion with the insulating film, adhesive strength, and the like.

The cover films according to the present invention 3 to 6 thus constituted can be produced by coating the adhesive compositions for circuit boards according to the present invention 3 to 6, which are colored black, white or the like without color unevenness or aggregates and are constituted as described above, with an insulating film 40 using a comma roll coater, a reverse roll coater or the like to form an adhesive layer, drying the adhesive layer to form a semi-cured state (a state in which the composition is dried or a state in which a curing reaction is caused in a part of the composition), and then laminating a separator (release film) 60 as the protective layer, thereby having characteristics such as low relative permittivity and dielectric loss tangent, and excellent adhesiveness, heat resistance, dimensional stability, flame retardancy and the like.

[ prepregs according to the 3 rd to 6 th aspects of the present invention ]

The prepreg according to the invention 3 to 6 is characterized in that the adhesive composition for circuit boards according to the invention 3 to 6, which is formed by impregnating at least the structure formed of 1 or more kinds of fibers selected from the group consisting of carbon-based fibers, cellulose-based fibers, glass-based fibers, and aramid-based fibers, is free from color unevenness and aggregates, and is colored black, white, or the like, is impregnated with the adhesive composition.

The prepreg according to any one of the 3 rd to 6 th aspects of the present invention can be used as a constituent material for a multilayer flexible printed wiring board or the like, is a dust-free and low-fluidity prepreg, and can be provided as a sheet or the like in a state in which the fibers are impregnated with the adhesive composition, dried, and semi-cured.

Examples of the fibers used in the prepreg include: more than 1 type of fiber selected from the group consisting of carbon-based fiber, cellulose-based fiber, glass-based fiber, and aramid-based fiber, specifically, there may be mentioned: 1 or more fibers selected from the group consisting of E glass fibers, D glass 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 the prepreg to the maximum, it is particularly preferable to use NE glass fibers having a lower relative permittivity and dielectric loss coefficient than other glass fibers (relative permittivity of about 4.8 and dielectric loss coefficient of about 0.0015).

The prepreg is configured to have a thickness of 15 to 500 μm, and when used for a circuit board, the prepreg is preferably thinner about 15 to 50 μm.

The prepregs according to the invention 3 to 6 thus constructed are used together with a material to be bonded to an interlayer constituting material such as a multilayer flexible printed wiring board, and thus provide a prepreg which is colored black, white or the like and has excellent properties such as low relative permittivity and dielectric loss tangent, and excellent adhesiveness, heat resistance, dimensional stability, flame retardancy and the like, and which is free from color unevenness and aggregates.

[ electronic devices according to any one of claims 3 to 6]

The electronic devices according to the 3 rd to 6 th aspects of the present invention use the thermosetting resin insulating material obtained from the thermosetting resin composition of each fluorine-containing resin according to the 3 rd to 6 th aspects of the present invention, and can be used, for example, for various electronic devices requiring excellent electrical characteristics (low relative permittivity and low dielectric loss tangent) and electrical insulation, such as insulating materials for bodies and parts of various electronic devices represented by thin mobile phones, game machines, router devices, WDM devices, personal computers, televisions, local servers, thin displays, hard disks, printers, and DVD devices.

In the present invention 3 to 6, even if the thermosetting resin composition of fluorine-containing resin according to the above-mentioned invention 3 to 6 is colored with a pigment or a dye to impart functions such as concealing properties, optical properties, light-shielding properties, light-reflecting properties, and design properties, a cured product of the thermosetting resin composition, which is colored in black, white, or the like, based on heat resistance, mechanical properties, sliding properties, insulating properties, a reduced dielectric constant, reduced dielectric loss tangent, or other electrical properties, excellent processability, and which is free from color unevenness and aggregates, an insulating material, a flexible printed wiring board, a cover film, and an electronic device including the above-mentioned circuit board using the adhesive composition for circuit board, and further, a film and an insulating material based on the thermosetting resin composition are used, and are suitably used for an insulating film, an interlayer insulating film for wiring board, an interlayer insulating film, a wiring board, and the like, Various tapes (belt), tape, and pipe, such as surface protective layer, sliding layer, release layer, fiber, filter material, wire covering material, bearing, paint, heat insulating shaft, disc, and seamless belt.

(7 th to 10 th inventions: polyimide precursor solution composition

The polyimide precursor solution composition of the present invention is constituted by the following inventions 7 to 10.

The present invention of claim 7 is characterized by comprising at least: the invention of claim 8 is a fluorine-based resin fine powder, a compound represented by the formula (I), a coloring material, and a polyimide precursor solution, and is characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: the invention 9 is characterized by containing fine particles of a fluorine-based resin, a compound represented by the formula (I) and a nonaqueous solvent, at least: a fluorine-based resin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the above formula (I), and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent, and the invention 10 is characterized by containing at least: a fluorine-based resin fine powder coloring material dispersion and a polyimide precursor solution, wherein the fluorine-based resin fine powder coloring material dispersion contains at least: fine powder of fluorine-based resin, compound represented by the formula (I), coloring material, and non-aqueous solvent

The polyimide precursor solution compositions according to the present invention are described in detail below with reference to the respective embodiments of the present invention 7 to 10. In addition, in the case where the fine powder of the fluororesin, the compound represented by the formula (I), the nonaqueous solvent, the coloring material, and the like used in the invention 7 to the invention 10 are the same as those in the invention 1, the invention 3, and the like, the description thereof will be omitted, and the differences will be described in detail below.

[ invention 7: polyimide precursor solution composition

The fine powder of the fluorine-based resin used in the present invention 7 can be the fine powder of the fluorine-based resin described in detail in the above invention 1, and the preferable particle size of the fine powder of the fluorine-based resin can be appropriately selected depending on the application as in the above invention 1, and is preferably small in view of sufficiently exhibiting the stability of the polyimide precursor solution composition and the properties of the obtained polyimide and the like. The fine powder of the fluororesin preferably has a primary particle diameter of 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less. The lower limit value of the primary particle size, the better the value, but from the viewpoint of manufacturability, cost and the like, the lower the value is preferably 0.05 μm or more and 0.3 μm or less.

The method and apparatus for measuring the primary particle diameter of the fine particles of the fluororesin are the same as those in the above-described invention 1, and thus are omitted.

As described in detail in the above invention 1, the fine particles of the fluororesin to be used may be obtained by mixing 2 or more kinds of fine particles having different primary particle diameters, or may be obtained by mixing 2 or more kinds of fine particles of the fluororesin in a dispersed state having different average particle diameters, or may be obtained by mixing 2 or more kinds of fine particles of the fluororesin having different primary particle diameters and average particle diameters. By using fine powders of 2 or more kinds of fluorine-based resins having different particle diameters, the viscosity can be adjusted, the filling ratio can be increased, and the surface state of polyimide or the like can be controlled.

Further, as described in detail in the above invention 1, the fine powder of the fluorine-based resin can be subjected to various surface treatments.

In the invention of claim 7, the fine powder of the fluorine-based resin is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, based on the total solid content of the polyimide precursor solution composition.

When the content is less than 5% by mass, the properties of the fluorine-based resin cannot be sufficiently imparted to the final polyimide or the like, and when the content exceeds 70% by mass, the mechanical strength of the final polyimide or the like is extremely weakened, which is not preferable.

The compound represented by the above (I) used in the present invention 7 can be a compound described in detail in the above invention 1, and has a structure having a butyraldehyde group, an acetyl group, and a hydroxyl group, and by changing the ratio of these 3 structures (each ratio of l, m, and n), the solubility in a nonaqueous solvent, the compatibility with a polyimide precursor solution, and the like, and further the chemical reactivity can be controlled.

The content of the compound represented by the above (I) is preferably 0.01 to 30% by mass based on the fine powder of the fluororesin. When the content of the compound is less than 0.01% by mass, dispersion stability is deteriorated, and the fluorine-based fine powder is liable to settle, and when it exceeds 30% by mass, the viscosity of the polyimide precursor solution is increased, which is not preferable.

Further, in consideration of the characteristics of the polyimide to be obtained, the amount is more preferably 0.01 to 5% by mass, particularly preferably 0.01 to 2% by mass.

Examples of the coloring material used in the present invention 7 include: at least 1 selected from the group consisting of the inorganic pigments, organic pigments and dyes described in detail in invention 3.

The inorganic pigments, organic pigments and dyes that can be used are not particularly limited as long as they are conventionally used for imparting functions such as concealing properties, optical properties, light shielding properties, light reflecting properties, design properties and the like to polyimide materials such as polyimide films, cover films and flexible printed wiring boards, and preferably, from the viewpoint of further exhibiting the effects of the invention 7 without impairing the properties such as insulation properties, low dielectric constant, low dielectric loss tangent and the like, processability and the like, among the inorganic pigments and organic pigments described in detail in the above invention 3, there can be mentioned: at least 1 selected from carbon black pigment, oxide black pigment and white pigment.

In the present invention 7, in consideration of the use of polyimide materials (polyimide films, polyimide insulating films, cover films, flexible printed wiring boards, etc.), the inclusion of coloring materials to exhibit desired light-shielding properties, and reflection properties, the most preferable coloring material is selected from inorganic pigments, organic pigments, and dyes, which are coloring materials to be used, as described above.

In the invention of claim 7, the coloring material used is determined in an appropriate amount in consideration of the use, concealing property, optical property, light shielding property, light reflecting property, design property, and other functions of the polyimide material (polyimide film, polyimide insulating film, cover film, flexible printed wiring board, and the like), and the lower limit is 0.1 mass% or more, more preferably 1 mass% or more, with respect to the total solid content of the polyimide precursor solution composition, and the upper limit is preferably 30 mass% or less, from the viewpoint of not impairing the properties such as mechanical strength of the final polyimide and the like, from the viewpoint of not impairing the properties such as insulation property, low dielectric constant, low dielectric loss tangent, and other properties such as electrical properties and processability, and from the viewpoint of exhibiting other functions such as desired concealing property, optical property, light shielding property, light reflecting property, and design property due to the content of the coloring material, More preferably 20% by mass or less.

Polyimide precursor solution

The polyimide precursor solution used in the present invention 7 may be any polyimide precursor used for producing a general polyimide, and for example, the polyimide precursor solution may contain at least a tetracarboxylic dianhydride and/or a derivative thereof, a diamine compound, and a nonaqueous solvent, and may be prepared by reacting a tetracarboxylic dianhydride and/or a derivative thereof with a diamine compound in the presence of a nonaqueous solvent. In the present invention 1, the "polyimide precursor solution" is a concept containing a nonaqueous solvent to be used.

Examples of tetracarboxylic dianhydrides and/or derivatives thereof that can be used include: 1,2,5, 6-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-naphthalenetetracarboxylic dianhydride, 2 ' -bis (3, 4-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, perylene-3, 4,9, 10-tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ', 4 ' -biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,6, 7-naphthalenetetracarboxylic dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, vinyltetracarboxylic dianhydride, ethylene glycol dianhydrosulfinate, 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxa-3-furyl) naphtho [1,2-c ] furan-1, 3-dione, 1,2,3, 4-butanetetracarboxylic dianhydride, and the like, and in addition, there can be mentioned: the tetracarboxylic dianhydride, which is a derivative of the tetracarboxylic dianhydride, may be used alone or in combination with 2 or more kinds of tetracarboxylic acid having the same skeleton, acid chloride of the tetracarboxylic acid, ester of the tetracarboxylic acid with a lower alcohol having 1 to 4 carbon atoms, and the like.

It is preferable to use 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (s-BPDA).

The content of the tetracarboxylic dianhydride and/or derivative thereof varies depending on the productivity, the use of the polyimide, the required properties, and the like.

Examples of the diamine compound that can be used include: hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylenediamine, 3-methylheptamethylenediamine, 4-dimethylheptamethylenediamine, 2, 11-diaminododecane, 1, 2-bis-3-aminopropoxyethane, 2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2, 5-dimethylhexamethylenediamine, 2, 5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 4 '-diaminodiphenyl ether, 4' -diaminodiphenylmethane, 3 '-dichlorobenzidine, 3' -dimethylbenzidine, N-methyl-diphenylene-diamine, N-methyl-2-methyl-N-propylenediamine, N-methyl-hexamethylenediamine, N-, 4,4 '-diaminodiphenyl sulfide, 3' -diaminodiphenyl sulfone, 1, 5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3 '-dimethyl-4, 4' -biphenyldiamine, benzidine, 3 '-dimethylbenzidine, 3' -dimethoxybenzidine, 4 '-diaminodiphenyl sulfone, 4' -diaminodiphenylpropane, 2, 4-diaminotoluene, bis (4-amino-3-carboxyphenyl) methane, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane, bis [ 4- (4-aminophenoxy) phenyl ] sulfone, p-phenylenediamine, p-, 2, 4-bis (. beta. -amino-tert-butyl) toluene, bis (. beta. -amino-tert-butylphenyl) ether, bis (. beta. -methyl-6-aminophenyl) benzene, bis (. beta. -methyl-5-amino-pentyl) benzene, 1-isopropyl-2, 4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, di (p-aminocyclohexyl) methane, 2, 17-diaminoeicosane, 1, 4-diaminocyclohexane, 1, 10-diamino-1, 10-dimethyldecane, 1, 12-diaminooctadecane, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane and the like, and they may be used alone or in admixture of 2 or more.

Preferably, p-phenylenediamine (PPD), bis (4-amino-3-carboxyphenyl) Methane (MBAA), 4' -diaminodiphenyl ether (ODA) and 2, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane (BAPP) are preferably used.

The content of the diamine compound varies depending on the productivity, the use of the polyimide, the required properties, and the like.

The combination of the tetracarboxylic dianhydride and/or its derivative and the diamine compound preferably includes: 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (s-BPDA) in combination with 4,4 ' -diaminodiphenyl ether (ODA), s-BPDA in combination with p-phenylenediamine (PPD), etc.

In the present invention 7, the nonaqueous solvent described in detail in the above-mentioned invention 1 can be used for adjusting the viscosity of the polyimide precursor solution or the polyimide precursor solution composition.

In the nonaqueous solvent, the amount varies depending on the material used, the application of the polyimide, and the like, and preferable examples thereof include: acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, gamma-butyrolactone, sulfolane, halogenated phenols, xylene and acetone.

The content of the nonaqueous solvent used in the polyimide precursor solution used in the invention 7 is the balance of the tetracarboxylic dianhydride and/or the derivative thereof and the diamine compound.

Invention 7: polyimide precursor solution composition

The polyimide precursor solution composition according to the invention 7 is characterized by containing at least: the fine powder of the fluorine-based resin, the compound represented by the formula (I), the coloring material, and the polyimide precursor solution are prepared by, for example, dissolving and polymerizing the tetracarboxylic dianhydride and/or the derivative thereof and the diamine compound in a nonaqueous solvent, and adding a predetermined amount of the fine powder of the fluorine-based resin, the compound represented by the formula (I) (butyral resin), and the coloring material to the obtained polyimide precursor solution and mixing them.

In the polyimide precursor solution composition of the invention 7, by adding predetermined amounts of the fine powder of the fluorine-based resin, the compound represented by the formula (I) and the coloring material to a polyimide precursor solution prepared in advance and mixing them, the fine powder of the fluorine-based resin and the coloring material can be uniformly dispersed in fine particles in the composition without aggregation or sedimentation.

The polyimide precursor solution used in the present invention 7 can be prepared by adding a tetracarboxylic dianhydride and/or a derivative thereof and a diamine compound in a predetermined composition ratio to a nonaqueous solvent and stirring, for example, by a known method and under predetermined conditions. The total concentration of the tetracarboxylic dianhydride and/or its derivative and the diamine compound in the polyimide precursor solution is set according to various conditions, and is preferably 5 to 30% by mass of the total amount of the reaction solution (the total amount of the polyimide precursor solution). The reaction conditions when they are stirred are not particularly limited, and the reaction temperature is preferably 80 ℃ or less, particularly 5 to 50 ℃. When the reaction temperature is too low, the reaction does not proceed, or it takes too much time until the reaction proceeds, and when it is too high, problems such as imidization proceed occur. The reaction time is preferably 1 to 100 hours.

The polyimide precursor solution composition can be prepared by stirring, mixing, and dispersing using a mixer such as a disperser or a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet mill, for example.

The polyimide precursor solution composition of the present invention 7 can use various additives such as a surfactant, a dispersant, and an antifoaming agent, filler materials such as silica particles and acrylic particles, and elastomers, as long as the effects of the present invention 7 are not impaired.

The water content of the polyimide precursor solution composition of the invention 7 based on the Karl Fischer method is preferably 5000ppm or less (0. ltoreq. water content. ltoreq.5000 ppm). By setting the water content of the final polyimide precursor solution composition to 5000ppm or less in consideration of the mixing of water from the material, the mixing of water in the production stage, and the like, fine particles of the fluorine-based resin and the coloring material (pigment) can be uniformly present without aggregation, and a polyimide precursor solution composition having more excellent storage stability can be obtained.

(the present invention 8: polyimide precursor solution composition

The polyimide precursor solution composition according to the 8 th aspect of the present invention is characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: the fine powder of the fluorine-based resin, the compound represented by the formula (I), the nonaqueous solvent, the components, and the like are described in detail in the same manner as in the above-described 1 st and 7 th inventions, and therefore, the description thereof is omitted.

In the present invention according to 8, compared with the above invention according to 7, a fluororesin fine powder dispersion prepared in advance is used, the fluororesin fine powder dispersion containing at least: the fine powder of a fluorine-containing resin, the compound represented by the formula (I) and the nonaqueous solvent are added to the polyimide precursor solution in a predetermined amount and mixed, whereby a polyimide precursor solution composition containing the fine powder of a fluorine-containing resin and the coloring material in the composition uniformly dispersed as fine particles and free from aggregation and sedimentation can be obtained.

The fluororesin fine powder dispersion according to the invention of claim 8 can be produced by stirring, mixing, and dispersing the fine powder of the fluororesin by using, for example, a disperser such as a disperser or a homomixer, a disperser such as an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, or a wet jet mill, and the like, and the average particle diameter (50% volume diameter, median particle diameter) of the fine powder of the fluororesin in the dispersed state based on the volume basis by the dynamic light scattering method or the laser diffraction/scattering method is preferably 10 μm or less. Generally, the particles are fine particles having large particle diameters in the form of secondary particles, in which primary particles are aggregated. The secondary particles of the fine powder of the fluororesin are dispersed so as to have a particle diameter of 10 μm or less, and are dispersed by using a disperser such as a disperser and a homomixer, an ultrasonic disperser, a triple roll mill, a wet ball mill, a bead mill, a wet jet mill, a high-pressure homogenizer, or the like, to obtain a dispersion having a low viscosity and being stable even when stored for a long period of time.

In the polyimide precursor solution composition of the present invention 8, as in the polyimide precursor solution composition of the present invention 7, various additives such as a surfactant, a dispersant, and an antifoaming agent, filler materials such as silica particles and acrylic particles, elastomers, and the like can be used as long as the effects of the present invention are not impaired.

Further, in the polyimide precursor solution composition according to the invention 8 (including the invention 9 and the invention 10 described later), the water content by Karl Fischer's method is preferably 5000ppm or less [ 0. ltoreq. water content. ltoreq.5000 ppm ] as in the polyimide precursor solution composition according to the invention 1. By setting the water content of the final polyimide precursor solution composition to 5000ppm or less in consideration of the mixing of water from the material, the mixing of water in the production stage, and the like, fine particles of the fluorine-based resin and the coloring material (pigment) can be uniformly present without aggregation, and a polyimide precursor solution composition having more excellent storage stability can be obtained.

[ the present invention at 9: polyimide precursor solution composition

The polyimide precursor solution composition according to the present invention is characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the formula (I), and the non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and the non-aqueous solvent, and the detailed description of each component and the like is the same as the above-described 1 st invention, 7 th invention and the like, and therefore, the description thereof is omitted.

In the present invention according to 9, compared with the above inventions 7 and 8, a fluororesin fine powder dispersion prepared in advance and a coloring material dispersion or a coloring material solution are used, the fluororesin fine powder dispersion containing at least: a polyimide precursor solution composition which comprises a fine powder of a fluorine-based resin, a compound represented by the formula (I), and a nonaqueous solvent, wherein the coloring material dispersion or coloring material solution contains at least a coloring material and a nonaqueous solvent, and wherein the fine powder of the fluorine-based resin, such as a composition in which fine particles are uniformly dispersed, and the coloring material are not aggregated or precipitated, can be obtained by adding a predetermined amount of the dispersion or solution to the polyimide precursor solution and mixing the same.

The coloring material dispersion according to the 9 th aspect of the present invention can be obtained by, for example, dispersing an inorganic pigment or an organic pigment including the carbon-based black pigment, the oxide-based black pigment, the white pigment, or the like in a nonaqueous solvent, and if necessary, dispersing the inorganic pigment or the organic pigment using a surfactant, a dispersant, a pigment derivative (synergist), an antifoaming agent, or the like, as far as the effects of the present invention are not impaired.

The device used for dispersion can be prepared by stirring, mixing, and dispersing with a disperser such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, or the like, as in the case of the fine powder dispersion of the fluororesin.

The volume-based average particle diameter (50% volume diameter, median particle diameter) of the coloring material (pigment) in a dispersed state by a dynamic light scattering method or a laser diffraction/scattering method is preferably 3 μm or less. The coloring material (pigment) is dispersed so as to have a particle diameter of 3 μm or less, and is dispersed by using a dispersing machine such as a disperser or a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, or a high-pressure homogenizer, whereby a dispersion having a low viscosity and being stable even when stored for a long period of time can be obtained.

The coloring material solution according to the present invention 9 can be obtained by dissolving various dyes such as the oil-soluble dye, the acid dye, the direct dye, the basic dye, the mordant dye, or the acid mordant dye in a nonaqueous solvent.

The device used for dissolution may be any device capable of stirring, mixing, and dissolution, such as a disperser and a homomixer, or an ultrasonic irradiation device, and when a coloring material (dye) having low solubility is used, the coloring material may be dissolved by stirring while heating a nonaqueous solvent.

A precursor solution composition can be obtained.

[ the present invention 10: polyimide precursor solution composition

The polyimide precursor solution composition according to the 10 th aspect of the present invention is characterized by containing at least: a fluorine-based resin fine powder coloring material dispersion and a polyimide precursor solution, wherein the fluorine-based resin fine powder coloring material dispersion contains at least: the fine powder of a fluorine-based resin, the compound represented by formula (I), the coloring material, and the nonaqueous solvent are the same as those in the above 7 th invention, and the detailed description thereof will be omitted.

In the present invention according to 10, compared with the above inventions 7, 8 and 9, a fluororesin fine powder coloring material dispersion containing at least: the fine powder of a fluorine-containing resin, the compound represented by the formula (I), the colorant and the nonaqueous solvent are added to the polyimide precursor solution in a predetermined amount and mixed to obtain a polyimide precursor solution composition in which the fine powder of a fluorine-containing resin and the coloring material are uniformly dispersed in fine particles without aggregation or sedimentation.

The fluororesin fine powder coloring material dispersion according to the 10 th aspect of the present invention can be obtained by dispersing fine powder of a fluororesin, a compound represented by the formula (I), and a colorant in a nonaqueous solvent, and if necessary, can be dispersed using a surfactant, a dispersant, a pigment derivative (synergist), an antifoaming agent, or the like, as long as the effects of the present invention are not impaired.

The device used for dispersion can be prepared by stirring, mixing, and dispersing with a mixer such as a disperser and a homomixer, an ultrasonic disperser, a three-roll mill, a wet ball mill, a bead mill, a wet jet mill, or the like, as in the fine powder dispersion and the coloring material dispersion of the fluororesin.

By carrying out the invention according to each of the invention 7 to the invention 10, a polyimide precursor solution composition in which fine particles of a fluororesin or the like are uniformly dispersed in fine particles and a coloring material is obtained without aggregation or sedimentation.

In the above 7 th to 10 th inventions, the nonaqueous solvent may be used in combination with other solvents or may be used in combination with other solvents, and an appropriate nonaqueous solvent is selected depending on the application of the polyimide to be used (including a wiring board of a circuit board, a cover film, an insulating material, and the like).

[ preparation of polyimide, polyimide film, polyimide insulating film, etc. from the polyimide precursor solution compositions according to the invention 7 to 10]

The polyimide, the polyimide film, the polyimide insulating film and the like according to the 7 th to 10 th aspects of the present invention can be obtained by imidizing the polyimide precursor in the polyimide precursor solution composition according to the 7 th to 10 th aspects of the present invention prepared as described above, and thus, there can be obtained colored polyimide, polyimide film, polyimide insulating film, covering film, flexible wiring board and the like, which are colored with a fluorine-containing resin, a coloring material, a pigment or a dye to impart hiding properties, optical properties, light shielding properties, light reflecting properties, design properties and other functions, and which are also highly insulating, and which are excellent in heat resistance, electrical properties (low dielectric constant, low dielectric loss tangent), processability and the like, by uniformly dispersing fine particles.

In the present invention 7 to the present invention 10, examples of the method for producing a polyimide include the following methods for producing a polyimide: the method is characterized by comprising the following steps: a step of producing a fluorine-based resin fine powder coloring material dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the formula (I), a coloring material, and a nonaqueous solvent; a step of mixing at least a tetracarboxylic acid dihydrate and/or a derivative thereof with a diamine compound to prepare a polyimide precursor solution composition; a step of mixing the fluorine-based resin fine powder coloring material dispersion with the polyimide precursor solution composition to prepare a polyimide precursor solution composition; and a step of curing the polyimide precursor solution composition to obtain a polyimide, and examples of a method for producing a polyimide film include the following methods: the method for producing a polyimide precursor solution composition is characterized by comprising the following steps: the polyimide precursor solution composition is applied and cured to obtain a polyimide film, and the following polyimide insulating film production methods are exemplified as the polyimide insulating film production method: the polyimide precursor solution composition is prepared by the same steps as the above-mentioned polyimide production method, and the method further comprises the steps of: the polyimide precursor solution composition is applied and cured to obtain a polyimide insulating film. In the above-mentioned production methods, the curing treatment (imidization method) is not particularly limited, and may be carried out by a known method.

For example, when a polyimide, a polyimide film, or a polyimide insulating material in which a fluorine-based resin is dispersed and which is colored in a predetermined color, for example, black or white, is produced, the following can be obtained: the polyimide film can be obtained by applying the polyimide precursor solution composition obtained above to the surface of a polyimide substrate or a polyimide film substrate to form a film-like material (coating film), and then subjecting the film-like material to a heat treatment to remove the solvent and to a curing treatment (imidization reaction).

The shape and material of the usable substrate are not particularly limited as long as the substrate has a dense structure to the extent of being substantially impermeable to liquid and gas, and examples thereof include: a film-forming substrate such as a tape, a die, a roll, or a drum, which is known per se and used for producing a general film, an electronic component such as a circuit board having a polyimide film formed as an insulating protective film on the surface thereof, an electric wire, a sliding component having a coating film formed on the surface thereof, a product, a multilayered film formed by forming a polyimide film, a single film in the case of a copper-clad laminated board, a copper foil, and the like.

As a method for applying the polyimide precursor solution composition to these substrates, for example, a known method per se such as a spray coating method, a roll coating method, a spin coating method, a bar coating method, an ink jet method, a screen printing method, a slit coating method, or the like can be suitably used.

The film, thin film, insulating material, and the like formed from the polyimide precursor solution composition applied to the substrate can be defoamed by heating at a relatively low temperature, such as room temperature or lower, under reduced pressure or normal pressure.

A film-like material formed from the polyimide precursor solution composition on a substrate can be cured (imidized) by removing the solvent by heat treatment to form a polyimide, a polyimide film, or a polyimide insulating material. The heat treatment is suitably as follows: compared with the sudden high-temperature heat treatment, the solvent is removed at a lower temperature of 100-140 ℃ at first, and then the temperature is raised to the maximum heat treatment temperature for imidization. The maximum heat treatment temperature may be 200 to 600 ℃, and the heat treatment may be performed preferably at 300 to 500 ℃, more preferably at 250 to 500 ℃. Alternatively, the imidization reaction may be advanced by using a catalyst such as an amine compound in place of the heat treatment or in combination with the heat treatment. Further, as a dehydrating agent for rapidly removing water generated in the imidization process, carboxylic anhydride or the like may be used.

The thickness of the polyimide, the polyimide film, and the polyimide insulating material can be suitably adjusted according to the application, and for example, a polyimide film or film having a thickness of 0.1 to 200 μm, preferably 3 to 150 μm, and more preferably 5 to 130 μm is suitably used. When the heating temperature is lower than 250 ℃, imidization does not proceed sufficiently, and when it exceeds 450 ℃, there is a problem of deterioration of mechanical properties due to thermal decomposition or the like. When the film thickness exceeds 200 μm, the solvent cannot be sufficiently volatilized, and problems such as deterioration of mechanical properties and foaming during heat treatment may occur.

The concentration of the fine particles of the fluorine-based resin in the colored polyimide film, the colored polyimide insulating material, and the like obtained from each of the polyimide precursor solution compositions of the inventions 7 to 10 is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 10 to 35% by mass, based on the total mass of the cured product obtained by curing the polyimide precursor solution composition of the present invention. When the concentration of the fine powder of the fluorine-based resin is too small, the effect of adding the fine powder of the fluorine-based resin is not obtained, and when the concentration of the fine powder of the fluorine-based resin is too large, the mechanical properties of the polyimide and the like are deteriorated.

The concentration of the coloring material of the fluorine-based resin in the colored polyimide insulating material such as the colored polyimide insulating film is not particularly limited, but is preferably 0.1 to 30 mass%, more preferably 1 to 20 mass%, and further preferably about 5 to 20 mass% with respect to the entire mass of the cured product obtained by curing the polyimide precursor solution composition of the present invention. If the concentration of the coloring material is too low, the effects of hiding properties, optical properties, light-shielding properties, light-reflecting properties, design properties, and the like are not exhibited, and if the concentration of the coloring material is too high, the electrical properties, mechanical properties, and the like of the polyimide are degraded.

The colored polyimide film obtained from each of the polyimide precursor solution compositions of the inventions 7 to 10 can be used as a heat-resistant light-weight white material in a white polyimide material such as a white polyimide film obtained by using a white pigment such as titanium oxide as a pigment, specifically as a reflective material for LED (light emitting diode), organic EL light emission, or a base material for a metal layer white film, and can be suitably used for LED, organic EL, a flexible printed wiring board on which other light emitting elements are mounted, and the like.

Further, the black polyimide materials such as black polyimide films obtained from the polyimide precursor solution compositions of the inventions 7 to 10 are excellent in the shielding property, optical characteristics, and light shielding property in electronic parts and mounted parts to be protected.

[ Flexible printed Circuit Board including Circuit Board ]

The flexible printed wiring board including a circuit board according to any one of the 7 th to 10 th aspects of the present invention is characterized in that a colored polyimide film obtained from each of the polyimide precursor solution compositions according to the 7 th to 10 th aspects of the present invention is used.

The flexible printed circuit board including the circuit substrate of the present invention can be manufactured, for example, as follows: a Flexible Printed Circuit (FPC) is manufactured by bonding an insulating polyimide film obtained from the polyimide precursor solution composition to a metal foil using an adhesive composition such as an epoxy resin or a cyanate resin to produce a metal foil laminate (CCL), and applying a circuit to the metal foil.

The thickness of the polyimide film of the present invention as the insulating film may be selected from suitable ranges in consideration of sufficient electrical insulating properties, the thickness of the metal foil laminate, flexibility, and the like, and is preferably 5 to 50 μm, and more preferably 7 to 45 μm.

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

Examples of the metal foil include: examples of the metal foil having conductivity include: gold, silver, copper, stainless steel, nickel, aluminum, alloys thereof, and the like. From the viewpoint of conductivity, ease of handling, price, and the like, copper foil and stainless steel foil can be suitably used. As the copper foil, a copper foil manufactured by a rolling method or an electrolytic method can be used.

The thickness of the metal foil may be set to an appropriate range in consideration of conductivity, interface adhesion with the insulating film, flexibility of the laminate, improvement in bending resistance, easy formation of fine patterns in circuit processing, conductivity between wirings, and the like, and is, for example, preferably within a range of 1 to 35 μm, more preferably within a range of 5 to 25 μm, and particularly preferably within a range of 8 to 20 μm.

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

The flexible printed wiring boards including circuit boards according to the present invention 7 to 10 thus constituted can be provided with a circuit board having excellent heat resistance, electrical characteristics (low dielectric constant, low dielectric loss tangent), processability, etc. and having high insulating properties, as well as functions such as coloring with pigments or dyes, imparting concealing properties, optical characteristics, light-shielding properties, light reflection properties, design properties, etc., by using, as an insulating film, a polyimide film obtained from each of the polyimide precursor solution compositions according to the present invention 1 to 4.

[ covering film ]

Next, the cover films according to the 7 th to 10 th aspects of the present invention are characterized in that an insulating polyimide film obtained from each of the polyimide precursor solution compositions according to the 7 th to 10 th aspects of the present invention and an adhesive layer on at least one surface of the polyimide film are formed.

As the adhesive layer used, an adhesive composition such as an epoxy resin or a cyanate resin used for the circuit board can be used.

The cover films according to the 7 th to 10 th aspects of the present invention are used as surface protective films for flexible printed circuit boards (FPCs) and the like, and an adhesive layer is formed on the obtained polyimide film, and a separator (release film) such as paper or a PET film as a protective layer is bonded to the adhesive layer. The separator (release film) may be provided as needed in consideration of workability, storage stability, and the like.

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

The cover films according to the 7 th to 10 th aspects of the present invention thus constituted can be produced as follows: a cover film having low relative permittivity and dielectric loss tangent, and excellent properties such as heat resistance, dimensional stability, and electrical properties can be produced by forming an adhesive layer formed of the adhesive composition by coating on a polyimide film obtained from each of the polyimide precursor solution compositions according to the above-mentioned inventions 7 to 10 using a comma roll coater, a reverse roll coater, or the like, drying the adhesive layer, and forming a semi-cured state (a state in which the composition is dried or a state in which a curing reaction is carried out in a part of the composition), and then laminating the separator (release film) as the protective layer.

[ electronic devices according to any one of claims 7 to 10]

In the present invention, the electronic devices according to the present invention 7 to 10 use the polyimide insulating materials obtained from the polyimide precursor solution compositions according to the present invention 7 to 10, and can be used, for example, for various electronic devices requiring excellent electrical characteristics (low relative permittivity and low dielectric loss tangent) and electrical insulation, such as insulating materials for bodies and parts of various electronic devices represented by thin mobile phones, game machines, router devices, WDM devices, personal computers, televisions, local servers, thin displays, hard disks, printers, and DVD devices.

In the present invention, the polyimide film, and the polyimide insulating material are used to impart functions such as concealing properties, optical properties, light shielding properties, light reflecting properties, and design properties, heat resistance, mechanical properties, sliding properties, insulating properties, electrical properties such as low dielectric constant and low dielectric loss tangent, and processability to the polyimide, the polyimide film, and the polyimide insulating material, and the flexible printed wiring board, the cover film, and the electronic device including the circuit board are preferably used as an insulating film, an interlayer insulating film for a wiring board, a surface protective layer, a sliding layer, a release layer, a fiber, a filter material, a wire covering material, a bearing, a coating material, a heat insulating shaft, a disk, a heat insulating shaft, and a disk, and the like, even when the polyimide, the film, and the polyimide insulating material are colored with a pigment or a dye, which are obtained from the polyimide, Various belts such as seamless belts, narrow belts, pipes, and the like.

Examples

Hereinafter, the present invention 1 to the present invention 10, and further, the present invention will be described in detail with reference to examples and comparative examples. The present invention 1 to 10 is not limited to the following examples and the like.

[ invention 1: preparation of non-aqueous dispersion of fluorine-based resin: dispersion 1 to 4]

In the formulation compositions shown in Table 1 below, the formulation numbers [ 1] to [ 4] were blended in predetermined amounts and then sufficiently stirred and mixed. Thereafter, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill.

The average particle diameter of PTFE (average particle diameter analyzed by cumulative method in scattering intensity distribution) in dispersions 1 to 4 composed of the above formulation Nos. [ 1] to [ 4] was measured by a dynamic light scattering method based on FPAR-1000 (available from Otsuka Denshi Co., Ltd.) (see Table 2 below).

Further, dispersions 1 to 4 were prepared by adding and sufficiently stirring and mixing dispersions 1 and 2 having the formulation numbers [ 1] to [ 4] according to the formulation number [5 ].

The water content of the dispersions 1 to 4 thus obtained was measured, and as a result, the water content was in the range of 800 to 1800ppm by Karl Fischer's method.

[ Table 1]

(total amount 100% by mass)

Tuo 1Slecbk BL-10 [ butyral (PVB) resin, produced by hydroprocess chemical industries, hydroxy group 28 mol%, butyralation degree 71 + -3 mol%, molecular weight 1.5 ten thousand ]

Tuo 2Slecbk BM-1 [ butyral (PVB) resin, produced by hydroprocess chemical industries, hydroxy group 34 mol%, butyralation degree 65. + -.3 mol%, molecular weight 4 ten thousand ]

[ Table 2]

After the obtained dispersions 1 to 4 were left to stand and stored at 40 ℃ for 1 week in a closed container, the sedimentation state of the particles was visually confirmed, and as a result, no sediment was found and a good state was maintained.

Examples 1 and 2 and comparative examples 1 to 3: preparation of thermosetting resin composition containing fluorine-based resin ]

Using the dispersions 1 to 4 thus obtained, thermosetting resin compositions of fluorine-containing resins were prepared according to the compounding recipe shown in Table 3 below. Further, comparative example 3 was prepared as a composition containing only the resin to which the PTFE dispersion was not added.

After mixing at the compounding ratios shown in examples 1 and 2 and comparative examples 1 to 3, the PTFE dispersion and the resinous material were uniformly mixed by stirring with a dispersing device, thereby obtaining a thermosetting resin composition containing a fluorine-containing resin.

In all of examples 1 and 2 and comparative examples 1 and 2, the mixture was very uniform, and no agglomerates of PTFE were observed.

[ Table 3]

(parts by mass)

Examples 3 and 4 and comparative examples 4 to 6: preparation of a thermosetting resin cured product of a fluorine-containing resin ]

The thermosetting resin compositions of the fluorine-containing resins obtained in examples 1 and 2 and comparative examples 1 to 3 were applied to the entire surface of one side of a polyimide film (thickness: 25 μm) using a coater so that the dried thickness became about 25 μm and became a uniform thickness, dried at about 120 ℃ for about 10 minutes, and then cured by heating at 180 ℃ for 60 minutes to prepare samples for evaluation of relative dielectric constant.

[ evaluation of relative dielectric constant ]

The relative dielectric constant was measured at 1GHz using an impedance Analyzer (impedance Analyzer) in accordance with the test standards of JIS C6481-1996.

[ evaluation of adhesion Strength ]

A sample for evaluation of adhesion was prepared by coating a roughened surface of a single-sided roughened copper foil (18 μm thick) with a100 μm thick screen as a spacer, applying the thermosetting resin composition of the fluorine-containing resin obtained in examples 1 and 2 and comparative examples 1 to 3, drying the solvent at 50 ℃ for 5 minutes, laminating the composition with the single-sided roughened copper foil (18 μm thick) covered with the roughened surface facing the composition, heating the composition at 160 ℃ for 60 minutes, and curing the composition by heating at 180 ℃.

Evaluation of adhesion strength test pieces cut to a width of 1cm were prepared, and T-type peeling was performed by a push-pull force tester.

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

[ Table 4]

As shown in table 4, the cured thermosetting resins of the fluorine-containing resins of examples 3 and 4 of the present invention 1 have a lower relative dielectric constant than comparative example 6 containing no fluorine-containing resin, and have higher adhesive strength than comparative examples 4 and 5 containing no urethane fine particles.

[ invention 2: preparation of non-aqueous dispersion of fluorine-based resin: dispersion 5 to 8]

In the formulation compositions shown in Table 5 below, the formulation numbers [ 6] to [ 9] were blended in predetermined amounts and then sufficiently stirred and mixed. Thereafter, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill.

The average particle diameter of PTFE (average particle diameter analyzed by cumulative quantitative analysis in the scattering intensity distribution) in dispersions 5 to 8 composed of the above formulation Nos. [ 6] to [ 9] was measured by a dynamic light scattering method based on FPAR-1000 (available from Otsuka Denshi Co., Ltd.) (see Table 6 below).

Further, dispersions 5 to 8 were prepared by adding and sufficiently stirring the dispersions 5 and 6 having the formulation numbers [ 6] to [ 9] according to the formulation numbers [ 10] and [ 11 ].

The water content of the dispersions 5 to 8 obtained was measured, and as a result, the water content was in the range of 800 to 1800ppm by Karl Fischer's method.

[ Table 5]

(total amount 100% by mass)

[ Table 6]

After the obtained dispersions 5 to 8 were stored in a closed container at 40 ℃ for 1 week, the sedimentation state of the particles was visually confirmed, and as a result, no sediment was found and the good state was maintained.

Examples 5 and 6 and comparative examples 7 to 9: preparation of thermosetting resin composition containing fluorine-based resin ]

Using the dispersions 5 to 8 thus obtained, thermosetting resin compositions of fluorine-containing resins were prepared according to the compounding recipe shown in Table 7 below. Further, comparative example 9 was prepared as a composition containing only the resin to which the PTFE dispersion was not added.

After mixing at the compounding ratios shown in examples 5 and 6 and comparative examples 7 to 9, the PTFE dispersion and the resinous material were uniformly mixed by stirring with a dispersing device, to obtain a thermosetting resin composition containing a fluorine-containing resin.

In all of examples 5 and 6 and comparative examples 7 and 8, the mixture was very uniform, and no agglomerates of PTFE or the like were observed.

[ Table 7]

(parts by mass)

Examples 7 and 8 and comparative examples 10 to 12: preparation of a thermosetting resin cured product of a fluorine-containing resin ]

The thermosetting resin compositions of the fluorine-containing resins obtained in examples 5 and 6 and comparative examples 7 to 9 were applied to the entire surface of one side of a polyimide film (thickness: 25 μm) so that the thickness after drying was about 25 μm and uniform, dried at about 120 ℃ for about 10 minutes, and then cured by heating at 180 ℃ for 60 minutes, thereby producing samples for evaluation of relative permittivity.

[ evaluation of relative dielectric constant ]

[ evaluation of adhesion Strength ]

A sample for evaluation of adhesion was prepared by coating a roughened surface of a single-sided roughened copper foil (thickness 18 μm) with a100 μm screen as a spacer, applying the thermosetting resin composition of the fluorine-containing resin obtained in examples 5 and 6 and comparative examples 7 to 9, drying the solvent at 50 ℃ for 5 minutes, laminating the composition with the single-sided roughened copper foil (thickness 18 μm) covered with the roughened surface facing the composition, and heating the composition at 160 ℃ for 60 minutes to cure the composition.

For evaluation of adhesion strength, test pieces each having a width of 1cm were prepared and subjected to T-type peeling by a push-pull force tester.

The evaluation results of the relative dielectric constant and the adhesive strength are shown in table 8 below.

[ Table 8]

As shown in table 8, the cured products of the thermosetting resins as the fluorine-containing resins of examples 7 and 8 of the present invention 2 had a lower relative dielectric constant than comparative example 9 containing no fluorine-containing resin, and also had a higher adhesive strength than comparative examples 7 and 8 containing no thermoplastic elastomer.

(invention 3 to invention 6: fluorine-based resin fine powder dispersion, fluorine-based resin fine powder coloring material dispersion, and preparation of coloring material dispersion ]

The fluororesin fine powder dispersions, the fluororesin fine powder coloring material dispersions, and the coloring material dispersions used in the thermosetting resin compositions of examples and comparative examples used in the present invention 3 to the present invention 6 were prepared by the respective preparation methods shown below.

(preparation of fluorine-based resin Fine powder Dispersion)

The compound represented by formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 9 below, and then a PTFE fine powder, which is a fine powder of a fluorine-based resin, was added and further stirred and mixed. Thereafter, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a fluorine-based resin fine powder dispersion A.

(preparation of fluorine-based resin Fine powder coloring Material Dispersion)

The compound represented by formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 10 below, and then a PTFE fine powder as a fine powder of a fluorine-based resin and a black pigment or a white pigment as a coloring material were added and further stirred and mixed. Thereafter, the obtained PTFE + pigment mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a pigment-containing fluororesin fine powder coloring material dispersion B, C.

The average particle diameter of PTFE in the resulting fluororesin fine powder dispersion A was measured by a dynamic light scattering method based on FPAR-1000 (available from Otsuka Denshi Co., Ltd.), and the average particle diameter of PTFE in the resulting dispersion A was 0.30. mu.m.

(preparation of coloring Material Dispersion)

The compound represented by the formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 11 below, and then a black pigment or a white pigment as a coloring material was added thereto and further stirred and mixed. Thereafter, the obtained pigment mixture was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a coloring material dispersion D, E.

[ Table 9]

Preparation of fluorine-based resin Fine powder Dispersion (Total 100% by mass)

1, 1: slecbk BM-1 [ butyral (PVB) resin, produced by hydroprocess chemical industries, hydroxyl group 34 mol%, butyralation degree 65. + -.3 mol%, molecular weight 4 ten thousand ]

[ Table 10]

Preparation of fluororesin Fine powder coloring Material Dispersion (Total 100% by mass)

	B	C
			PTFE micropowder (average particle size of primary particle 0.3 μm)	20	20
Black pigment (Printex25) 2	4
			White pigment (ITT-2 TiO)₂ CR-50)＊3		4
A compound of the formula (I) 1	2	1.5
			Nonaqueous solvent (methyl ethyl ketone, MEK)	74	74.5

1, 1: slecbk BM-1 (butyral (PVB) resin, produced by hydroprocess chemical industries, hydroxy group of 34 mol%,

Butyralation degree of 65. + -.3 mol%, molecular weight of 4 ten thousand%

A, 2: evonik Industries, Inc

3, a: dadonghua chemical industry Co., Ltd

[ Table 11]

Preparation of coloring Material Dispersion (Total 100% by mass)

	D	E
			Black pigment (Printex25) 2	20
White pigment (ITT-2 TiO)₂ CR-50)＊3		20
			A compound of the formula (I) 1	3	1
Nonaqueous solvent (methyl ethyl ketone, MEK)	77	79

A, 2: evonik Industries, Inc

3, a: dadonghua chemical industry Co., Ltd

Examples 9 to 18 and comparative examples 13 to 18: preparation of thermosetting resin composition ]

The fluorine-based resin fine powder dispersion, the fluorine-based resin fine powder coloring material dispersion, and the coloring material dispersion prepared as described above were mixed according to the compounding recipe shown in table 12 below, and then sufficiently stirred by a disperser, thereby obtaining each of the thermosetting resin compositions.

The obtained thermosetting resin compositions were evaluated for settling property and redispersibility by the following evaluation methods.

These results are shown in table 12 below.

(method of evaluating Settlability and redispersibility)

Each of the thermosetting resin compositions was allowed to stand at room temperature (25 ℃) for 30 minutes, and then the state of sedimentation of each particle (fine fluororesin powder, pigment particle) was visually confirmed, and each state of sedimentation and redispersibility was functionally evaluated by the following evaluation criteria.

Evaluation criteria for Settlement Property:

o: no settlement layer is found at the lower part

And (delta): the lower part can be seen with a sedimentation layer (easy to redisperse)

X: the lower part can be seen a sedimentation layer (difficult to redisperse)

Evaluation criteria for redispersibility:

o: the sediment is easy to redisperse when stirred

X: the sediment is difficult to redisperse when stirred

[ Table 12]

(parts by mass)

A, 2: evonik Industries, Inc

The results in Table 12 show that in examples 9 to 18, which are the scope of the present invention 3 to the present invention 7, examples 10, 12, 15 and 17 using titanium oxide showed a small amount of precipitates, but all of them were easily redispersed and were at a level not problematic in terms of handling.

In contrast, in comparative examples 13 to 15, comparative examples 13 and 14 were general thermosetting resin compositions containing no fluorine-based resin fine powder and no coloring material (pigment), and no evaluation was made on the settling property and redispersibility, while comparative examples 15 to 18 were thermosetting resin compositions containing no fluorine-based resin fine powder and no coloring material (black pigment, white pigment).

The water content of the obtained thermosetting resin compositions of examples 9 to 18 and comparative examples 13 to 18 was measured, and the water content was in the range of 800 to 2500ppm by Karl Fischer's method.

Examples 19 to 28 and comparative examples 19 to 24: evaluation of insulating Material composition

The thermosetting resin compositions obtained in examples 9 to 18 and comparative examples 13 to 18 were used as insulating material compositions, and applied to the entire surface of one side of a polyimide film (thickness: 25 μm) using a coater so that the thickness after drying was about 25 μm and uniform, dried at about 120 ℃ for about 10 minutes, and then cured by heating at 180 ℃ for 60 minutes to prepare evaluation samples in which the insulating material compositions were cured.

(evaluation of Electrical characteristics)

The relative dielectric constant of the obtained evaluation sample was measured at 1GHz using an impedance Analyzer (impedance Analyzer) in accordance with the test standards of JIS C6481-1996. The volume resistivity was measured in accordance with the test standard of JIS C2151. The results are shown in table 5 below.

[ Table 13]

As shown in table 13 above, even when carbon black was contained as a black pigment, the evaluation samples obtained by curing the insulation material compositions of examples 19, 21, 23, 24, 26, and 28 were low in relative permittivity and high in volume resistivity as compared with comparative examples 13 and 14 containing no pigment and comparative examples 15 and 16 containing carbon black as a black pigment. Even when titanium oxide was contained, the evaluation samples obtained by curing the insulating material compositions of examples 21, 23, 26 and 28 were lower in relative permittivity than those of comparative examples 21 and 23.

[ evaluation of adhesive composition for Circuit Board ]

The thermosetting resin compositions obtained in examples 9 to 18 and comparative examples 13 to 18 were used as adhesive compositions for circuit boards.

(examples 29 to 38, comparative examples 25 to 30: laminate for Circuit Board)

The adhesive compositions for circuit boards obtained in examples 9 to 18 and comparative examples 13 to 18 were applied to the entire surface of one side of a polyimide film (thickness: 25 μm) using a coater so that the thickness after drying was about 10 μm and uniform, thereby forming an adhesive resin layer, and then dried to be semi-cured. Then, a similar adhesive resin layer was formed on the opposite side of the polyimide film to prepare an adhesive sheet.

Then, copper foils (thickness: about 12 μm, roughness of matte side (Rz): 1.6 μm) were laminated on both sides of the adhesive sheet, and then at 170 ℃ at 40kgf/cm²The pressure of (3) was applied, and the resultant was cured at 170 ℃ for 5 hours to produce a laminated board for a circuit board.

The resulting laminated boards for circuit boards of examples 29 to 38 and comparative examples 25 to 30 were used as evaluation samples.

(examples 39 to 48, comparative examples 31 to 36: cover film)

The adhesive compositions for circuit boards obtained in examples 9 to 18 and comparative examples 13 to 18 were applied to the entire surface of one side of a polyimide film (thickness: 25 μm) so that the thickness after drying was about 25 μm and uniform, dried at about 120 ℃ for about 10 minutes, and then release-coated release paper having a thickness of 125 μm was laminated to produce a cover film.

The cover films of examples 39 to 48 and comparative examples 31 to 36 were laminated in this order of polyimide film/adhesive surface of cover film/copper foil (12 μm), and then the laminate was heated at 180 ℃ to 40kgf/cm²Hot pressing was performed for 60 minutes under the pressure of (2) to prepare an evaluation sample.

(evaluation of Electrical characteristics)

(method of evaluating Heat resistance)

A sample having a size of 50mm X50 mm was prepared, subjected to moisture absorption treatment at 120 ℃ under 0.22MPa for 12 hours, and then treated at 260 ℃ for 1 minute, and the state of the sample was visually observed. As evaluation criteria, it is indicated as "O" if there is no abnormality such as peeling, deformation, or swelling, and as "X" if there is an abnormality such as peeling, deformation, or swelling.

(method of evaluating adhesive Strength)

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

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

[ Table 14]

[ Table 15]

[ evaluation of prepreg ]

(examples 49 to 58, comparative examples 37 to 42: prepreg)

Each of the adhesive compositions for circuit boards obtained in examples 9 to 18 and comparative examples 13 to 18 was impregnated with NE glass cloth having a thickness of about 100 μm, and then dried at about 120 ℃ for about 10 minutes to produce a thermosetting prepreg having a total thickness of about 125 μm.

The prepregs of examples 49 to 58 and comparative examples 37 to 42 were laminated in the order of polyimide film (12.5 μm)/prepreg/polyimide (12.5 μm), and then the prepregs were laminated at 180 ℃ at 40kgf/cm²Hot pressing was performed for 60 minutes under the pressure of (2) to prepare an evaluation sample.

(evaluation of Electrical characteristics)

(method of evaluating Heat resistance)

(method of evaluating adhesive Strength)

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

[ Table 16]

As shown in tables 14 and 15, the laminate sheets for circuit boards of examples 29 to 38 and the cover films of examples 39 to 48 using the thermosetting resin compositions of examples 9 to 18 as the adhesive compositions for circuit boards were colored black and white, but were judged to be lower in dielectric constant and equivalent in heat resistance and adhesiveness to the laminate sheets for circuit boards of comparative examples 25 to 30 and the cover films of comparative examples 31 to 36 using the thermosetting resin compositions of comparative examples 13 to 18 as the adhesive compositions for circuit boards.

As shown in Table 16, although the prepregs of examples 49 to 58 using the thermosetting resin compositions of examples 9 to 18 were colored black and white, it was confirmed that they had a lower dielectric constant and equivalent heat resistance and adhesiveness to those of the prepregs of comparative examples 37 to 42 using the thermosetting resin compositions of comparative examples 13 to 18.

(7 th invention to 10 th invention: preparation of fluorine-based resin Fine powder Dispersion, coloring Material Dispersion, and polyimide precursor solution ]

The fluororesin fine powder dispersion, the fluororesin fine powder coloring material dispersion, the coloring material dispersion and the polyimide precursor solution used in the polyimide precursor solution compositions of examples and comparative examples used in the present invention 7 to the present invention 10 were prepared by the following preparation methods.

(preparation of fluorine-based resin Fine powder Dispersion)

The compound represented by formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 17 below, and then a PTFE fine powder, which is a fine powder of a fluorine-based resin, was added and further stirred and mixed. Thereafter, the obtained PTFE mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a fluorine-based resin fine powder dispersion A.

(preparation of fluorine-based resin Fine powder coloring Material Dispersion)

The compound represented by formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 18 below, and then a PTFE fine powder as a fine powder of a fluorine-based resin and a black pigment or a white pigment as a coloring material were added and further stirred and mixed. Thereafter, the obtained PTFE + pigment mixed solution was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a pigment-containing fluororesin fine powder coloring material dispersion B, C.

The average particle diameter of PTFE in the resulting fluororesin fine powder dispersion A was measured by a dynamic light scattering method based on FPAR-1000 (available from Otsuka Denshi Co., Ltd.), and the average particle diameter of PTFE in the resulting dispersion A was 0.32. mu.m.

(preparation of coloring Material Dispersion)

The compound represented by formula (I) was sufficiently stirred and mixed in a nonaqueous solvent by a compounding formula shown in table 19 below, and then dissolved, and a black pigment or a white pigment as a coloring material was added thereto and further stirred and mixed. Thereafter, the resultant pigment mixture liquid was dispersed with zirconia beads having a diameter of 0.3mm by using a horizontal bead mill to prepare a coloring material dispersion D, E.

(preparation of polyimide precursor solution)

To a glass vessel equipped with a stirrer and a nitrogen gas pipe, 400 parts by mass of N, N-dimethylformamide, 27 parts by mass of p-phenylenediamine, and 73 parts by mass of 3,3 ', 4, 4' -biphenyltetracarboxylic acid dihydrate were added and mixed, and sufficiently stirred to obtain a polyimide precursor solution having a solid content concentration of 18 mass%.

[ Table 17]

Preparation of fluorine-based resin Fine powder Dispersion (Total 100% by mass)

1, 1: slecbk BM-1 [ butyraldehyde-reduced (PVB) resin, produced by hydroprocess chemical industries, hydroxyl group 34 mol%, butyralization degree 65. + -.3 mol%, molecular weight 4 ten thousand ]

[ Table 18]

	B	C
			PTFE micropowder (average particle size of primary particle 0.3 μm)	20	20
Black pigment (Printex25) 2	4
			White pigment (ITT-2 TiO)₂ CR-50)＊3		4
A compound of the formula (I) 1	2	1.5
			Nonaqueous solvent (dimethylacetamide, DMAc)	74	74.5

A, 2: evonik Industries, Inc

3, a: dadonghua chemical industry Co., Ltd

[ Table 19]

Preparation of coloring Material Dispersion (Total 100% by mass)

	D	E
			Black pigment (Printex25) 2	20
White pigment (ITT-2 TiO)₂ CR-50)＊3		20
			A compound of the formula (I) 1	3	1
Nonaqueous solvent (dimethylacetamide, DMAc)	77	79

A, 2: evonik Industries, Inc

3, a: dadonghua chemical industry Co., Ltd

[ examples 59 to 63 and comparative examples 43 to 45 ]

The fluorine-based resin fine powder dispersion, the fluorine-based resin fine powder coloring material dispersion, the coloring material dispersion, and the polyimide precursor solution prepared as described above were mixed by a compounding recipe shown in table 20 below, and then sufficiently stirred by a disperser, thereby obtaining each polyimide precursor solution composition.

The obtained polyimide precursor solution compositions were evaluated for sedimentation property and redispersibility by the following evaluation methods.

These results are shown in table 20 below.

(method of evaluating Settlability and redispersibility)

Each polyimide precursor solution composition was allowed to stand at room temperature (25 ℃) for 30 minutes, and then the state of sedimentation of each particle (fluorine-based resin fine powder, pigment particle) was visually observed, and each state of sedimentation and redispersibility was evaluated for functionality according to the following evaluation criteria.

Evaluation criteria for Settlement Property:

o: no settlement layer is found at the lower part

X: the lower part can be seen a sedimentation layer (difficult to redisperse)

Evaluation criteria for redispersibility:

o: the sediment is easy to redisperse when stirred

X: the sediment is difficult to redisperse when stirred

[ Table 20]

(parts by mass)

A, 2: evonik Industries, Inc

The results in Table 20 show that examples 59 to 63, which are the scope of the present invention from the 7 th to the 10 th inventions, show that examples 60 and 62 using titanium oxide show a slight amount of sediment, but they are easily redispersed and have no problem in terms of handling.

In contrast, in comparative examples 43 to 45, comparative example 43 was a normal polyimide precursor solution (composition) containing no fluorine-based resin fine powder and no coloring material (pigment), and no evaluation was made on the settling property and redispersibility, while comparative examples 44 and 45 were polyimide precursor solution compositions containing no fluorine-based resin fine powder and no coloring material (pigment).

The water content of the polyimide precursor solution compositions of examples 59 to 63 and comparative examples 43 to 45 was measured, and the water content was in the range of 800 to 3000ppm by Karl Fischer's method.

(preparation of polyimide film/polyimide film)

The polyimide precursor solution compositions of examples 59 to 63 and comparative examples 43 to 45 obtained above were applied to a glass plate as a substrate by a coater, and were defoamed and predried at 25 ℃ under reduced pressure for 50 minutes, then subjected to a heat treatment at 120 ℃ for 45 minutes, at 150 ℃ for 30 minutes, at 200 ℃ for 15 minutes, at 250 ℃ for 10 minutes and at 400 ℃ for 10 minutes under a nitrogen atmosphere, to form a polyimide film having a thickness of 30 μm. The polyimide film was peeled from the glass substrate to obtain a polyimide film.

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

The results of these evaluations and measurements are shown in table 21 below.

(method of evaluating the State of polyimide film)

The polyimide film was visually observed, and the state was evaluated for functionality according to the following evaluation criteria.

Evaluation criteria:

o: free of foreign matter such as PTFE aggregates and has a smooth surface

X: foreign matter such as PTFE aggregates was confirmed

(method of measuring relative permittivity of polyimide film)

For each of the polyimide films obtained, the relative dielectric constant was measured at 25 ℃ and a frequency of 1kHz using an impedance Analyzer (impedance Analyzer) in accordance with the test standards of JIS C6481-1996.

(method of measuring volume resistivity of polyimide film)

Each of the polyimide films obtained was measured in accordance with the test standard of JIS C2151.

[ Table 21]

The results in Table 21 show that examples 59 to 63 have a relative dielectric constant equivalent to that of comparative example 43 made of polyimide alone. On the other hand, it was confirmed that comparative examples 44 and 45 have improved relative permittivity, but examples 59 to 63 have equivalent relative permittivity or can suppress the increase.

Industrial applicability

The fluorine-containing resin thermosetting resin composition using the fluorine-containing resin non-aqueous dispersion according to the invention of the invention 1 and 2 has a fine particle diameter, a low viscosity, an excellent storage stability, and is suitable for mixing with various resin materials, and the cured product thereof can achieve a low dielectric constant and a low dielectric loss tangent and can suppress the decrease in adhesion strength and adhesive strength, and therefore can be suitably used for an insulating layer of a multilayer printed wiring board, an adhesive for a circuit board, a laminate for a circuit board, a cover film, a prepreg, and the like.

The thermosetting resin composition containing a fluororesin according to any of the inventions 3 to 6 is a thermosetting resin composition which can give a colored thermosetting resin composition having high insulation properties and excellent heat resistance, electric characteristics (low dielectric constant, low dielectric loss tangent), processability and the like even when a non-aqueous dispersion of a fluororesin is colored with a coloring material such as an organic pigment, an inorganic pigment or a dye to impart functions such as concealing properties, optical characteristics, light-shielding properties, light-reflecting properties and design properties, and which can be suitably used for a flexible printed circuit board including a circuit board, a cover film, an electronic device using an insulating material based on a thermosetting resin composition such as an insulating film or a related insulating film for a wiring board using the thermosetting resin composition, and a surface protective layer, a sliding layer, a release layer, a surface protective layer, a, Fibers, filter materials, wire coating materials, bearings, paints, various belts, pipes, etc., for example, heat-insulating shafts, disks, seamless belts, etc.

In the polyimide precursor solution composition according to the 7 th to 10 th aspects of the present invention, the non-aqueous dispersion of the fluorine-based resin can be suitably used for a colored polyimide, a polyimide film or the like having high insulation properties and excellent heat resistance, electric characteristics (low dielectric constant, low dielectric loss tangent), processability or the like even if it is colored with a coloring material such as an organic pigment, an inorganic pigment or a dye to impart functions such as hiding properties, optical characteristics, light-shielding properties, light reflectivity, design properties or the like, a flexible printed wiring board including a circuit board, a cover film, and an electronic device using a polyimide insulating material such as an insulating film or a related insulating film for a wiring board using the polyimide, the polyimide film, the polyimide insulating material, and a surface protective layer, a sliding layer, Various tapes, pipes, etc. such as a release layer, fibers, a filter material, a wire covering material, a bearing, a coating material, a heat-insulating shaft, a coil, a seamless tape, etc.

Claims

1. A thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin,

in the formula (I), l, m and n are positive integers.

2. A thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a resin composition containing a cyanate ester resin and/or an epoxy resin, wherein the fluorine-based resin fine powder dispersion contains at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a nonaqueous solvent,

in the formula (I), l, m and n are positive integers.

3. A thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluororesin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a resin composition containing a cyanate ester resin and/or an epoxy resin, the fluororesin fine powder dispersion containing at least: a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent,

in the formula (I), l, m and n are positive integers.

4. A thermosetting resin composition containing a fluorine-containing resin, characterized by containing at least: a fluororesin fine powder coloring material dispersion containing at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material and a nonaqueous solvent,

in the formula (I), l, m and n are positive integers.

5. A polyimide precursor solution composition characterized by containing at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material, and a polyimide precursor solution,

in the formula (I), l, m and n are positive integers.

6. A polyimide precursor solution composition characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a nonaqueous solvent,

in the formula (I), l, m and n are positive integers.

7. A polyimide precursor solution composition characterized by containing at least: a fluorine-based resin fine powder dispersion, a coloring material dispersion or a coloring material solution, and a polyimide precursor solution, wherein the fluorine-based resin fine powder dispersion contains at least: a fine powder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent, wherein the coloring material dispersion or the coloring material solution contains at least a coloring material and a non-aqueous solvent,

in the formula (I), l, m and n are positive integers.

8. A polyimide precursor solution composition characterized by containing at least: a fluorine-based resin fine powder coloring material dispersion containing at least: fine powder of a fluorine-based resin, a compound represented by the following formula (I), a coloring material and a nonaqueous solvent,

in the formula (I), l, m and n are positive integers.