TWI713510B - Non-aqueous dispersion containing fluorine resin, polyimide precursor solution composition containing fluorine resin, polyimide using the same, polyimide film, adhesive composition for circuit board, and the like Manufacturing method - Google Patents

Abstract

The present invention is to provide a dispersion in which the dispersion state of a fluorine resin is uniformly controlled, a polyimide precursor solution composition using the dispersion, an adhesive composition, and the heat resistance obtained by the composition , Mechanical properties, low dielectric constant, low dielectric tangent and other electrical properties, excellent processability, polyimide, polyimide film, its manufacturing method, circuit board using the polyimide film, Cover film, and provide a polyimide precursor solution composition and adhesive composition containing fluorine-based resin, which is characterized by containing: fine powder containing fluorine-based resin, and at least containing fluorine-containing groups and lipophilic groups Non-aqueous dispersions of fluorine-based additives or fluorine-based resins of butyraldehyde resin; and polyimide precursor solutions.

Description

Non-aqueous dispersion containing fluorine resin, polyimide precursor solution composition containing fluorine resin, polyimide using the same, polyimide film, adhesive composition for circuit board, and the like Manufacturing method

The present invention relates to a non-aqueous dispersion containing a fluorine-based resin, a polyimide precursor solution composition containing a fluorine-based resin, a polyimide using the same, a polyimide film, and their manufacturing methods, In detail, it relates to the polyimide precursor solution composition that uniformly controls the dispersion state of the fluorine-based resin, and the heat resistance, mechanical properties, and electrical properties (low dielectric constant, low Dielectric tangent), polyimide, polyimide film with excellent processability, and their manufacturing methods, adhesive composition for circuit substrates used in the manufacture of circuit substrates, and circuit substrates using them Laminates, cover films, prepregs, etc.

In recent years, along with advances in the speed and functionality of electronic devices, there has been a demand for higher communication speeds. Among them, low dielectric constant and low dielectric tangent of various electronic equipment materials are required, especially for insulating materials or substrate materials. 化 etc.

One of the electronic equipment materials includes a circuit board. This circuit board uses a copper-clad laminate, and the electrically insulating film and the copper foil are joined via an adhesive layer.

In addition, the copper clad laminate is used by processing the copper foil portion and forming a wiring pattern. In order to protect this wiring pattern, it is covered with an insulating cover film, and this cover film is also bonded via an adhesive layer.

In addition, in the manufacture of a prepreg used for insulation between layers and bonding, and rigidity with respect to the circuit board, various fibers are impregnated with an adhesive for use.

In the past, polyimides including polyimide films, etc., have been widely used for electrical and electronic applications due to their excellent heat resistance, electrical insulation, chemical resistance, and mechanical properties. For example, when polyimide is used as a film, it is used as an insulating substrate for electronic circuit materials, and it can also be processed into an adhesive film or adhesive tape for use. In addition, when used as a coating agent, the polyimide precursor solution composition is coated and dried, and then heat-treated to make it imidized. It can also be used as an insulating layer for electronic circuits (interlayer insulating material for multilayer wiring substrates), Surface protective film of semiconductor elements, etc.

Generally, the polyimide film is attached to the copper foil using an adhesive, or processed into a layer composed of a thin film layer and a copper foil by vapor deposition, electroplating, sputtering, or casting. Plywood (polyimide film with copper foil), or use as a base film for flexible printed multilayer circuit boards.

This copper clad laminate is processed by processing the copper foil part and forming wiring patterns, etc. In use, this wiring pattern is covered and protected by an insulating cover film. The base material of this cover film is also mainly made of a polyimide film, and is bonded via an adhesive layer.

In addition, in the manufacture of a prepreg used for insulation between layers and bonding, and rigidity with respect to the circuit board, various fibers are impregnated with an adhesive for use.

In particular, in recent years with high-density packaging of circuit boards or semiconductor packaging substrates, in order to achieve high-speed signal transmission, insulating resins with low dielectric constant and low dielectric tangent are used as interlayer insulating films, etc. , Is gradually becoming the mainstream. For polyimides including polyimide films, low dielectric constant, low dielectric tangent and other electrical properties are also required.

Therefore, in order to improve the electrical properties, a method of using a fluorine resin with high heat resistance and excellent electrical properties in combination with polyimide has been gradually proposed.

In the past, polyimide compositions and polyimide films containing fluorine-based resins, for example, are known as: 1) A polyimide composition containing fluorine-based resins and a manufacturing method thereof, which are characterized by : Fluorine resin powder, in the presence of a surfactant compound having a fluorine atom, uniformly dissolved in the aromatic tetracarboxylic acid component mainly composed of biphenyl tetracarboxylic acid and the aromatic diamine component Polyimide can be dissolved in an organic polar solvent (for example, refer to Patent Document 1); 2) a polyimide resin characterized by: relative to a polyimide resin having a repeating unit represented by a specific formula 100 parts by weight, containing 3 to 60 parts by weight of fluororesin and 3 to 60 parts by weight of aromatic polyamide (for example, refer to Patent Literature 2); 3) A manufacturing method of insulating materials for high-frequency electronic parts, which includes the steps of dissolving soluble polyimide in a volatile organic solvent to provide a polyimide solution, and adding carbon fluoride particles to The polyimide solution is uniformly dispersed, and the step of providing the polyimide solution dispersed with fluorocarbon resin, the step of coating the polyimide solution with fluorocarbon resin dispersed on the substrate, and The step of drying it (for example, refer to Patent Document 3); 4) A single-layer substrate, which is a single-layer substrate used for electronic or electrical purposes as a component of a single or multilayer structure, characterized by: a single-layer substrate, A polymer blend containing at least a polyimide component and a fluoropolymer component derived from a fluoropolymer fine powder with a specific average particle size. A single-layer substrate has an outer surface and an inner core material. The amount of the fluoropolymer component present in the inner core material is a larger amount of the fluoropolymer component, and the inner core material contains a larger amount of the polyimide component present in the outer surface of the polyimide component, Having a total thickness within a specific range, the aforementioned polymer blend is prepared by incorporating the aforementioned fluoropolymer fine powder into polyamic acid and treating the polyamic acid by an imidization process (for example, refer to the patent Document 4); 5) A polyimide composite film and its manufacturing method, which is a film containing a mixture of polyimide and fluororesin particles and heat-cured, characterized by being present near the surface of the film It is known that at least a part of the fluororesin particles melt and flow on one side or both sides of the aforementioned film to precipitate and form a fluororesin film partially or completely (for example, refer to Patent Document 5).

Among the polyimide compositions containing fluorine-based resin powders and the like described in the above Patent Documents 1 to 5, and the production method thereof, conventionally used fluorine When the resin is dispersed, a fluorine-containing surfactant or dispersant such as alkane fluoride is generally used.

However, polyimide materials containing fluorine-containing resin dispersions using these fluorine-containing surfactants or dispersants can reduce the dielectric constant or dielectric tangent by the effect of the fluorine-based resin However, surfactants or dispersants containing fluorine generally increase the dielectric constant or dielectric tangent, and it is difficult to fully improve the electrical properties.

In addition, the presence of this additive also has problems in terms of adhesion, adhesion, and heat resistance of polyimide materials.

Furthermore, fluorine-containing surfactants or dispersants may be thermally decomposed and may become hydrogen fluoride during the heat treatment during polyimidization or when the waste liquid is burned and discarded, which may cause harm to the environment. Concerns about negative effects.

Therefore, there are technical issues or restrictions regarding the improvement of sufficient electrical or physical properties, and the negative impact on the environment, etc. At present, there are few negative impacts on the environment that can further improve the electrical properties or physical properties. There is still a demand for polyimide composition and polyimide film made of fluorine resin.

Adhesive compositions for circuit boards are known as, for example, an adhesive composition for the manufacture of circuit boards, which is characterized by containing a cyanate (cyanate ester) resin and dispersed in the aforementioned cyanic acid (cyanic acid). Ester) the fluorine resin powder and rubber component in the ester resin (for example, refer to Patent Document 6); or an adhesive epoxy resin composition, which is characterized by containing: epoxy resin, epoxy resin represented by a specific formula The compound is used as the main component Reactive diluent and hardener (for example, refer to Patent Document 7).

However, in the adhesive composition for manufacturing a circuit board described in Patent Document 6, it is difficult to uniformly control the dispersion state of the fluorine-based resin powder in the resin composition, and a problem remains for the improvement of sufficient electrical characteristics. In addition, the cyanate ester resins or epoxy resins described in the aforementioned Patent Documents 6 and 7, which are currently widely used as adhesive compositions for circuit boards, have relatively high relative permittivity or dielectric tangent. High, there are technical issues or limitations for improving electrical characteristics, and there is still a demand for adhesive compositions for circuit boards that can further improve electrical characteristics.

On the other hand, the fluorine-based resin of polytetrafluoroethylene (PTFE) is a material with excellent heat resistance, electrical insulation, low dielectric properties, low friction properties, non-adhesive properties, and weather resistance. It is used in electronic equipment, Sliding materials, automobiles, kitchen supplies, etc. Polytetrafluoroethylene with this characteristic is added as a fine powder to various resin materials (anti-corrosion materials) or rubber, adhesives, lubricants or greases, printing inks or coatings, etc., and is used for the purpose of improving product characteristics. use.

This fine powder of PTFE fluorine resin is usually polymerized with tetrafluoroethylene (TFE) in the presence of water, polymerization initiator, fluorinating agent, paraffin wax and other stabilizers by emulsion polymerization After obtaining an aqueous dispersion containing polytetrafluoroethylene fine particles, it is prepared by concentration, agglomeration, and drying (for example, refer to Patent Document 8).

The method of adding this fluorine-based resin fine powder to the resin material, for example, in addition to the method of direct mixing, is known to be dispersed in A method of mixing in water or oily solvent as a fluorine-based resin dispersion. It can be mixed uniformly by dispersing in water or oil solvent before adding.

However, the fluorine-based resin fine powder has a strong cohesive force between particles, and particularly in an oily solvent, it has a problem that it is difficult to disperse in a form with a particle diameter, low viscosity, and excellent storage stability.

Furthermore, when added to non-water-soluble resins or anti-corrosive materials, etc., oily solvent-based polytetrafluoroethylene dispersions are required, and inventions related to aqueous polytetrafluoroethylene dispersions are known. There are many (for example, refer to Patent Documents 9 and 10), but compared with this aqueous dispersion, there are almost no reports about oily solvent-based polytetrafluoroethylene dispersions (for example, refer to Patent Documents 11 and 12) .

The technology described in Patent Document 11 is composed of PTFE particles and at least one monomer or polyolefin unsaturated oil or oil mixture. The molecules of the olefin unsaturated oil are attached to the surface of the PTFE (primary) particles. The co-bond/chemical bond is formed by free radical reaction, and there is permanent charge separation between the oil molecules bonded to the surface of the PTFE particles, and the fine dispersion of the PTFE particles in the oil or oil mixture for a long time Stable oil-PTFE dispersion. The preparation method uses a modified PTFE (emulsion) polymer with persistent perfluoro (peroxy) free radicals together with at least one olefin-based unsaturated oil It is obtained by mixing and then applying mechanical stress to the modified PTFE (emulsion) polymer. This method is more complicated. In addition, it does not use general-purpose PTFE particles. This technical idea (composition and effect) It is completely different from the present invention.

In addition, the technique described in Patent Document 12 described above describes "a fluoropolymer non-aqueous dispersion liquid characterized by a non-aqueous medium such as a fluoropolymer such as PTFE and an organic solvent having a boiling point of 40 to 250°C. , And as a dispersant, choose from the general formula: Rf ¹ -(X) _n -Y [In the formula, Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group with 1-12 carbon atoms, and n is 0 or 1, X is -O-, -COO- or -OCO-, Y is -(CH ₂ ) _p H, -(CH ₂ ) _p OH or -(OR ¹ ) _q (OR ² ) _r OH, p Is an integer from 1 to 12, q is an integer from 1 to 12, r is an integer from 0 to 12, R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms; but R ¹ and R ^{2 are} different] At least one of the fluorine compounds shown" and so on.

However, in the aforementioned Patent Document 12, there is no description or suggestion related to "polytetrafluoroethylene fine powder with a primary particle diameter of 1 μm or less". In paragraph [0041] of Patent Document 12, it is stated that "when dispersing a powdery fluoropolymer, by dispersing in a size of 5 to 500 μm, a dispersion that is not easy to reaggregate can be obtained." In the description of the experimental examples 1 to 12, as the fluoropolymer, "Ruburon L-2 (PTFE)" manufactured by Daikin Industry Co., Ltd. is used (in the technical data, the average particle size (50%) is based on the dry laser method. )3.5μm). In addition, the system describes "the size of 0.05-5 μm when the aqueous dispersion is phase-inverted." In this way, Patent Document 12 does not assume the use of particles of 1 μm or less when using polytetrafluoroethylene fine powder, or it implies that it is difficult to disperse the powder.

In addition, paragraph [0057] of this patent document 12 states that "additives such as quartz sand, carbon black, diamond, tourmaline, germanium, alumina, silicon nitride, extended pigments, etc. can be simply contained", and so on. Composition is arbitrary As for the ingredients, there is no description or suggestion as to what effect these ingredients exert in the fluoropolymer non-aqueous dispersion liquid, and in Document 12, the effects and the like are not verified by examples.

Therefore, although the above-mentioned patent document 12 discloses the related technology of the present invention, the technical idea (the structure and the result of the action) of the patent document 12 is different from the present invention.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Laid-Open No. 2-286743 (application scope, examples, etc.)

Patent Document 2: Japanese Patent Application Laid-Open No. 3-292365 (application scope, examples, etc.)

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-203430 (application scope, examples, etc.)

Patent Document 4: Japanese Patent Application Publication No. 2005-142572 (application scope, examples, etc.)

Patent Document 5: Japanese Patent Application Laid-Open No. 2007-30501 (application scope, examples, etc.)

Patent Document 6: Japanese Special Publication No. 2015-509113 (application scope, examples, etc.)

Patent Document 7: Japanese Patent Application Laid-Open No. 2015-13950 (application scope, examples, etc.)

Patent Document 8: Japanese Patent Application Publication No. 2012-92323 (Patent application (Scope, Examples, etc.)

Patent Document 9: Japanese Patent Application Laid-Open No. 2006-169448 (application scope, examples, etc.)

Patent Document 10: Japanese Patent Application Publication No. 2009-179802 (application scope, examples, etc.)

Patent Document 11: Japanese Special Publication No. 2011-509321 (application scope, examples, etc.)

Patent Document 12: Japanese Patent Application Laid-Open No. 2011-225710 (application scope, examples, etc.)

The present invention was created in view of the above-mentioned conventional problems and current situation, etc., in order to solve these problems. The object is to provide a non-aqueous dispersion containing a fluorine-based resin and a polyimide that uniformly controls the dispersion state of the fluorine-based resin Precursor solution composition, and polyamide with excellent heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant, low dielectric tangent and other electrical properties and processability obtained from the composition Amine, polyimide film, and their manufacturing methods, and circuit substrates, cover films, insulating films, related insulating films for wiring boards, surface protection layers, and sliding films using the polyimide or polyimide film Various belts, tapes, tubes, etc. such as layers, peeling layers, fibers, filter materials, wire coating materials, bearings, coatings, insulation shafts, brackets, seamless belts, etc.

The inventors of the present invention conducted intensive studies in order to solve the problems of the past and found that a non-aqueous dispersion containing a fluorine-based resin, a polyimide precursor solution composition containing a fluorine-based resin for the above-mentioned purpose, and a fluorine-containing resin A resin adhesive composition, a polyimide using the resin, a cover film, etc., have completed the present invention.

That is, the present invention exists in the following (1) to (37).

(1) A non-aqueous dispersion of fluorine-based resin, which contains fine powder of fluorine-based resin, and fluorine-based additives containing fluorine-containing groups and lipophilic groups.

(2) The non-aqueous dispersion of fluorine-based resin according to (1), wherein in the aforementioned fluorine-based resin fine powder dispersion, the average particle size of the fluorine-based resin fine powder in the dispersed state is 1 μm or less.

(3) The non-aqueous dispersion of the fluorine resin according to (1) or (2), wherein the water content measured by Karl Fischer titration method is below 5000 ppm.

(4) The non-aqueous dispersion of fluorine resin according to any one of (1) to (3), wherein the fine powder of the aforementioned fluorine resin is selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, One or more fluorine series in the group consisting of perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene Fine powder of resin.

(5) The non-aqueous dispersion of fluorine resin according to any one of (1) to (4), wherein the solvent used in the aforementioned non-aqueous dispersion contains From γ-butyrolactone, acetone, butanone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, Methyl n-pentanone, methyl isobutyl ketone, methyl isopentanone, 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, dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol Monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, Methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, phenyl methyl ether, ethyl benzyl ether, Cresol methyl ether, diphenyl ether, dibenzyl ether, ethoxybenzene, butyl phenyl ether, benzene, ethylbenzene, diethylbenzene, amylbenzene, cumene, toluene, Xylene, isopropyl toluene, trimethylbenzene, methanol, ethanol, 2-propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether , Methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methyl phenol monoglycidyl ether, ethyl phenol monoglycidyl ether, butyl phenol monoglycidyl ether Glyceryl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofuran acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, methyl Glycidyl acrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoro Ether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, Dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetaminophen, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N -Acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethyl Acetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfide, diethyl sulfide, dimethyl sulfide, diethyl sulfide, γ-butyrolactone, cyclobutane One solvent, or two or more of these solvents in the group consisting of halogenated phenols and various silicone oils.

(6) A polyimide precursor solution composition containing fluorine-based resin, characterized in that: the non-aqueous dispersion of fluorine-based resin as in any one of (1) to (5) contains polyimide Imine precursor solution.

(7) A polyimide characterized in that it is obtained by using the polyimine precursor solution composition containing a fluorine-based resin as in (6).

(8) A polyimide film characterized in that it is obtained by using the polyimide precursor solution composition containing a fluorine-based resin as in (6).

(9) A manufacturing method of polyimide, which is characterized by comprising the step of making a non-aqueous dispersion of fluorine-based resin, mixing the non-aqueous dispersion of fluorine-based resin with a polyimide precursor solution, and making The step of preparing a polyimide precursor solution composition containing a fluorine-based resin, and by imidizing the polyimide precursor solution composition in the polyimide precursor solution composition to obtain dispersed fluorine-based resins The step of polyimide resin.

(10) A manufacturing method of polyimide film, characterized in that: It includes the step of obtaining polyimide as in (9), and further includes the step of obtaining polyimide film.

(11) A circuit board characterized by using the polyimide film obtained by the manufacturing method as in (10).

(12) A cover film characterized by using the polyimide film obtained by the manufacturing method as in (10).

(13) An adhesive composition for a circuit board, characterized in that the non-aqueous dispersion of fluorine-based resin as in any one of (1) to (5) contains a cyanate ester resin or epoxy resin The formed resin composition.

(14) A laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, and a laminate for a circuit board, characterized by It is: the adhesive layer is the adhesive composition for a circuit board as in (13).

(15) The circuit board laminate according to (14), wherein the aforementioned insulating film is selected from polyimide (PI: Polyimide), liquid crystal polymer (LCP: Liquid Crystal Polymer), and polyethylene terephthalate Diester (PET: Polyethylene Terephthalate), Polyethylene Naphthalate (PEN: Polyethylene Naphthalate), Polyphenylene Sulfide (PPS: Polyphenylene Sulfide), Polyetherimide (PEI: Polyetherimide), Polyphenylene ether (modified) PPE (Polyphenylene Ether)), polyester, para-aromatic polyamide, polylactic acid, nylon, polyglycol urea, polyether ether ketone (PEEK: Polyether Ether Ketone) consisting of more than one type film.

(16) A cover film formed with an insulating film, and A cover film having an adhesive layer formed on at least one surface of the insulating film is characterized in that the adhesive layer is the adhesive composition for a circuit board as in (13).

(17) The cover film of (16), wherein the aforementioned insulating film is selected from polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate Ethylene formate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamide, polylactic acid, nylon, poly One or more films in the group consisting of ethylenediurea and polyetheretherketone (PEEK).

(18) A prepreg characterized by being formed by more than one fiber selected from the group consisting of carbon fiber, cellulose fiber, glass fiber, or aromatic polyamide fiber The structure is impregnated with the adhesive composition for circuit boards as in (13).

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

〔式(I)中，l、m、n為正整數〕

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

(20) The polyimide precursor solution composition containing a fluorine-based resin as in (19), wherein the polyimine precursor solution contains tetracarboxylic dianhydride and/or the derivative, and a diamine compound .

(21) The polyimide precursor solution composition containing a fluorine resin as in (20), which contains a non-aqueous solvent.

(22) The polyimide precursor solution composition containing a fluorine resin according to (21), wherein the polyimine precursor solution contains tetracarboxylic dianhydride and/or the derivative, and a diamine compound .

(23) The polyimide precursor solution composition containing fluorine resin according to any one of (19) to (22), wherein the fine powder of the fluorine resin is selected from polytetrafluoroethylene, fluorinated resin Ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene One or more fluorine resin fine powder.

(24) The fluorine-based resin-containing polyimide precursor solution composition of any one of (19) to (22), wherein the fluorine-based resin fine powder dispersion is dispersed The average particle size of the resin fine powder is 10 μm or less.

(25) A fluorine-based resin-containing polyimide, characterized in that it is obtained by using the fluorine-based resin-containing polyimide precursor solution composition of any one of (19) to (24).

(26) A polyimide film containing fluorine-based resin, characterized in that the polyimide film containing fluorine-based resin as in any one of (19) to (24) is used Obtained from the composition of the imine precursor solution.

(27) A polyimide insulating material containing fluorine-based resin, characterized in that it is obtained by using the polyimide precursor solution composition containing fluorine-based resin as in any one of (19) to (24) .

(28) A method for producing polyimide containing fluorine-based resin, characterized by comprising: preparing fine powder containing fluorine-based resin, a compound represented by the following formula (I), and fluorine-based resin with non-aqueous solvent In the step of fine powder dispersion, the tetracarboxylic dianhydride and/or the derivative and the diamine compound are mixed to prepare the polyimide precursor solution composition, and the fluorine resin fine powder dispersion is mixed with the A step of preparing a polyimide precursor solution composition containing a fluorine-based resin, and curing the polyimide precursor solution composition containing a fluorine-based resin Process to obtain a polyimide containing fluorine-based resin.

〔式(I)中，l、m、n為正整數〕。

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

(29) A method for producing a polyimide film containing a fluorine-based resin, which is characterized in that it contains the polyimide film containing a fluorine-based resin as described in (28) The step of imine further includes the step of obtaining a polyimide film containing fluorine-based resin.

(30) A method for manufacturing a polyimide insulating film containing a fluorine-based resin, which is characterized in that it includes the step of obtaining a polyimide containing a fluorine-based resin as in (28), and further includes obtaining a polyimide-containing resin The step of polyimide insulating film.

(31) A circuit board characterized by using the polyimide film containing fluorine-based resin as in (26).

(32) A cover film characterized by using the polyimide film containing fluorine-based resin as in (26).

(33) An electronic device characterized by using the polyimide insulating material containing fluorine-based resin as in (27).

(34) The non-aqueous dispersion of the fluorine-based resin as in (1) or (2), wherein the fluorine-based resin is polytetrafluoroethylene and contains fine-particle ceramics, and the water content measured according to the Karl Fischer titration method is Below 20000ppm.

(35) The non-aqueous dispersion according to (34), wherein the aforementioned fine particle ceramic contains any one element of B, Na, Mg, Al, Si, P, K, Ca, and Ti.

(36) The non-aqueous dispersion according to (34) or (35), wherein the aforementioned fine particle ceramics are made of any one of Al ₂ O ₃ , SiO ₂ , CaCO ₃ , ZrO ₂ , SiC, Si ₃ N ₄ , and ZnO. The compound is composed.

(37) The non-aqueous dispersion according to any one of (34) to (36), wherein the aforementioned ceramic particles are surface-treated.

According to the present invention, the non-aqueous dispersion of the fluorine resin of polytetrafluoroethylene has a fine particle diameter, low viscosity, and excellent storage stability, and has excellent redispersibility after long-term storage. In addition, even if it is added to various resin materials, rubbers, adhesives, lubricants or greases, printing inks or paints, they can be mixed uniformly. In addition, we provide non-aqueous dispersions containing fluorine resins that can uniformly disperse fluorine resins with improved electrical properties (low dielectric constant, low dielectric tangent), physical properties, etc., and uniform control of fluorine resins. The polyimide precursor solution composition in the dispersed state, and the electrical properties such as heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant, and low dielectric tangent obtained by the composition , Polyimide, polyimide film with excellent processability, and their manufacturing methods, and related to circuit boards, cover films, insulating films, and wiring boards using the polyimide or polyimide film Insulating film, surface protection layer, sliding layer, peeling layer, fiber, filter material, wire coating material, bearing, paint, heat insulation shaft, bracket, seamless belt, etc. various belts, tapes, tubes, insulating materials, circuit boards Adhesive compositions, laminates for circuit boards, prepregs, electronic devices using these, etc. Furthermore, fluorine-containing surfactants or dispersants may become hydrogen fluoride during the heat treatment during polyimination or when the waste liquid is burned and discarded. However, no fluorine-containing surfactants or dispersants are used. Part of the embodiment of the present invention has the advantage of suppressing negative effects on the environment.

10‧‧‧Insulating film

20‧‧‧Adhesive composition layer for circuit board

30‧‧‧Metal foil

Fig. 1 is a schematic view showing an example of the embodiment of the circuit board laminate of the present invention in a cross-sectional view.

Fig. 2 is a schematic view showing an example of the embodiment of the circuit board laminate of the present invention in a cross-sectional view.

Fig. 3 is a schematic diagram showing an example of the embodiment of the cover film of the present invention in a cross-sectional view.

The following is a detailed description of embodiments of the present invention.

The polyimide precursor solution composition containing fluorine-based resin of the present invention is characterized by containing: fine powder of fluorine-based resin, and fluorine-based additives containing at least fluorine-containing groups and lipophilic groups, and at least: The water content measured by Karl Fischer titration method is a non-aqueous dispersion of fluororesin and a polyimide precursor solution with a water content of 20,000 ppm or less.

〔Non-aqueous dispersion of fluorine resin〕

The non-aqueous dispersion of fluorine-based resin of polytetrafluoroethylene used in the present invention contains fine powder of fluorine-based resin, and fluorine-based additives containing at least fluorine-containing groups and lipophilic groups. As a preferred embodiment, it is a non-aqueous dispersion with a water content of 20,000 ppm or less, preferably 5,000 ppm or less, as measured by Karl Fischer titration. Although it is not particularly limited, for example, it is possible to use at least fine powder of fluorine-based resin with a primary particle diameter of 1 μm or less Finally, it is prepared with a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and a solvent. In addition, as a particularly preferred embodiment, the non-aqueous dispersion of polytetrafluoroethylene is characterized by containing at least: polytetrafluoroethylene, fine particle ceramics, and fluorine-based additives containing fluorine-containing groups and lipophilic groups.

The fine powder of the fluorine resin that can be used in the present invention, for example, can be selected from polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), chlorine Trifluoroethylene (CTFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE/CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE)), polychlorotrifluoroethylene (PCTFE) At least one kind of fine powder of fluorine-based resin, and these preferably have a primary particle diameter of 1 μm or less.

Among the above-mentioned fluorine-based resin fine powders, especially as a material with low relative permittivity and low dielectric tangent, it is preferable to use polytetrafluoroethylene (PTFE, relative permittivity 2.1), which has the most excellent characteristics among resin materials. .

The fine powder of the fluorine-based resin is obtained by an emulsion polymerization method. For example, it can be obtained by a method described in the Fluoro Resin Handbook (Edited by Kurokawa Takatoshi, Nikkan Kogyo Shimbun) and other generally used methods. Then, the fine powder of the fluorine-based resin obtained by the emulsion polymerization is aggregated and dried to recover the fine powder of the secondary particles aggregated as the primary particles. Various generally used methods for producing fine powders can be used.

The primary particle diameter of the fluorine resin fine powder is based on the volume-based average particle diameter (50% volume diameter, median diameter) measured by laser diffraction scattering method, dynamic light scattering method, image imaging method, etc. If it is less than 1μm, it is better to be stably dispersed in an oily solvent, and it is preferably less than 0.5μm, It is more preferably 0.3 μm or less, whereby a more uniform dispersion can be obtained.

When the primary particle diameter of the fluorine resin fine powder exceeds 1 μm, it is easy to settle in an oily solvent and it is difficult to stably disperse, which is not preferable. In addition, the lower limit of the above-mentioned average particle size is preferably as low as possible, and from the viewpoint of manufacturability and cost, it is preferably 0.05 μm or more.

The primary particle diameter of the fluorine-based resin of the present invention is expressed as a value measured by a laser diffraction scattering method or a dynamic light scattering method in the production stage of the fine powder, and it becomes a powder state after drying. In the case of fine powder, the cohesion of the primary particles is strong, and it is difficult to easily measure the diameter of the primary particles by the laser diffraction scattering method or the dynamic light scattering method, so it can be expressed as a value measured by the image imaging method. The measuring device can be, for example, a dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction scattering method based on Microtrac (manufactured by Nikkiso Co., Ltd.), or Mac-VIEW (Mountech Co., Ltd.) image imaging method, etc.

In the present invention, relative to the total amount of the non-aqueous dispersion, the fluorine resin-containing fine powder is preferably 5 to 70% by mass, particularly preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass.

When the content is less than 5% by mass, the viscosity is extremely reduced due to the large amount of solvent. Not only is the fluorine-based resin fine powder particles easy to settle, but also sometimes caused by mixing with the polyimide precursor solution. Defects caused by the large amount of solvent, such as the extremely low viscosity of the polyimide precursor solution composition containing fluorine-based resin, or the time-consuming removal of the solvent. On the other hand, when it exceeds and exceeds 70% by mass, The fine powders of the fluorine-based resin tend to aggregate with each other, and it is extremely difficult to stably maintain the state of the fine particles in a fluid state, which is not preferable.

The fluorine-based additive that can be used in the non-aqueous dispersion of the present invention is not particularly limited as long as it has at least a fluorine-containing group and a lipophilic group, and others may also contain a hydrophilic group.

By using a fluorine-based additive having at least a fluorine-containing group and a lipophilic group, the surface tension of the oily solvent used as the dispersion medium can be reduced, and the wettability of the fine powder surface of the fluorine-based resin can be improved to enhance the micro The dispersibility of the powder, and the fluorine-containing group is adsorbed on the surface of the fine powder of the fluorine-based resin. The lipophilicity is based on the extension in the oily solvent that becomes the solvent, and the steric obstacle of the lipophilic group prevents the agglomeration of the fine powder of the fluorine-based resin , And further improve dispersion stability.

Examples of fluorine-containing groups include perfluoroalkyl groups, perfluoroalkenyl groups, etc. Lipophilic groups include, for example, one or two or more of alkyl groups, phenyl groups, and siloxane groups. Hydrophilic groups, For example, ethylene oxide, or one or two or more of amide groups, ketone groups, carboxyl groups, and sulfonyl groups can be cited.

Specific fluorine-based additives that can be used include Surflon S-611 (manufactured by AGC Seimi Chemical), Megafac F-555, Megafac F-558, Megafac F-563 and other Megafac series containing perfluoroalkyl groups. (Manufactured by DIC Corporation), Unidyne series such as Uniddyne DS-403N (manufactured by Daikin Industrial Co.), etc.

These fluorine-based additives can be appropriately selected according to the type of the fluorine-based resin fine powder and the solvent used, and can be used alone or in combination of two or more.

The content of the aforementioned fluorine-based additives is 0.1-50% by mass relative to the mass of the fluorine-based resin fine powder, preferably 5-35% by mass, more preferably 5-30% by mass, particularly preferably 15-25 quality%.

When this content is less than 0.1% by mass relative to the mass of the fluorine-based resin fine powder, the surface of the fluorine-based resin fine powder cannot be sufficiently wetted with solvents such as oily solvents. On the other hand, when it exceeds 50% by mass, the dispersion The increased foaming of the dispersion reduces the efficiency of dispersion, and when the dispersion itself is processed or later mixed with resin materials, etc., defects may sometimes occur, which is not good.

In the non-aqueous dispersion of the fluorine-based resin fine powder of the present invention, other surfactants can be used in combination with the above-mentioned fluorine-based additives within the range that does not impair the effects of the present invention.

For example, nonionic, anionic, and cationic surfactants, or nonionic, anionic, and cationic polymer surfactants, etc. can be cited, but they are not limited to these and can be used.

The solvent used in the above-mentioned non-aqueous dispersion of the present invention includes, for example, a solvent selected from γ-butyrolactone, acetone, butanone, hexane, heptane, octane, 2-heptanone, cycloheptanone, and cycloheptanone. Hexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl n-pentanone, methyl isobutyl ketone, methyl isopentanone, 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, dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 3-ethane Ethyl oxypropionate, dioxane, methyl lactate, lactic acid Ethyl acetate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, phenyl methyl ether, ethyl benzyl Base ether, cresol methyl ether, diphenyl ether, dibenzyl ether, ethoxybenzene, butyl phenyl ether, benzene, ethylbenzene, diethylbenzene, amylbenzene, cumene , Toluene, xylene, isopropyl toluene, trimethylbenzene, methanol, ethanol, 2-propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl mono Glycidyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methyl phenol monoglycidyl ether, ethyl phenol monoglycidyl ether, butyl Phenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofuran acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate , Glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon , Hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, dimethyl imidazoline, tetrahydrofuran, pyridine, formamide, acetaminophen, dioxolane, o-cresol, m-cresol , P-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide Amine, N,N-dimethylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethylsulfinium, diethylsulfinium, One solvent or two or more of these solvents from the group consisting of dimethyl sulfide, diethyl sulfide, γ-butyrolactone, cyclobutane, halogenated phenols, and various silicone oils.

Among these solvents, although it depends on the purpose of the polyimide used, etc. Variations, but preferably exemplified formamide, acetaminophen, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl -2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfide, γ-butyrolactone, cyclobutane, halogenated phenols, two Toluene, acetone.

In the present invention, the above-mentioned solvent is used, but it can also be used in combination with other solvents or other solvents, and a more suitable one can be selected according to the application of the polyimide used (circuit substrate, cover film, etc.).

Depending on the polarity of the solvent used, it can be considered that the compatibility with water is high, but when the amount of water is large, the dispersibility of the fluorine resin fine powder in the solvent will be hindered, and the viscosity may increase or the particles may agglomerate. .

In the present invention, the solvent used has a water content of 20,000 ppm or less as measured by Karl Fischer titration, preferably 5,000 ppm or less [0≦moisture content≦5000 ppm]. In the present invention (including the embodiments described below), the measurement of the moisture content based on Karl Fischer titration is based on JIS K 0068:2001, and can be measured by, for example, MCU-610 (manufactured by Kyoto Electronics Industry Co., Ltd.). By making the water content in the solvent less than 5000 ppm, it is possible to form a non-aqueous dispersion of fluorine resin fine powder with a particle diameter, low viscosity, and better storage stability. It is more preferably 3000 ppm or less, and particularly preferably 2500 ppm or less. , Particularly preferably below 2000ppm. For the adjustment of the above-mentioned moisture content or less, a dehydration method using commonly used solvents such as oily solvents can be used. For example, molecular sieves can be used.

The content of the solvent of the non-aqueous dispersion used in the present invention is the remainder of the fine powder of the fluorine resin and the fluorine additive.

The fine particle ceramic used in combination as one of the preferred embodiments of the present invention is contained in the fluororesin, especially to maintain the dispersion stability of the non-aqueous dispersion of PTFE to a higher degree.

The particulate ceramics that can be used are not particularly limited, and preferably contain any one or more elements of B, Na, Mg, Al, Si, P, K, Ca, and Ti, and may be selected from containing these elements At least one kind of fine particle ceramics of oxide system, hydroxide system, carbide system, carbonate system, nitride system, halide system and phosphate system.

Particularly good fine particle ceramics are preferably selected from Al ₂ O ₃ , SiO ₂ , from the viewpoint of further dispersion stability of non-aqueous dispersions, compatibility with other ingredients, availability, and workability. CaCO ₃ , ZrO ₂ , SiC, Si ₃ N ₄ , and ZnO are composed of at least one inorganic compound.

In such fine particle ceramics, the primary particle diameter is preferably 0.5 μm or less.

The primary particle diameter of this fine particle ceramic is determined by using the volume-based average particle diameter (50% volume diameter, median diameter) measured by the laser diffraction scattering method, dynamic light scattering method, image imaging method, etc. Those with a diameter of 0.5μm or less are preferably dispersed stably in the non-aqueous system and maintain the dispersion stability of the non-aqueous dispersion of PTFE to a higher degree, preferably 0.3μm or less, more preferably 0.1μm or less, thereby , The dispersion stability of non-aqueous dispersion is more excellent. In addition, the lower limit of the primary particle diameter is preferably as low as possible, and it is preferably 0.02 μm or more from the viewpoint of manufacturability and cost.

In the measurement of the primary particle diameter of the fine particle ceramic of the present invention, the cohesion between the ceramics is strong, and it is difficult to use the laser diffraction scattering method or dynamic light scattering When the primary particle diameter is easily measured by the method, etc., it can be expressed as a value measured by the image imaging method. The measuring device can be, for example, a dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction scattering method based on Microtrac (manufactured by Nikkiso Co., Ltd.), or Mac-VIEW (Mountech Co., Ltd.) image imaging method, etc.

The content of these particulate ceramics is preferably 0.01 to 5% by mass, and more preferably 0.1 to 3% by mass relative to the total amount of the non-aqueous dispersion.

When the content is less than 0.01% by mass, the effect of containing fine ceramic particles cannot be exerted, and the dispersion stability of the non-aqueous dispersion of PTFE cannot be maintained to a higher degree. On the other hand, when it exceeds 5% by mass, the characteristics of fine-particle ceramics are too strong, hindering the dispersion stability of non-aqueous PTFE dispersions, and when added to various resin materials or rubber, adhesives, lubricants or greases, printing In the case of ink or paint, sometimes the performance will decrease, which is not good.

These ceramic particles are pre-dispersed in the solvent (dispersion medium) used in the non-aqueous dispersion of PTFE, and can be added before, during, and after the dispersion of PTFE, or they can be mixed with PTFE powder. Disperse together.

In the solvent (dispersion medium), although it varies depending on the use of the dispersion, etc., preferably, butanone, dimethylformamide, cyclohexanone, propylene glycol monomethyl ether acetate, N -Methylpyrrolidone, γ-butyrolactone, 2-propanol, etc.

The above-mentioned solvent of the present invention may further contain a silicone-based defoamer. Especially when the fluorine-based resin fine powder is 70% by mass, or the fluorine-based additive is used at a high concentration of 50% by mass relative to the fluorine-based resin fine powder, the foaming of the dispersion is important for the manufacture of the dispersion Steps, stability, mixing with resin materials, etc. sometimes cause problems.

The defoamers that can be used include silicone-based emulsification type, self-emulsification type, oil type, oil compound type, solution type, powder type, solid type, etc., and can be combined with the oily solvent used. Choose the fittest. In particular, compared to the interface between oily solvent and PTFE, since it exists at the interface between oily solvent and air, it is preferable to use, for example, a hydrophilic or water-soluble silicone defoamer, but it is not limited to these. be usable. Although the content of the antifoaming agent varies with the content (concentration) of the fine powder of the fluorine-based resin, etc., it is preferably 1% by mass or less based on the active ingredient relative to the total amount of the non-aqueous dispersion.

In the non-aqueous dispersion of the present invention, in the dispersed state, the average particle size of the fluorine resin fine powder measured by the laser diffraction scattering method or the dynamic light scattering method is 1 μm or less.

Even if a fluorine-based resin fine powder having a primary particle diameter of 1 μm or less is used, the primary particles generally aggregate to form a fine powder with a particle diameter of 1 μm or more and serve as secondary particles. By dispersing the secondary particles of this fluorine-based resin fine powder to a particle size of 1 μm or less, for example, using an ultrasonic disperser, three rolls, wet ball mill, bead mill, wet jet mill, high pressure homogenizer, etc. The dispersing machine is used to disperse, even if it is stored for a long time under low viscosity, a stable dispersion can be obtained.

Furthermore, in the present invention, the water content of the non-aqueous dispersion of the fluorine-based resin fine powder measured according to the Karl Fischer titration method is preferably 5000 ppm or less [0≦moisture content≦5000 ppm]. In addition to the amount of water contained in the oil-based solvent, the water contained in the material itself such as fluorine-based resin fine powder or fluorine-based additives is also considered, or in the manufacturing process of dispersing the fluorine-based resin fine powder in the solvent By mixing the moisture in the fluorine-based resin, the moisture content of the non-aqueous dispersion of the fluorine-based resin is finally set to 5000 ppm or less, thereby obtaining a non-aqueous dispersion of the fluorine-based resin with better storage stability. It is more preferably 3000 ppm or less, particularly preferably 2500 ppm or less, and particularly preferably 2000 ppm or less. For the adjustment of the above-mentioned moisture content or less, a dehydration method using commonly used solvents such as oily solvents can be used. For example, molecular sieves can be used. In addition, the non-aqueous dispersion of the fluorine resin can be used in a state where the moisture content is sufficiently reduced by dehydrating it by heating or reducing pressure. Furthermore, after the non-aqueous dispersion of fluorine-based resin is produced, molecular sieves or membrane separation methods can be used to remove water. However, other than the above methods, as long as it can reduce the water content of the non-aqueous dispersion of fluorine-based resin , There is no special limitation, and all can be used.

In a non-aqueous dispersion of fluorine resin fine powder, the smaller the average particle size of the fluorine resin fine powder used, or the average particle size in the dispersed state, the more easily affected by moisture. Especially when the thickness is less than 1μm, not only the storage stability of the non-aqueous dispersion is significantly deteriorated, but also when the fluorine-based resin fine powder is easily agglomerated and settled during mixing and addition with the polyimide precursor solution, it is difficult to maintain uniform dispersion. The state of fluorine-based resin fine powder has defects such as a significant increase in viscosity during storage. Furthermore, when removing the solvent In the stage, the coagulation of the fine powder of the fluorine-based resin is easy to proceed, which will also adversely affect the physical and electrical properties of the polyimide or polyimide film finally obtained.

In the PTFE non-aqueous dispersion, which is one of the preferred embodiments of the present invention, the water content measured according to Karl Fischer titration is preferably below 20000 ppm [0≦moisture content≦20000 ppm]. In addition to the amount of water contained in the solvent (dispersion medium), the water contained in the material itself such as fine powder of PTFE or fluorine-based additives is also considered, or in the manufacturing process of dispersing PTFE in the solvent (dispersion medium) By mixing the moisture in the PTFE, the moisture content of the PTFE non-aqueous dispersion is finally set to 20,000 ppm or less, thereby obtaining a PTFE non-aqueous dispersion with more excellent storage stability. For the adjustment of the above-mentioned moisture content or less, the dehydration method of generally used oily solvent can be used, for example, molecular sieve can be used. In addition, PTFE can be used in a state where the moisture content is sufficiently reduced by dewatering by heating or decompression. Furthermore, after preparing the PTFE non-aqueous dispersion, molecular sieves or membrane separation methods can be used to remove water. However, other than the above methods, as long as it can reduce the water content of the non-aqueous dispersion, it is not particularly limited. be usable.

The PTFE non-aqueous dispersion of the present invention constituted in this way contains at least: PTFE, fine particle ceramics, and a fluorine-based additive containing a fluorine-containing group and a lipophilic group, and has a fine particle diameter, low viscosity, and excellent filter permeability. , It is excellent in storage stability and redispersibility after long-term storage. The mechanism can be estimated as follows.

That is, by using at least a fluorine-containing group and a lipophilic group Additives can reduce the surface tension of the non-aqueous solvent that becomes the dispersion medium, improve the wettability of the PTFE surface to improve the dispersibility of PTFE, and the fluorine-containing group is adsorbed on the PTFE surface. The lipophilicity is based on the solvent that becomes the dispersion medium. Elongation, and the steric barrier of the lipophilic group prevents the aggregation of PTFE and further improves the dispersion stability. Furthermore, the inclusion of fine-particle ceramics prevents the contact of PTFE particles with each other and improves fluidity, so it is excellent in filtration permeability, storage stability, and re-dispersibility even after long-term storage.

Therefore, the non-aqueous PTFE dispersion of the present invention can be uniformly mixed even if it is added to various resin materials or rubbers, adhesives, lubricants or greases, printing inks or paints. For example, the non-aqueous dispersion of PTFE of the present invention can be widely used as a resist material by adding to a photoresist such as a color filter or a black matrix, a screen printing resist, etc. In the epoxy resin material of the substrate or sealing material of electronic equipment, it can be further reduced in dielectric constant and low dielectric tangent, so it can be used more suitably for the application of anti-corrosion material and epoxy resin material. use.

The content of the fine powder of the fluorine resin having an average particle size of 1 μm or less in the above-mentioned dispersion state used in the present invention is due to the content of the fine powder of the fluorine resin and the solvent contained in the dispersion. The type of each component of the imine precursor solution varies, and the non-aqueous dispersion of fluorine resin or the solvent in the polyimide precursor solution is ultimately composed of the polyimide precursor solution containing fluorine resin. After the product, it is removed during the production of polyimide containing polyimide film, etc., so when it contains polyimide The content of the fine powder of the fluorine resin in the polyimide film, etc. is preferably adjusted to 1 to 70% by mass, and more preferably 5 to 50% by mass to use the dispersion.

By setting the content of the fluorine-based resin fine powder to 1% by mass or more, the relative permittivity or dielectric tangent of the electrical properties of polyimide films including polyimide films can be reduced. On the other hand, By setting it to 70% by mass or less, the effects of the present invention can be exerted without impairing various characteristics or stability of polyimide including polyimide film or the like.

In addition, the above-mentioned non-aqueous dispersion of fluorine resin contains fine powder of fluorine resin with an average particle size of 1 μm or less in the dispersed state, so it has a fine particle diameter, low viscosity, and excellent storage stability. After long-term storage, Dispersibility is also excellent. In addition, even if a large amount of fluorine-based additives is contained, the defoaming property is excellent, and even if it is added to the polyimide precursor solution, it can be uniformly mixed.

〔Polyimide precursor solution〕

The polyimide precursor solution used in the present invention is obtained by reacting tetracarboxylic dianhydride and/or the derivative with a diamine compound in the presence of a solvent. In the present invention, "polyimide precursor solution" sometimes includes the concept of the solvent used.

The preparation of the polyimide precursor solution should adopt conventional methods or specific conditions.

The tetracarboxylic dianhydride that can be used includes, for example, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2'-bis (3,4-Dicarboxyl Phenyl) propane dianhydride, bis(3,4-dicarboxyphenyl) dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, pyromellitic dianhydride (PMDA), 3, 3',4,4'-Diphenylketonetetracarboxylic dianhydride, 3,3',4,4'-Biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3',4' -Biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, ethylene tetracarboxylic dianhydride , Ethylene glycol double dehydrated trimellitate, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphthalene [1,2 -c] Furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride, etc., which can be used alone or in combination of two or more.

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

Diamine compounds that can be used include, for example, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, and diamino groups. Propyltetramethylene, 3-methylheptamethylene diamine, 4,4-dimethylheptamethylene diamine, 2,11-diaminododecane, 1,2-bis-3 -Anylpropoxyethane, 2,2-dimethylpropanediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5- Dimethylheptamethylene diamine, 3-methylheptamethylene diamine, 5-methyl nonamethylene diamine, 4,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenylmethane, 3,3'-Diaminodiphenylmethane, 3,3'-Dichlorobenzidine, 4,4'-Diaminodiphenylsulfide, 3,3'- Diaminodiphenyl diamine, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-Dimethylbenzidine, 3,3'-Dimethoxybenzidine, 4,4'-Diaminodiphenylene, 4,4'-Diaminodiphenylpropane, 2 ,4-Diaminotoluene, bis(4-amino-3-carboxyphenyl)methane, 1,3-bis(4-aminophenoxy) Benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)benzene Oxy)phenyl) sulfite, 2,4-bis(β-amino-tertiary butyl) toluene, bis(p-β-amino-tertiary butylphenyl) ether, bis(p-β- Methyl-6-aminophenyl)benzene, bis-p-(1,1-dimethyl-5-amino-pentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, M-xylenediamine, p-xylenediamine, di(p-aminocyclohexyl)methane, 2,17-diaminoeicosane, 1,4-diaminocyclohexane, 1,10-diamino -1,10-Dimethyldecane, 1,12-Diaminooctadecane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, etc., these can be used alone Or mix two or more kinds to use.

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

In the present invention, the combination of the above-mentioned tetracarboxylic dianhydride and/or the derivative and diamine compound is preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) and 4,4'-Diaminodiphenyl ether (ODA), s-BPDA and p-phenylenediamine (PPD).

In the present invention, the solvent used for the preparation of the polyimide precursor solution is preferably an organic polar solvent that can dissolve the polyimide precursor and has a boiling point of 300°C or less under normal pressure, and can be used for fluorine It is the solvent of non-aqueous dispersion of resin. For example, acetone, butanone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl normal Pentanone, 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 , Dipropylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 3-ethoxypropionic acid Ethyl, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropionic acid Ethyl ester, phenyl methyl ether, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, ethoxybenzene, butyl phenyl ether, benzene, ethyl benzene, di Ethylbenzene, pentylbenzene, cumene, toluene, xylene, cumene, trimethylbenzene, methanol, ethanol, 2-propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidol Ether, butyl monoglycidyl ether, phenyl monoglycidyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methylphenol monoglycidyl Ether, ethyl phenol monoglycidyl ether, butyl phenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofuran acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, methacrylic acid 2-hydroxyethyl, hydroxypropyl methacrylate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, Methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, perfluoropolyether, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetaminophen, Dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethyl methyl Amide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-Diethylacetamide, 1,3-Dimethyl-2-imidazolidinone, dimethyl sulfide, diethyl sulfide, dimethyl sulfide, diethyl sulfide, γ-butyl Lactone, cyclobutane, halogenated phenols, etc., these solvents can be used alone or in combination of two or more.

Preferably, formamide, acetaminophen, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrole are used Pyridone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfide, γ-butyrolactone, cyclobutylene, halogenated phenols, xylene, acetone.

The polyimide precursor solution used in the present invention can be prepared by adding tetracarboxylic dianhydride and/or the derivative, and a diamine compound with a predetermined composition ratio to a solvent and stirring. The total concentration of the tetracarboxylic dianhydride and/or the derivative and the diamine compound in the solvent can be set according to various conditions, and is usually 5 to 30% by weight in the total amount of the reaction solution. The reaction conditions when stirring these are not particularly limited, and the reaction temperature is preferably set below 80°C, particularly preferably set at 5-50°C. When the reaction temperature is too low, the reaction does not proceed or it takes time until the reaction proceeds, and when it is too high, problems such as the progress of imidization may occur. In addition, the reaction time is preferably 1 to 100 hours.

<Compound represented by formula (I)>

The compound represented by the formula (I) used in one of the embodiments of the present invention is a so-called butyraldehyde resin, and the fine powder of the fluorine-based resin can be uniformly and stably formed in the polyimide precursor solution. When dispersing fine particles, the molecular structure is composed of vinyl butyraldehyde/vinyl acetate/vinyl alcohol. Metapolymer, which reacts polyvinyl alcohol (PVA) with butyraldehyde (BA), and has the structure of butyraldehyde, acetyl and hydroxyl groups. By changing the ratio of these three structures (each of l, m, n) Ratio) to control the solubility to non-aqueous solvents, the compatibility with polyimide precursor solutions, and chemical reactivity.

As the compound represented by formula (I), commercially available products can be used. Specific examples include S-Lec B series manufactured by Sekisui Chemical Co., Ltd., K(KS) series, SV series, and Mowital series manufactured by Kuraray Corporation.

Specific examples include the product name manufactured by Sekisui Chemical Industry Co., Ltd.; S-Lec BM-1 (hydroxyl content: 34 mol%, butyraldehyde degree 65 ± 3 mol%, molecular weight 40,000), the same BH-3 (Hydroxyl amount: 34mol%, butyraldehyde degree 65±3 mol%, molecular weight 110,000), the same BH-6 (hydroxyl amount: 30mol%, butyraldehyde degree 69±3 mol%, molecular weight 92,000), The same BX-1 (hydroxyl amount: 33±3mol%, butyraldehyde degree 66 mol%, molecular weight 100,000), the same BX-5 (hydroxyl amount: 33±3mol%, butyraldehyde degree 66 mol%, molecular weight 130,000), the same BM-2 (hydroxyl amount: 31mol%, butyraldehyde degree 68±3mol%, molecular weight 52,000), the same BM-5 (hydroxyl amount: 34mol%, butyraldehyde degree 65±3mol Ear%, molecular weight 53,000), the same BL-1 (hydroxyl amount: 36mol%, butyraldehyde degree 63±3 mol%, molecular weight 19,000), the same BL-1H (hydroxyl amount: 30mol%, butyraldehyde degree 69±3 mol%, molecular weight 20,000), the same BL-2 (hydroxyl content: 36 mol%, butyraldehyde degree 63±3 mol%, molecular weight 27,000), the same BL-2H (hydroxyl content: 29 mol%, Butyraldehyde degree 70±3 mol%, molecular weight 28,000), the same BL-10 (hydroxyl amount: 28mol%, butyraldehyde degree 71±3 mol%, molecular weight 15,000), the same KS-10 (hydroxyl content: 25mol%, butyraldehyde degree 65±3 mol%, molecular weight 17,000), etc., or Kuraray Product name manufactured by the company; Mowital B145 (hydroxyl amount: 21~26.5 mol%, butyraldehyde degree 67.5-75.2 mol%), the same B16H (hydroxyl amount: 26.2-30.2 mol%, butyraldehyde degree 66.9-73.1 mole%, molecular weight 10,000~20,000) etc.

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

The content of the compound represented by formula (I) is preferably 0.01 to 30% by mass relative to the fine powder of the fluorine resin. When the content of this compound is less than 0.01% by mass, the dispersibility becomes poor and the fine powder of the fluorine resin is likely to settle. When the content exceeds 30% by mass, the viscosity of the polyimide precursor solution containing the fluorine resin becomes high, so Bad.

Furthermore, considering the properties of the obtained polyimide and the like, it is more preferably 0.01 to 5 mass%, and most preferably 0.01 to 2 mass%.

When a fluorine-based additive is not contained but the compound of formula (I) is contained, the primary particle diameter of the fluorine-based resin fine powder is 10 μm or less, preferably 5 μm or less, and more preferably 1 μm or less. In addition, the lower limit of the primary particle diameter is preferably as low as possible, and from the viewpoint of manufacturability and cost, it is preferably 0.05 μm or more and 0.3 μm or less.

[Preparation of polyimide precursor solution composition containing fluorine resin]

The polyimide precursor solution composition containing fluorine-based resin of the present invention is characterized by containing: fine powder of the above-mentioned fluorine-based resin, and fluorine-based additives containing fluorine-containing groups and lipophilic groups, or according to formula (I) The compound shown, It also contains at least: a non-aqueous dispersion of a fluorine resin with a water content of 20,000 ppm or less, preferably 5,000 ppm or less, and a polyimide precursor solution measured according to Karl Fischer titration.

In the fluorine-based resin-containing polyimide precursor solution composition of the present invention, it means that the aforementioned non-aqueous dispersion containing fluorine-based resin is dissolved with tetracarboxylic dianhydride and/or the derivative and diamine compound The composition after mixing the polyimide precursor solution of polyimide polymerization can also add tetracarboxylic dianhydride and/or the derivative and diamine compound to the aforementioned non-aqueous dispersion containing fluorine resin and dissolve it Polymerize to form a polyimide precursor solution composition containing fluorine-based resin. In addition, it is also possible to add and mix the aforementioned non-aqueous dispersion containing fluorine-based resin into a polyimide precursor solution in which tetracarboxylic dianhydride and/or the derivative and diamine compound are dissolved and polymerized to form a composition containing The polyimide precursor solution composition of the fluorine resin, as long as it does not cause the fluorine resin in the non-aqueous dispersion containing the fluorine resin to agglomerate or settle and can be uniformly mixed, then the addition and mixing The order is not limited.

The monomer concentration during the polymerization reaction in this preparation, that is, the total concentration of the tetracarboxylic dianhydride and/or the derivative, and the diamine compound in the solvent can be set according to various conditions, and usually the total amount of the reaction solution Among them, it is preferably 5 to 30% by mass.

When the concentration is less than 5% by mass, the reactivity of the tetracarboxylic dianhydride and/or the derivative and the diamine compound becomes poor, and it takes time until the reaction proceeds, or the amount of solvent removed during film formation Increase, etc., which is not economical. On the other hand, when the concentration exceeds 30% by mass, the viscosity during polymerization becomes Too high, or problems such as precipitation. In addition, the reaction temperature is preferably set below 80°C, particularly preferably set at 5-50°C. When the reaction temperature is 5°C lower than the above temperature, the reaction does not proceed or it takes too much time until the reaction proceeds. On the other hand, when the reaction temperature exceeds 80°C and is too high, problems such as progress of imidization may occur. The reaction time is preferably about 1 to 100 hours.

[Preparation of polyimide and polyimide film obtained from the aforementioned fluorine-based resin-containing polyimide precursor solution composition, and manufacturing method thereof]

The polyimide and polyimide film of the present invention can obtain fluorine by imidizing the polyimide precursor in the polyimide precursor solution composition containing the fluorine-based resin prepared above. Polyimide and polyimide film in which the resin is uniformly dispersed with fine particles.

In addition, the production methods of the polyimide and polyimide films of the present invention are characterized by the step of preparing a non-aqueous dispersion of fluorine-based resin, at least mixing the non-aqueous dispersion of fluorine-based resin and polyimide A step of preparing a polyimide precursor solution composition containing a fluorine-based resin, and by making the polyimide precursor solution composition in the polyimide precursor solution Aminating to obtain a polyimide or polyimide film in which the fluorine-based resin is uniformly dispersed with fine particles. The method of imidization is not particularly limited, and can be performed by a generally known method.

For example, when making polyimide or polyimide films dispersed with fluorine-based resin, the polyimide precursor solution composition containing fluorine-based resin obtained above can be applied to polyimide. The surface of the substrate and the substrate for polyimide film is formed into a film (coating film), and the place is heated It is obtained by treating the membrane, removing the solvent, and performing an imidization reaction.

The base material that can be used, for example, as long as it has a compact structure that does not substantially allow liquid or gas to penetrate, the shape or material is not particularly limited, and it can be suitably enumerated: the use of ordinary thin films It is commonly used as a base material for thin film formation such as belts, molds, rollers, rollers, etc., and electronic parts or wires such as circuit boards with polyimide film formed on the surface as an insulating protective film, A sliding member or product with a film formed on the surface, a polyimide film and a multilayer film or a copper-clad laminate substrate, a film or copper foil.

In addition, the method of coating the polyimide precursor solution composition on these substrates, for example, spray method, roll coating method, spin coating method, bar coating method, inkjet method, screen printing method, The slit coating method itself is a generally known method.

Films, films, etc. composed of polyimide precursor solution composition formed by coating on a substrate, for example, can be heated under reduced pressure or normal pressure, at a relatively low temperature below room temperature, etc. The method to defoam.

The film, etc., composed of the polyimide precursor solution composition formed on the substrate, is heated to remove the solvent and undergo imidization to form polyimide and polyimide film. The heat treatment is better than the heat treatment directly at a high temperature. It is better to initially remove the solvent at a relatively low temperature below 140°C, and then increase the temperature to the highest heat treatment temperature for the heat treatment of imidization. The maximum heat treatment temperature can be in the temperature range of 200 to 600°C, preferably 300 to 500°C, and particularly preferably in the temperature range of 250 to 450°C. In addition, It is also possible to use a catalyst such as an amine compound to perform the imidization reaction instead of the heat treatment or to use it in combination with the heat treatment. Furthermore, carboxylic acid anhydride or the like can also be used as a dehydrating agent for rapidly removing water generated in the process of imidization.

For polyimide and polyimide films, the thickness of the film can be adjusted appropriately depending on the application. For example, a polyimide with a thickness of 0.1~200μm, preferably 3~150μm, and particularly preferably 5~130μm can be used. Imide film, film. When the heating temperature is lower than 250°C, the imidization cannot be sufficiently performed, and when it exceeds 450°C, problems such as deterioration of mechanical properties due to thermal decomposition and the like may occur. In addition, when the film thickness exceeds 200 μm, the solvent cannot be sufficiently volatilized, which may cause problems such as a decrease in mechanical properties or foaming during heat treatment.

The polyimide film obtained from the polyimide precursor solution composition containing the fluorine-based resin, and the fine powder concentration of the fluorine-based resin in the polyimide film is not particularly limited. It is relative to the polyimide The quality of the product is preferably 1 to 70% by mass, particularly preferably 5 to 50% by mass, and more preferably 10 to 35% by mass. If the concentration of the fine powder of the fluorine resin is too small, the effect of adding the fine powder of the fluorine resin is not obtained. In addition, when the concentration of the fine powder of the fluorine resin is too high, the mechanical properties of the polyimide and the like will be reduced.

〔Resin composition〕

In the adhesive composition of one embodiment of the present invention, the resin composition used includes cyanate ester resin or epoxy resin. These resins are matrix resins that become the adhesive composition for circuit boards, as long as they are Whatever can be used suitably for adhesive resin is not particularly limited, and all can be used.

The cyanate resins that can be used include at least 2-functional aliphatic cyanate esters, at least 2-functional aromatic cyanate esters, or mixtures thereof. For example, examples include: selected from 1,3 ,5-Tricyanoxybenzene, 1,3-dicyanooxynaphthalene, 1,4-dicyanooxynaphthalene, 1,6-dicyanooxynaphthalene, 1,8-dicyanooxynaphthalene, 2 ,6-Dicyanoxynaphthalene and 2,7-dicyanoxynaphthalene, at least one polyfunctional cyanate polymer; bisphenol A type cyanate resin or hydrogenated ones, bisphenol F type cyanate ester resin or those hydrogenated, 6F bisphenol A dicyanate resin, bisphenol E type dicyanate resin, tetramethyl bisphenol F dicyanate resin, bisphenol M two Cyanate resin, dicyclopentadiene bisphenol dicyanate resin, or cyanate phenol resin, etc. In addition, commercial products of these cyanate ester resins can also be used.

Furthermore, in the aforementioned cyanate ester resin, a cyanate ester curing accelerator may be used as necessary.

This cyanate ester hardening accelerator can use organic acid metal salts or β-diketonate complexes, such as iron, copper, zinc, cobalt, nickel, manganese, tin and other organic acid metal salts or β- Diketonate complex. Specifically, the aforementioned cyanate ester curing accelerators include manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octoate, copper octoate, zinc octoate, and cobalt octoate. And other organic acid metal salts; lead acetopyruvate, cobalt acetopyruvate and other β-diketonate complexes.

These cyanate ester curing accelerators are based on the concentration of the metal and are compared with the aforementioned cyanate ester resin in terms of reactivity, curability, and moldability. 100 parts by mass, 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

Epoxy resins that can be used include epoxy resins containing one or more epoxy groups (oxirane ring) on average. Examples include bisphenol F epoxy resins and bisphenol A epoxy resins. , Phenol-phenolic epoxy resin, cresol novolac epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, aralkyl epoxy resin, biphenyl At least one type of aralkyl type epoxy resin, hydrogenated type epoxy resin that hydrogenates the phenyl groups of the aforementioned various epoxy resins, and alicyclic type epoxy resin.

The epoxy resin that can be used in the present invention is not limited to the above-mentioned resins as long as it has one or more epoxy groups in one molecule, but bisphenol A, hydrogenated bisphenol A, and cresol novolac are preferred. Wait.

When using the above-mentioned epoxy resin, it is preferable to use a curing agent in terms of reactivity, curability, and moldability. Hardeners that can be used include, for example, ethylenediamine, triethylenediamine, hexamethylenediamine, dimer acid modified ethylenediamine, N-ethylaminopiperazine, and isophorone Aliphatic amines such as diamines; m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'- Aromatic amines such as diaminodiphenylmethane and 4,4'-diaminodiphenyl ether; mercaptans such as mercaptopropionate and epoxy terminal mercapto compounds; bisphenol A, bisphenol Phenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A , Tetrafluorobisphenol A, diphenol, dihydroxynaphthalene, 1,1,1-tris(4-hydroxyphenyl)methane, 4,4-(1-(4-(1-(4-hydroxyphenyl) -1-methylethyl) phenylethylene) Phenolic resins such as bisphenol, phenol-phenolic, cresol phenolic, bisphenol A phenolic, brominated phenol-phenolic, brominated bisphenol A phenolic; polyols that hydrogenate the aromatic ring of these phenolic 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, methyl-norbornane-2,3-dicarboxylic anhydride, etc. Alicyclic anhydrides; aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole And other imidazoles and their salts; amine adducts obtained by the reaction of aliphatic amines, aromatic amines, and/or imidazoles with epoxy resin; hydrazine such as dihydrazine adipate Class; tertiary amines such as dimethylbenzylamine, 1,8-diazobicyclo[5.4.0]undecene-7, etc.; organic phosphines such as triphenylphosphine; dicyandiamine, etc. At least one.

Among these, alicyclic acid anhydrides and aromatic acid anhydrides are preferred, alicyclic acid anhydrides are particularly preferred, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and norcamphor are particularly preferred. Alkane-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride.

The amount of these hardeners depends on the type of epoxy resin used and the hardener used, and it is preferable to mix epoxy equivalent and amine equivalent or active hydrogen equivalent. By mixing the same equivalent, the cross-linking reaction can be sufficiently advanced, and a cured product of the adhesive for circuit board excellent in light resistance and heat resistance can be obtained.

[Adhesive composition for circuit boards]

The adhesive composition for a circuit board of the present invention contains at least: a fine powder containing a fluorine-based resin, and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and is measured according to the Karl Fischer titration method Non-aqueous dispersion of fluorine resin with moisture content below 5000ppm; and resin composition composed of cyanate ester resin or epoxy resin; and may further contain rubber dispersed in the aforementioned cyanate ester resin or epoxy resin ingredient.

The adhesive composition for circuit boards of the present invention, in order to be used in the manufacture of flexible printed circuit boards that can bend wiring or substrates, etc., the composition itself must also have sufficient flexibility (Flexible, the same below), in order to supplement For this flexibility, the adhesive composition for circuit boards described above preferably further contains a rubber component.

The rubber components that can be used include natural rubber (NR) or synthetic rubber, preferably styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber ( NBR), ethylene propylene diene monomer (EPDM) rubber, polybutadiene rubber, and modified polybutadiene rubber, etc. It is preferable to use EPDM rubber with an ethylene content of 10-40% by mass, or SBR, NBR, etc., is particularly preferably EPDM rubber that can reduce the relative dielectric constant and dielectric loss coefficient of the resin composition.

The content of these rubber components, from the point of further exerting the effects of the present invention, as well as the point of adhesive force and heat resistance, is 1 to 100 parts by mass of the aforementioned resin (cyanate resin or epoxy resin) 80 parts by mass, preferably 10 to 70 parts by mass, particularly preferably 20 to 60 parts by mass.

The adhesive composition for circuit boards of the present invention can be obtained by A non-aqueous dispersion of a fluorine-based resin containing fine powder of a fluorine-based resin, and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and the water content measured by Karl Fischer titration is below 5000ppm ; It is produced by the usual method of mixing with a resin composition composed of cyanate ester resin or epoxy resin, etc., preferably a resin composition containing cyanate ester resin or epoxy resin and further containing rubber components, It is produced by adding to non-aqueous dispersion of fluorine resin and mixing.

The adhesive composition for a circuit board of the present invention may further contain inorganic particles such as a phosphorus-based flame retardant in order to further supplement flame retardancy. Inorganic particles such as these phosphorus-based flame retardants are 1-30 parts by mass, preferably 5-20 parts by mass, relative to 100 parts by mass of the aforementioned cyanate ester resin or epoxy resin.

In addition, in the adhesive composition for circuit boards of the present invention, in addition to the above-mentioned components, curing accelerators, defoamers, colorants, phosphors, modifiers, anti-tarnishing agents, Conventionally known additives such as inorganic fillers, silane coupling agents, light diffusion agents, and thermally conductive fillers.

Hardening (reaction) accelerators other than the above, for example, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 1,8-diazobicyclo(5.4.0)undecene -7 tertiary amines and their salts; phosphines such as triphenylphosphine; phosphonium salts such as triphenylphosphonium bromide; aminotriazoles; tin octoate, dibutyltin dilaurate, etc. Series: zinc octoate, such as zinc, aluminum, chromium, cobalt, zirconium, and other metal catalysts such as acetylpyruvate. These hardening (reaction) accelerators can be used alone or in combination of two or more kinds.

The adhesive composition for a circuit board of the present invention can be molded and cured by the same method as generally known cyanate ester resin composition and epoxy resin composition to form a cured product. The molding method and curing method can be the same methods as commonly known cyanate ester resins and epoxy resin compositions. The method unique to the circuit board adhesive composition of the present invention is not required, and is not particularly limited. .

The adhesive composition for a circuit board of the present invention can be further configured in various forms such as a laminate, a molded product, an adhesive, a coating film, and a thin film.

The adhesive composition for a circuit board of the present invention uses a non-aqueous dispersion in which fine powder of a fluorine resin is stably and uniformly dispersed to obtain the adhesive composition for a circuit board, so the relative dielectric constant and dielectric tangent are low. Adhesion, heat resistance, dimensional stability, flame retardancy, etc. also have excellent characteristics, suitable for circuit board adhesive materials, such as laminates, cover films, prepregs, bonding sheets, etc. that use them之 Manufacturing. The aforementioned cover film, prepreg, bonding sheet, etc. can be applied to circuit boards, such as flexible printed circuit boards (FPCBs) such as flexible metal foil laminates, and the adhesive composition for circuit boards of the present invention is used in the production of these It is possible to realize an adhesive composition for a circuit board with a lower relative dielectric constant and dielectric tangent, and excellent characteristics such as adhesiveness, heat resistance, dimensional stability, and flame retardancy.

〔PCB〕

The circuit board of the present invention is characterized by using a polyimide film obtained from the above-mentioned polyimide precursor solution composition containing a fluorine-based resin.

The circuit board of the present invention, for example, in a flexible printed circuit board (FPC), is obtained from the above-mentioned polyimide precursor solution containing fluorine-based resin by using an adhesive composition such as epoxy resin and cyanate resin The insulating fluorine-based resin-containing polyimide film obtained from the composition is bonded to a metal foil to produce a metal foil laminate (CCL), and a circuit is formed on the metal foil.

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

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

Examples of the aforementioned metal foil include conductive metal foils, such as gold, silver, copper, stainless steel, nickel, aluminum, alloys of these, and the like. From the viewpoints of conductivity, ease of handling, price, etc., copper foil, stainless steel foil, or the like can be suitably used. As the copper foil, either one produced by the rolling method or the electrolytic method can be used.

The thickness of the metal foil can take into account the electrical conductivity, the adhesion of the interface with the insulating film, the flexibility of the laminate, the improvement of the bending resistance, or the points that are easy to form fine patterns in the circuit processing, and the wiring between The point of continuity, etc., are set in a preferable range, for example, preferably in the range of 1 to 35 μm, particularly preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.

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

The circuit board of the present invention thus constituted can obtain the relative dielectric constant by using the polyimide film obtained from the polyimide precursor solution composition containing the fluorine-based resin of the present invention as the insulating film Circuit board with low dielectric tangent and excellent heat resistance, electrical insulation or mechanical properties.

〔Laminates for circuit boards〕

The laminate for a circuit board of the present invention is a laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, and is characterized by: This adhesive layer is comprised of the adhesive composition for circuit boards of the above-mentioned structure.

Fig. 1 is a schematic view of a metal foil laminated board (FPCB) showing an example of the embodiment of the circuit board laminate of the present invention in a cross-sectional view.

In the circuit board laminate A of this embodiment, the metal foil 30 is laminated on the insulating film 10 and at least contains an adhesive resin layer 20 interposed between the insulating film 10 and the metal foil 30. The sexual resin layer 20 is composed (bonded) of the adhesive composition for circuit boards configured as described above.

Figure 2 is a cross-sectional view showing the outline of the metal foil laminate (FPCB) of another example of the embodiment of the circuit board laminate of the present invention Figure.

The circuit board laminate B of this embodiment, as shown in Fig. 2, adopts a double-sided structure instead of the single-sided structure of Fig. 1, and metal foils 30 and 30 are laminated on both sides of the insulating film 10, and It contains at least adhesive resin layers 20, 20 interposed between the insulating film 10 and the metal foils 30, 30, respectively, and the adhesive resin layers 20, 20 are composed of the above-mentioned adhesive composition for circuit boards (Joint).

The insulating film 10 used in the circuit board laminate of the present invention shown in Figures 1 and 2 is not particularly limited as long as it has electrical insulation properties, and can be used with heat resistance and bending properties. Performance, mechanical strength, and thermal expansion coefficient of similar metals.

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

In addition, in terms of further enhancing the adhesion force of the interface with the adhesive resin layer 20, etc., a film formed from these materials is preferably a film that is further surface-treated with low-temperature plasma or the like. .

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

The adhesive resin layer 20 is composed (bonded) of the adhesive composition for circuit boards configured as described above. The thickness is determined from the points of adhesion to the insulating film interface, flexibility of the laminate, and adhesive strength. From a standpoint, it is preferably 1 to 50 μm, and particularly preferably 3 to 30 μm.

The aforementioned metal foil 30 may be a metal foil having conductivity, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and alloys thereof. From the viewpoints of conductivity, ease of handling, price, etc., copper foil, stainless steel foil, or the like can be suitably used. As the copper foil, either one produced by the rolling method or the electrolytic method can be used.

The thickness of the metal foil can take into account the electrical conductivity, the adhesion of the interface with the insulating film, the flexibility of the laminate, the improvement of the bending resistance, or the points that are easy to form fine patterns in the circuit processing, and the wiring between The point of continuity, etc., are set in a preferable range, for example, preferably in the range of 1 to 35 μm, particularly preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.

In addition, the surface roughness Rz (ten-point average roughness) of the matte surface of the metal foil used is preferably in the range of 0.1~4μm, particularly preferably in the range of 0.1~2.5μm, particularly preferably 0.2~2.0 Within the range of μm.

The production of the circuit board laminate of the present invention structured in this way (for example, FIG. 1 and FIG. 2, etc.) can be performed by coating the insulating film 10 with the adhesive composition for circuit board of the present invention structured as described above, for example. Above, after forming the adhesive resin layer 20, it is dried to a semi-cured state, and then the metal foil 30 is laminated on the adhesive resin layer 20 and thermally pressed (thermally laminated) to produce the relative dielectric constant Tangent to Dielectric Low, adhesive, heat resistance, dimensional stability, flame retardancy, etc. also have excellent characteristics for circuit board laminates. At this time, by post-curing the flexible metal foil laminate, the adhesive resin layer 20 in the semi-cured state is completely cured, and the final flexible metal foil laminate can be obtained.

〔Cover Film〕

Next, the cover film of the present invention is a cover film in which an insulating film is formed and an adhesive layer is formed on at least one surface of the insulating film, and is characterized in that the adhesive layer is used for a circuit board having the above-mentioned structure Adhesive composition.

Fig. 3 is a schematic diagram showing an example of the embodiment of the cover film of the present invention in a cross-sectional view.

The cover film C of this embodiment is used as a surface protection film for flexible printed circuit boards (FPC), etc., and an adhesive resin layer 50 is formed on the insulating film 40, and an adhesive resin layer 50 is bonded to A release sheet (release film) 60 of paper or PET film used as a protective layer. The separator (peel film) 60 can be installed as needed in consideration of workability, storage stability, and the like.

The insulating film 40 used is the same as the insulating film 10 used in the above-mentioned circuit board laminate. For example, it can be selected from polyimide (PI), liquid crystal polymer (LCP), and polyterephthalic acid. Ethylene glycol (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic Polyamide, polylactic acid, nylon, polyethylene urea, polyether One or more films of the group consisting of ether ketone (PEEK).

In addition, in terms of further enhancing the adhesion of the adhesive resin layer 50 to the film formed from such materials, it is preferable to use a film whose surface is further surface-treated with low-temperature plasma. .

In particular, considering the heat resistance, dimensional stability, mechanical properties, etc. of the cover film, it is preferable to use a polyimide (PI) film, and it is particularly preferable to use a polyimide film after low-temperature plasma treatment as the cover film.

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

The adhesive resin layer 50 is composed (bonded) of the adhesive composition for circuit boards configured as described above, and the thickness is preferably from the viewpoints of interface adhesion with the insulating film, adhesive strength, etc. 1~50μm, particularly preferably 3~30μm.

The cover film of the present invention configured in this way can be coated on the insulating film 40 by using a doctor roll coater, a reverse roll coater, etc., to coat the adhesive composition for a circuit board of the present invention configured as above to form an adhesive layer , And dried into a semi-cured state (the composition is in a dry state or the state of the part undergoing a curing reaction), and then layered into the separation sheet (release film) 60 of the above-mentioned protective layer, whereby the relative dielectric constant and the A cover film with low dielectric tangent, adhesion, heat resistance, dimensional stability, flame retardancy and other excellent characteristics.

In the present invention, in addition to using the above-mentioned polyimide precursor Polyimide or polyimide film with excellent heat resistance, mechanical properties, sliding properties, insulation properties, low dielectric constant, low dielectric tangent, etc., and excellent processability In addition to the above-mentioned circuit boards and cover films, these polyimide or polyimide films can also be used, which are suitably used in insulating films, related insulating films for wiring boards, surface protective layers, sliding layers, release layers, and fibers. , Filter materials, wire coating materials, bearings, paints, heat-insulating shafts, brackets, seamless belts and other belts, tapes, tubes, etc.

Example

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

[Preparation of non-aqueous dispersion of fluorine resin: Dispersion 1~5]

After the fluorine-based additives were thoroughly stirred and mixed in the solvent and dissolved in the formulation shown in Table 1 below, the PTFE fine powder as the fine powder of the fluorine-based resin was added and further stirred and mixed. Then use a horizontal bead mill to disperse the resulting PTFE mixture with zircon beads with a diameter of 0.3 mm to obtain dispersions 1 to 5.

The average particle size of the PTFE in the obtained dispersions 1 to 5 was measured by a dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). In addition, the water content of each dispersion 1 to 5 according to Karl Fischer titration was measured.

The following table 1 shows the formulation of dispersions 1 to 5 and the resulting dispersion The average particle size and moisture content of PTFE in the body.

[Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of polyimide precursor solution composition containing fluorine resin] <Example 1>

(1-a) Preparation of polyimide precursor solution

400 parts by mass of N,N-dimethylacetamide, 27 parts by mass of p-phenylenediamine, and 73 parts by mass of 3,3',4,4'-biphenyltetracarboxylic acid dihydrate were added to A glass container equipped with a stirrer and a nitrogen pipe was mixed and stirred at 50°C for 10 hours to obtain a polyimide precursor solution with a solid content of 18% by mass.

(1-b) For the non-aqueous dispersion of fluororesin, Dispersion 1 in Table 1 above was used.

(1-c) Polyimide precursor solution composition containing fluorine resin Manufacturing method

18 parts by mass of Dispersion 1 (PTFE content: 30% by mass) was added to the polyimide precursor solution prepared in 1-a, stirred and mixed for 10 minutes, and the obtained PTFE contained 30% by mass relative to the resin component. Polyimide precursor solution composition containing fluorine resin.

(1-d) Manufacturing method of polyimide film containing fluorine-based resin

The polyimide precursor solution composition containing the fluorine-based resin obtained in 1-c was coated on a glass plate as a substrate by a bar coater, and decompression was performed at 25°C for 50 minutes under reduced pressure. After foaming and pre-drying, heat at 120°C for 45 minutes, 150°C for 30 minutes, 200°C for 15 minutes, 250°C for 10 minutes, and 400°C for 10 minutes under normal pressure and nitrogen atmosphere. Treatment to form a polyimide film with a thickness of 50 μm.

<Example 2>

By the same method as in Example 1, dispersion 2 was used and the blending ratio shown in Table 2 below was used to obtain a fluorine-based resin-containing polyimide precursor solution composition (2-b). In addition, the polyimide film (2-d) was formed by the same method as in Example 1.

<Example 3>

By the same method as in Example 1, dispersion 3 was used and the blending ratio shown in Table 2 below was used to obtain a fluorine-based resin-containing polyimide precursor solution composition (3-b). In addition, by the same method as in Example 1 Method to form a polyimide film (3-d).

<Comparative Example 1>

By the same method as in Example 1, dispersion 4 was used and the blending ratio shown in Table 2 below was used to obtain a polyimide precursor solution composition (4-b) containing a fluorine-based resin. In addition, the polyimide film (4-d) was formed by the same method as in Example 1.

<Comparative Example 2>

By the same method as in Example 1, dispersion 5 was used and the blending ratio shown in Table 2 below was used to obtain a fluorine-based resin-containing polyimide precursor solution composition (5-b). In addition, the polyimide film (5-d) was formed by the same method as in Example 1.

<Comparative Example 3>

Using the polyimide precursor obtained in Example 1 (dispersion not used: no PTFE), the polyimide film (6-d) was formed by the same method as in Example 1.

[Assessment]

The fluorine-based resin-containing polyimide precursor solution composition (1~5-c) obtained in Examples 1 to 3 and Comparative Examples 1 to 2 are the same as those obtained in Examples 1 to 3 and Comparative Examples 1 to 3 The evaluation of the polyimide film was carried out by the following methods.

(The average particle size of the fluororesin particles in the polyimide precursor solution composition containing fluororesin)

Use N,N-dimethylacetamide to dilute the polyimide precursor solution composition containing fluorine-based resin, and measure by dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) The average particle size of PTFE to evaluate the state of aggregation.

(Viscosity change, sedimentation and redispersion state of polyimide precursor solution composition containing fluorine-based resin)

The polyimide precursor solution composition containing fluorine-based resin was allowed to stand for 30 days at 25°C, and the viscosity before and after 30 days of standing was measured using the above-mentioned E-type viscometer, and evaluated according to the following evaluation criteria Viscosity changes.

In addition, the sedimentation state of the PTFE particles after being allowed to stand at 25°C for 30 days was visually confirmed, and the sedimentation and redispersibility states were subjected to sensory evaluation based on the following evaluation criteria.

Evaluation criteria for viscosity change:

A: The viscosity of the liquid changes within the range of ±10%

B: The viscosity of the liquid changes more than ±10%

Evaluation criteria for settlement:

A: Those who have not seen the sedimentation layer from the lower part

B: Those who can see the settlement layer from the bottom

Evaluation criteria for redispersibility:

A: The sediment is easy to redisperse during stirring

B: The sediment is not easy to be dispersed again during stirring

(Method of evaluating the state of polyimide film)

The state of the polyimide film was visually observed, and the state was subjected to sensory evaluation based on the following evaluation criteria.

Evaluation criteria for the state of polyimide film:

A: There is no impurities such as PTFE aggregates and forms a smooth surface

B: Those who have confirmed impurities such as PTFE aggregates

(The relative permittivity and dielectric tangent of polyimide film)

The polyimide films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were peeled off from the glass plate, and in accordance with the test specifications of JIS C6481-1996, using an impedance analyzer (Impedence Analyzer) at 25°C, 1kHz frequency Next, determine the relative dielectric constant and dielectric tangent.

Looking at the results of Table 2 and Table 3 above, the polyimide precursor solution composition containing fluorine resin of Examples 1 to 3 within the scope of the present invention has a small change in the particle size or viscosity of the fluorine resin. Very stable result. In addition, it was confirmed that the relative dielectric constant and dielectric tangent of the polyimide film were lowered compared with Comparative Example 3 that did not contain a fluorine-based resin. In addition, the mechanical properties of the polyimide films obtained in Examples 1 to 3 show almost the same performance as the polyimide film of Comparative Example 3. Furthermore, the fusion of the properties of polyimide and PTFE improves the characteristics of PTFE such as sliding properties, insulation properties, and releasability.

On the other hand, the amount of water used is the dispersion 4 outside the scope of the present invention In Comparative Example 1, the stability of the polyimide precursor solution composition containing the fluorine-based resin was low, the state of the polyimide film was also poor, and no effect was observed in the electrical properties. In addition, in Comparative Example 2 using Dispersion 5 of a fluorine-based resin with a large particle size, the polyimide precursor solution composition containing a fluorine-based resin has low stability. In addition, the state of the polyimide film Also bad. The polyimide film of Comparative Example 2 was in a worse state than Comparative Example 1, and the electrical characteristics could not be measured.

[Preparation of fluorine resin fine powder dispersion: Dispersion 6~12]

According to the formulation shown in Table 4 below, the compound represented by formula (I) was thoroughly stirred and mixed in a solvent and dissolved, and then PTFE fine powder as a fine powder of fluorine resin was added and further stirred and mixed. Then, a horizontal bead mill was used to disperse the resulting PTFE mixture with zircon beads with a diameter of 0.3 mm to obtain dispersions 6-12.

The average particle size of the PTFE in the dispersions 6-12 was measured by a dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). In addition, the viscosity of each dispersion 6-12 was measured using an E-type viscosity agent (manufactured by TOKIMEC).

The following Table 4 shows the formulations of dispersions 6-12, the average particle size and viscosity of PTFE in the resulting dispersion. In addition, the moisture content of the obtained dispersion 6-12 was measured, and the moisture content obtained by Karl Fischer titration was within the range of 700-3000ppm.

*1 Average particle size of primary particles

*3 S-Lec BL-10 (butyraldehyde (PVB) resin, manufactured by Sekisui Chemical Industry Co., Ltd., hydroxyl 28 mol%, butyraldehyde degree 71 ± 3 mol%, molecular weight 15,000)

*4 S-Lec BM-1 (butyraldehyde (PVB) resin, manufactured by Sekisui Chemical Industry Co., Ltd., hydroxyl 34 mol%, butyraldehyde degree 65 ± 3 mol%, molecular weight 40,000)

*5 S-Lec BH-3 (butyraldehyde (PVB) resin, manufactured by Sekisui Chemical Industry Co., Ltd., hydroxyl 34 mol%, butyraldehyde degree 65 ± 3 mol%, molecular weight 110,000)

*6 S-Lec KS-10 (butyraldehyde (PVB) resin, manufactured by Sekisui Chemical Co., Ltd., hydroxyl group 25 mol%, acetalization degree 74±3 mol%, molecular weight 17,000)

*2 Megafac F-563: manufactured by DIC, oligomer containing fluorine and lipophilic groups, 100wt% active ingredient

[Examples 4 to 10 and Comparative Example 4: Preparation of polyimide precursor solution composition containing fluorine resin] <Example 4>

(a) Preparation of polyimide precursor solution

400 parts by mass of N,N-dimethylacetamide, 27 parts by mass of p-phenylenediamine, and 73 parts by mass of 3,3',4,4'-biphenyltetracarboxylic acid dihydrate were added to A glass container with a stirrer and a nitrogen piping was mixed and thoroughly stirred to obtain a polyimide precursor solution with a solid content of 18% by mass.

(b) A fluorine-based resin fine powder dispersion, using Dispersion 6 in Table 4 above.

(c) Manufacture of polyimide precursor solution composition containing fluorine-based resin

18 parts by mass of Dispersion 6 (PTFE content: 30% by mass) was added to the polyimide precursor solution prepared in (a) above, and stirred and mixed for 10 minutes to obtain PTFE containing 30% by mass relative to the resin component The polyimide precursor solution composition containing fluorine resin.

(d) Manufacturing of polyimide film containing fluorine-based resin

The fluorine-based resin-containing polyimide precursor solution composition obtained in (c) above was coated on a glass plate as a substrate by a bar coater, and the solution was heated at 25°C for 50 minutes under reduced pressure. After defoaming and pre-drying, under normal pressure and nitrogen atmosphere, carry out 45 minutes at 120℃ and advance at 150℃ Heat treatment is performed for 30 minutes, 200°C for 15 minutes, 250°C for 10 minutes, and 400°C for 10 minutes to form a polyimide film (1) with a thickness of 50 μm.

<Example 5>

A polyimide film (2) was formed by the same method as in Example 4 except for using Dispersion 7 of Table 4 above as the fluorine-based resin fine powder dispersion.

<Example 6>

A polyimide film (3) was formed by the same method as in Example 4 except for using Dispersion 8 of Table 4 above as the fluorine-based resin fine powder dispersion.

<Example 7>

A polyimide film (4) was formed by the same method as in Example 4 except that the dispersion 9 of the above Table 4 was used as the fluorine-based resin fine powder dispersion.

<Example 8>

A polyimide film (5) was formed by the same method as in Example 4 except that the dispersion 10 of the above Table 4 was used as the fluorine-based resin fine powder dispersion.

<Example 9>

A polyimide film (6) was formed by the same method as in Example 4 except that the dispersion 11 in Table 4 was used as the fluorine-based resin fine powder dispersion.

<Example 10>

400 parts by mass of N,N-dimethylacetamide, 27 parts by mass of p-phenylenediamine, and 73 parts by mass of 3,3',4,4'-biphenyltetracarboxylic acid dihydrate were added to A glass container with a stirrer and a nitrogen piping was mixed and thoroughly stirred to obtain a polyimide precursor solution with a solid content of 18% by mass.

5.4 parts by mass of PTFE fine powder (primary particle size: 3μm) and 1.5% by mass of S-Lec BL-10 were added to the polyimide precursor solution, stirred and mixed for 2 hours to obtain PTFE relative to the resin component A polyimide precursor solution composition containing 30% by mass of fluorine-based resin.

The above-mentioned polyimide precursor solution composition containing fluorine-based resin was coated on a glass plate as a substrate by a bar coater, and defoamed and pre-dried at 25°C for 50 minutes under reduced pressure ，Under normal pressure and nitrogen atmosphere, heat treatment at 120°C for 45 minutes, 150°C for 30 minutes, 200°C for 15 minutes, 250°C for 10 minutes, and 400°C for 10 minutes to form a thickness of 50μm polyimide film (7).

<Comparative Example 4>

A polyimide film (8) was formed by the same method as in Example 4 except that the dispersion 12 of the above Table 4 was used as the fluorine-based resin fine powder dispersion.

[Assessment]

The state of viscosity change, sedimentation and redispersibility of the polyimide precursor solution composition containing fluorine-based resin obtained in the above Examples 4-10 and Comparative Example 4 is the same as that of Examples 4-10 and Comparative Example The evaluations of the state, relative permittivity, dielectric tangent, and adhesion of the polyimide films (1) to (8) obtained in 4 were performed by the following methods. These results are shown in Table 5 below.

In addition, the moisture content of the polyimide precursor solution composition containing the fluorine-based resin of Examples 4-10 and Comparative Example 4 was measured. The moisture content according to the Karl Fischer titration method is located at 700 Within the range of ~3000ppm.

(Method for measuring the average particle size of fluororesin particles in the composition of the polyimide precursor solution containing fluororesin)

Use N,N-dimethylacetamide (DMF) to dilute the polyimide precursor solution composition containing fluorine-based resin, and use dynamic light scattering according to FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) Method, the average particle size of PTFE is measured to evaluate the aggregation state.

(Evaluation method of viscosity change, sedimentation and redispersion state of polyimide precursor solution composition containing fluorine resin)

The polyimide precursor solution composition containing fluorine-based resin was allowed to stand for 30 days at 25°C, and the viscosity before and after 30 days of standing was measured using the above-mentioned E-type viscometer, and evaluated according to the following evaluation criteria Viscosity changes.

In addition, the sedimentation state of the PTFE particles after being allowed to stand at 25°C for 30 days was visually confirmed, and the sedimentation and redispersibility states were subjected to sensory evaluation based on the following evaluation criteria.

Evaluation criteria for viscosity change:

A: The viscosity of the liquid changes within the range of ±10%

B: The viscosity of the liquid changes more than ±10%

Evaluation criteria for settlement:

A: Those who have not seen the sedimentation layer from the lower part

B: Those who can see the sedimentation layer from the bottom (easy to disperse again)

C: Those who see the sedimentation layer from the bottom (not easy to disperse again)

Evaluation criteria for redispersibility:

A: The sediment is easy to redisperse during stirring

B: The sediment is not easy to be dispersed again during stirring

(Method of evaluating the state of polyimide film)

The state of the polyimide film was visually observed, and the state was subjected to sensory evaluation based on the following evaluation criteria.

Evaluation criteria for the state of polyimide film

A: There is no impurities such as PTFE aggregates and forms a smooth surface

B: Those who have confirmed impurities such as PTFE aggregates

(Measurement method of relative permittivity and permittivity tangent of polyimide film)

The polyimide films obtained in Examples 4 to 9 and Comparative Example 4 were peeled off from the glass plate, and in accordance with the test specifications of JIS C6481-1996, using an impedance analyzer (Impedence Analyzer), at a frequency of 25°C and 1kHz, Determine the relative dielectric constant and dielectric tangent.

(Evaluation method of adhesion of polyimide film)

Using two-component curing epoxy adhesives, the polyimide films (1) to (8) obtained in Examples 4 to 10 and Comparative Example 4 were compared with those in Example 1 without using a dispersion. The polyimide film (without PTFE) produced by the same method as the method was attached, and the peeling test was performed by the method specified in JIS K6854-, and the adhesion was evaluated based on the following evaluation criteria.

Follow-up evaluation criteria:

A: There is no peeling at the interface between the polyimide film and the epoxy adhesive, and the adhesive part is damaged

B: When peeling occurs at the interface between the polyimide film and the epoxy adhesive

From the results in Table 5, it can be seen that in Examples 4 to 10 and Comparative Example 4, the average particle size, viscosity change, sedimentation, redispersibility, and state of the polyimide film did not change particularly. On the other hand, the fluorine-based resin-containing polyimide precursor solution composition of Example 10 using PTFE fine powder with a larger particle size of 3 μm has a sedimentation property of B, but it is easy to redisperse. It is a practically problem-free level.

The relative dielectric constant and dielectric tangent of the polyimide film are higher than those of Examples 4-10, and Comparative Example 4 is a higher result. This is because a fluorine-based dispersant was used in Comparative Example 4, and it was confirmed that the electrical characteristics were inferior to those of Examples 4-10.

In addition, the adhesion of the polyimide film, in Comparative Example 4, peeling occurred at the interface between the polyimide film and the adhesive, which can be presumed to be due to the fluorine-based dispersant present on the surface of the polyimide film. Influence, cause the adhesiveness of the polyimide film to decrease. On the other hand, within the scope of the present invention In the polyimide films of Examples 4 to 10, there was no peeling at the interface between the polyimide film and the adhesive. It can be seen that damage occurred in the adhesive part to avoid the adhesiveness of the polyimide or The adhesion is reduced.

[Preparation of non-aqueous dispersion of fluorine resin: Dispersion 13~17]

After the fluorine-based additive was thoroughly stirred and mixed in the solvent and dissolved in the formulation shown in Table 6 below, the PTFE fine powder as the fine powder of the fluorine-based resin was added and further stirred and mixed. Then, a horizontal bead mill was used to disperse the obtained PTFE mixture with zircon beads with a diameter of 0.3 mm to obtain dispersions 13-17.

The average particle size of the PTFE in the dispersions 13 to 17 obtained was measured by a dynamic light scattering method based on FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). In addition, the water content of each dispersion 13 to 17 based on Karl Fischer titration was measured.

The following Table 6 shows the formulations of dispersions 13-17, the average particle size and moisture content of PTFE in the resulting dispersions.

[Examples 11 to 13 and Comparative Examples 5 to 6: Preparation of Adhesive Composition for Circuit Boards]

Using the obtained dispersions 13-17, the adhesive composition for a circuit board was produced with the formulation shown in Table 7 below.

After mixing at the compounding ratio shown in Examples 11 to 13 and Comparative Examples 5 to 6, it was stirred with a disperser to uniformly mix the PTFE dispersion and the resin, and each adhesive composition for circuit boards was obtained.

Here, the adhesive compositions I to III of Examples 11 to 13 of the adhesive compositions for circuit boards produced using the dispersions 11 to 13 show extremely uniform states, but the adhesive compositions made using the dispersion 16 In the adhesive composition IV of Comparative Example 5, which is the adhesive composition for circuit boards, a granular substance that can be regarded as agglomeration of PTFE particles was observed on the wall surface. In addition, the adhesive composition V of Comparative Example 6 of the adhesive composition for a circuit board produced by using the dispersion 17, when stored for a long period of time, sedimentation and separation of particles were observed.

(Examples 14-16, Comparative Examples 7-8: Manufacturing of cover film)

Using a coater, the adhesive compositions I to V obtained in Examples 11 to 13 and Comparative Examples 5 to 6 were applied to a polyimide film (thickness: 25 μm) so that the thickness after drying became approximately 25 μm ) Has a uniform thickness on the entire surface of one side, and after drying at about 120°C for about 10 minutes, the release paper with a thickness of 125 μm after release coating is laminated to produce a cover film.

(Examples 17-19, Comparative Examples 9-10: Manufacture of prepreg)

Make the adhesive composition obtained by Examples 11-13 and Comparative Examples 5-6 After being impregnated with NE glass cloth with a thickness of about 100μm, the objects I to V were dried at about 120°C for about 10 minutes to produce a thermosetting prepreg with a total thickness of about 125μm.

(Examples 20-22, Comparative Examples 11-12: Production of laminates for circuit boards)

Using a coater, the adhesive composition obtained in Examples 11 to 13 and Comparative Examples 5 to 6 was applied to the polyimide film (thickness: 25 μm) so that the thickness after drying became about 10 μm. After the adhesive resin layer is formed, the entire side surface has a uniform thickness, and this is dried to become a semi-cured state. Then, the same adhesive resin layer was formed on the opposite side of the polyimide film to produce an adhesive sheet.

Next, a copper foil (thickness: about 12μm, matte surface roughness (Rz): 1.6μm) was laminated on both sides of the aforementioned adhesive sheet, and then pressed at 170°C under a pressure of 40kgf/cm ² at 170°C After curing for 5 hours, a laminate for a circuit board was manufactured.

(Production of evaluation sample of cover film)

The cover films of Examples 14-16 and Comparative Examples 7-8 were laminated in the order of polyimide film of the cover film/adhesive surface of the cover film/copper foil (12μm), and then at 180°C, 40kgf/cm The pressure of ² is hot-pressed for 60 minutes to prepare an evaluation sample.

(Production of evaluation samples of prepreg)

The prepregs of Examples 17 to 19 and Comparative Examples 9 to 10 were laminated in the order of polyimide film (12.5μm)/prepreg/polyimide film (12.5μm), and then heated at 180°C , The pressure of 40kgf/cm ² is hot pressed for 60 minutes to make an evaluation sample.

(Production of evaluation samples of laminates for circuit boards)

The laminates for circuit boards of Examples 20-22 and Comparative Examples 11-12 were used as evaluation samples.

(Physical property evaluation)

Using the evaluation samples of Examples 14-22 and Comparative Examples 7-12 obtained above, the following physical property evaluations were performed.

(Evaluation method of electrical characteristics)

The relative dielectric constant and dielectric tangent are measured at 1 MHz using an impedance analyzer (Impedence Analyzer) in accordance with the test specifications of JIS C6481-1996.

(Method of evaluating heat resistance)

After adjusting a sample with a size of 50mm×50mm, it was subjected to moisture absorption treatment at 120°C and 0.22MPa for 12 hours, then floated in a solder tank at 260°C for 1 minute, and the state of the sample was observed with the naked eye.

Evaluation benchmark:

A: No abnormalities such as peeling, deformation, expansion, etc.

B: There are abnormalities such as peeling, deformation, and expansion

(Evaluation method of bonding strength)

A sample cut into 100mm×10mm was prepared, and the adhesive strength of the formed adhesive layer was measured using a Tensilon universal testing machine.

The evaluation results of the cover film are shown in Table 8 below, the evaluation results of the prepreg are shown in Table 9 below, and the evaluation results of the circuit board laminate are shown in Table 10 below.

As shown in Table 8 to Table 10 above, in Examples 14 to 22, the adhesive composition I to V has a low relative permittivity and a low dielectric tangent, thereby using the cover film and prepreg produced therefrom. , And laminates for circuit boards, compared with Comparative Examples 7 to 12, it can be confirmed that the heat resistance and bonding strength are equivalent, and the electrical characteristics are further improved.

[Examples 23 to 27 and Comparative Examples 13 to 14]

According to the formulation shown in Table 11 below (various PTFE powder (Finally, calcium carbonate particles and silica particles as fine particle ceramics, oligomers containing fluorine-containing groups and lipophilic groups as fluorine-based additives, butanone and dimethylformamide as non-aqueous dispersion media) , To make a non-aqueous dispersion of PTFE. At the time of production, after the fluorine-based additive was sufficiently stirred and dissolved in a non-aqueous solvent, PTFE and fine particle ceramics (only PTFE was added in the comparative example) were added, and further stirred and mixed.

Using a horizontal bead mill, the PTFE mixture obtained above was dispersed by zircon beads with a diameter of 0.3 mm to obtain the non-aqueous PTFE dispersions of Examples 23-27 and Comparative Examples 13-14. The water content of the non-aqueous dispersions of Examples 23 to 27 and Comparative Examples 13 to 14 according to Karl Fischer titration was measured, and it was confirmed that it was 20,000 ppm or less.

[Evaluation of dispersion]

As an evaluation of the obtained non-aqueous dispersion of PTFE, the average particle size and viscosity after dispersion were measured. Specifically, the average PTFE in each dispersion was measured by FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) The particle size (nm), and the viscosity (mPa‧s, 25℃) was measured with an E-type viscometer. In addition, after the obtained non-aqueous dispersion of PTFE was contained in a glass container with a lid, the sedimentation and redispersibility after storage at room temperature (25°C) for 1 month were evaluated by the following evaluation method Assessment. These results are shown in Table 11 below.

〔Method of Evaluating Sediment〕

By visual inspection, the sedimentation of the non-aqueous dispersion of PTFE after storage Sensory evaluation for the presence or absence of objects.

Evaluation benchmark:

A: No sediment

B: There is a small amount of sediment

C: There is a lot of sediment

〔Method of evaluating redispersibility〕

The obtained non-aqueous dispersion of PTFE was placed in a glass container with a lid (30 ml, the same below), and the redispersibility after storage at 25°C for 1 month was evaluated based on the following evaluation criteria.

Evaluation benchmark:

A: Easy to redistribute

B: Disperse again

C: A little stirring is required for redispersion

D: Full stirring is required for redispersion

Furthermore, as the evaluation of the dispersion, the liquid permeability of the filter was evaluated.

25mm的薄膜過濾器(孔徑5μm)施加100kPa的壓力並進行1分鐘的加壓後之PTFE之非水系分散體的通液重量進行測定。此外，關於實施例26及27與比較例14，係對

13mm的薄膜過濾器(孔徑5μm)施加100kPa的壓力並進行1分鐘的加壓後之PTFE之非水系分散體的通液重量進行測定。此等之結果如下述表12所示。 The evaluation method, regarding Examples 23-25 and Comparative Example 13, is a pair

The weight of the non-aqueous dispersion of PTFE after applying a pressure of 100 kPa to a 25 mm membrane filter (pore size 5 μm) for 1 minute was measured. In addition, regarding Examples 26 and 27 and Comparative Example 14, they are

The weight of the non-aqueous dispersion of PTFE after applying a pressure of 100 kPa to a 13 mm membrane filter (pore size 5 μm) for 1 minute was measured. These results are shown in Table 12 below.

*8 Primary particle size

*2 Megafac F-563 (DIC company), oligomer containing fluorine-containing group and lipophilic group, active ingredient 100wt%

*9 Ftergent 610FM (manufactured by Neos), oligomer containing fluorine-containing group and lipophilic group, active ingredient 50wt%

*10 Average particle size in dispersed state

From the above Table 11, it can be seen that any of the dispersions of Examples 23 to 27 within the scope of the present invention have an average particle size of about 300 nm or less, and it can be confirmed that they can be finely dispersed.

When viewing each example and comparative example individually, although Examples 23 to 25 have higher viscosity than Comparative Example 13, they become dispersions with high stability. In addition, in Examples 24 and 25, even if the amount of the fluorine-based additive was reduced, the dispersion was excellent in stability and filter permeability. Furthermore, Examples 26 and 27 have almost the same viscosity as Comparative Example 14, and are dispersions with high stability.

Next, from the above Table 12, it can be seen that the filter of Examples 23-25 has a larger liquid passing weight than that of Comparative Example 13, and it can be confirmed that the fluidity is good and the filter mesh is not easily clogged. In addition, in Examples 26 and 27, the weight of the filter passing through the filter was larger than that in Comparative Example 14. It was confirmed that the fluidity was good and the filter mesh was not easily blocked.

Taking these contents together, it can be seen that the non-aqueous dispersion of PTFE of the present invention has a fine particle diameter, low viscosity, and excellent storage stability. After long-term storage, it has excellent redispersibility, good fluidity, and no damage. The mesh of the filter is clogged, and even if it is added to various resin materials or rubbers, adhesives, lubricants or greases, printing inks or paints, it can be mixed uniformly.

〔Industrial applicability〕

It can be suitably applied to electrical properties such as heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant, and low dielectric tangent. Polyimide, polyimide film with excellent processability, dimensional stability, and flame retardancy, circuit board using the polyimide or polyimide film, laminate for circuit board, adhesive for circuit board Compositions, cover films, prepregs, insulating films, related insulating films for wiring boards, surface protective layers, sliding layers, peeling layers, fibers, filter materials, wire coating materials, bearings, resin materials such as anti-corrosion materials, coatings , Printing ink or the additives, heat insulation shafts, brackets, seamless belts and other belts, tapes, tubes, etc.

10‧‧‧Insulating film

20‧‧‧Adhesive composition layer for circuit board

30‧‧‧Metal foil

Claims (20)

A non-aqueous dispersion of fluorine resin, which contains: fine powder of fluorine resin, fluorine additives containing fluorine-containing groups and lipophilic groups, and fine-particle ceramics. Lasers of fine fluorine resin powder in the dispersion The average particle size of the diffraction scattering method or the dynamic light scattering method is 1 μm or less, and the water content measured according to the Karl Fischer titration method is 5000 ppm or less. The non-aqueous dispersion of fluorine-based resin according to claim 1, wherein the aforementioned fine-particle ceramic contains any one element of B, Na, Mg, Al, Si, P, K, Ca, and Ti. The non-aqueous dispersion of a fluorine-based resin according to claim 1 or 2, wherein the primary particle diameter of the aforementioned fine particle ceramic is 0.02 μm or more and 0.5 μm or less. The non-aqueous dispersion of fluorine-based resin according to claim 1 or 2, wherein the aforementioned fine particle ceramic is made of any inorganic compound of Al ₂ O ₃ , SiO ₂ , CaCO ₃ , ZrO ₂ , SiC, Si ₃ N ₄ , and ZnO Constituted. The non-aqueous dispersion of a fluorine-based resin according to claim 1 or 2, wherein the aforementioned ceramic particles are surface-treated. The non-aqueous dispersion of fluorine resin according to claim 1, wherein the fine powder of the fluorine resin is selected from polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene A fine powder of one or more fluorine resins in the group consisting of ethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, and polychlorotrifluoroethylene. Such as the non-aqueous dispersion of fluorine-based resin in claim 1, wherein The solvent in the aforementioned non-aqueous dispersion contains selected from γ-butyrolactone, acetone, butanone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, Methyl cyclohexane, ethyl cyclohexane, methyl n-pentanone, methyl isobutyl ketone, methyl isopentanone, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetic acid Ester, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diethyl ether, propylene glycol monoacetate, dipropylene glycol Monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, ethyl 3-ethoxypropionate, Dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, Phenyl methyl ether, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, ethoxybenzene, butyl phenyl ether, benzene, ethyl benzene, diethyl benzene , Pentylbenzene, cumene, toluene, xylene, cumene, trimethylbenzene, methanol, ethanol, 2-propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl Base monoglycidyl ether, phenyl monoglycidyl ether, methyl diglycidyl ether, ethyl diglycidyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methylphenol monoglycidyl ether, ethyl Base phenol monoglycidyl ether, butylphenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofuran acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxy methacrylate Ethyl ester, hydroxypropyl methacrylate, glycidyl methacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, styrene, Perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon Carbon, hydrofluorocarbon, perfluoropolyether, dimethyl imidazoline, tetrahydrofuran, pyridine, formamide, acetaminophen, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N -Methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylformamide Acetylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfide, diethyl sulfoxide, dimethyl sulfide, diethyl One solvent, or two or more of these solvents in the group consisting of sulfite, γ-butyrolactone, cyclobutyrol, halogenated phenols, and various silicone oils, and the aforementioned methacrylate contains methyl 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, glycidyl methacrylate, methyl methacrylate. A polyimide precursor solution composition containing a fluorine-based resin, which is characterized in that the non-aqueous dispersion of a fluorine-based resin according to claim 1 contains a polyimide precursor solution. A polyimide characterized in that it is obtained by using the polyimide precursor solution composition containing a fluorine-based resin as in claim 8. A polyimide film, characterized in that it is obtained by using the polyimide precursor solution composition containing a fluorine-based resin as in claim 8. A manufacturing method of polyimide, which is characterized by comprising the steps of making a non-aqueous dispersion of fluororesin as in claim 1, mixing the non-aqueous dispersion of fluororesin and a polyimide precursor solution, And the preparation of polyimide precursor solution composition containing fluorine resin Step, and the step of obtaining polyimide dispersed with fluorine-based resin by imidizing the polyimide precursor in the polyimide precursor solution composition. A method for manufacturing a polyimide film, characterized in that it includes the step of obtaining polyimide as in claim 11, and further includes the step of obtaining a polyimide film. A circuit board characterized by using a polyimide film obtained by the manufacturing method as claimed in claim 12. A cover film characterized by using a polyimide film obtained by the manufacturing method of claim 12. An adhesive composition for a circuit board, characterized in that the non-aqueous dispersion of a fluorine-based resin as in Claim 1 contains a resin composition composed of cyanate ester resin or epoxy resin. A laminate for a circuit board is a laminate for a circuit board comprising at least an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, and is characterized in that: the The adhesive layer is an adhesive composition for a circuit board as in Claim 15. The laminate for a circuit board according to claim 16, wherein the aforementioned insulating film is selected from polyimide (PI: Polyimide), liquid crystal polymer (LCP: Liquid Crystal Polymer), and polyethylene terephthalate Diester (PET: Polyethylene Terephthalate), Polyethylene Naphthalate (PEN: Polyethylene Naphthalate), Polyphenylene Sulfide (PPS: Polyphenylene Sulfide), Polyetherimide (PEI: Polyetherimide), Polyphenylene ether (modified) PPE (Polyphenylene Ether)), polyester, para-aromatic polyamide, polylactic acid, nylon, polyglycol urea, polyether ether ketone (PEEK: Polyether Ether Ketone) consisting of more than one type film. A cover film formed with an insulating film and an adhesive layer formed on at least one surface of the insulating film, characterized in that the adhesive layer is an adhesive for circuit substrates as in claim 15剂组合物。 Agent composition. Such as the cover film of claim 18, wherein the aforementioned insulating film is selected from polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate Ester (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aromatic polyamide, polylactic acid, nylon, polyethylene glycol One or more films of the group consisting of urea and polyetheretherketone (PEEK). A prepreg characterized by: a structure formed by more than one fiber selected from the group consisting of carbon fiber, cellulose fiber, glass fiber, or aromatic polyamide fiber , Impregnated with the adhesive composition for circuit boards as in claim 15.

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