KR102557635B1 - Fluorine-based resin-containing non-aqueous dispersion, fluorine-based resin-containing polyimide precursor solution composition, polyimide using the same, polyimide film, adhesive composition for circuit board and manufacturing method thereof - Google Patents

Abstract

Electrical properties such as heat resistance, mechanical properties, low permittivity, low dielectric dissipation, etc. of a dispersion obtained by uniformly controlling the dispersion state of a fluorine-based resin, a polyimide precursor solution composition, and an adhesive composition using the dispersion, obtained from the composition. In order to provide polyimide with excellent processability, polyimide film, method for producing the same, circuit board using the polyimide film, and coverlay film, a micropowder of a fluorine-based resin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group. Alternatively, a fluorine-based resin-containing polyimide precursor solution composition and an adhesive composition comprising a non-aqueous dispersion of a fluorine-based resin containing a butyral resin and a polyimide precursor solution are provided.

Description

Fluorine-based resin-containing non-aqueous dispersion, fluorine-based resin-containing polyimide precursor solution composition, polyimide using the same, polyimide film, adhesive composition for circuit board and manufacturing method thereof

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 a method for producing the same, and more particularly, to a uniformly controlled dispersion state of the fluorine-based resin. Polyimide precursor solution composition, polyimide excellent in heat resistance, mechanical properties, electrical properties (low dielectric constant, low dielectric loss tangent) and processability obtained by the composition, polyimide film, and method for producing the same , It relates to an adhesive composition for a circuit board used in the manufacture of a circuit board, and a laminate for a circuit board using the same, a coverlay film, a prepreg, and the like.

BACKGROUND ART [0002] With the recent progress in high-speed and high-functionality of electronic devices, high-speed communication and the like are required. In the midst of this, low dielectric constant and low dielectric constant tangent of various electronic device materials are required, and in particular, low dielectric constant and low dielectric constant tangent of insulating materials or substrate materials are required.

A circuit board may be mentioned as one of such electronic device materials. A copper-clad laminate is used as this circuit board, and an electrical insulating film and copper foil are bonded through an adhesive layer.

In addition, the copper clad laminate is used in which a copper foil portion is processed and a wiring pattern or the like is formed. In order to protect this wiring pattern, it is covered with an insulating coverlay film, but this coverlay film is also bonded via an adhesive layer.

Furthermore, various fibers are impregnated with adhesives and used in the manufacture of prepregs for insulation and adhesion between layers and imparting rigidity to circuit boards.

Conventionally, polyimide including polyimide films and the like has been widely used for electrical/electronic applications because of its 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 in some cases it is processed into an adhesive film or adhesive tape. In addition, when used as a coating agent, the polyimide precursor solution composition is imidized by heat treatment after coating and drying, and is used as an insulating layer of an electronic circuit (interlayer insulating material of a multi-layer wiring board), a surface protective film of a semiconductor element, etc. in some cases. .

Usually, a polyimide film is bonded to copper foil using an adhesive, or processed into a laminate made of a film layer and copper foil (polyimide film with copper foil) by a vapor deposition method, a plating method, a sputtering method, or a casting method, etc., thereby forming a flexible printed multilayer circuit. It is used as a base film of a substrate.

This copper-clad laminate is used in which a copper foil portion is processed and a wiring pattern or the like is formed. This wiring pattern is covered and protected by an insulating coverlay film. A polyimide film is also mainly used for this coverlay film substrate, and an adhesive layer is used. It is connected through

Furthermore, various fibers are impregnated with adhesives and used in the manufacture of prepregs for interlayer insulation, adhesion, and rigidity to circuit boards.

In particular, in recent high-density packaging, for example, circuit boards and semiconductor package substrates, it has become mainstream to use an insulating resin with a low dielectric constant and a low dielectric loss tangent as an interlayer insulating film in order to speed up signal transmission. Electrical properties such as low dielectric constant and low dielectric loss tangent are also beginning to be required for polyimide including mid films.

Here, in order to improve the electrical properties, a method of using a combination of a polyimide and a fluorine-based resin having high heat resistance and excellent electrical properties has been proposed.

Conventionally, as a polyimide composition or a polyimide film containing a fluorine-based resin, for example, 1) an aromatic tetracarboxylic acid containing biphenyltetracarboxylic acids as a main component in the presence of a surfactant compound in which a fluorine resin powder has a fluorine atom. A fluororesin-containing polyimide composition characterized in that an aromatic polyimide obtained from a carboxylic acid component and an aromatic diamine component is uniformly dissolved in an organic polar solvent capable of dissolving the aromatic polyimide, and a method for producing the same (eg, Patent Document 1 reference), 2) a polyimide resin comprising 3 to 60 parts by weight of a fluororesin and 3 to 60 parts by weight of an aromatic polyamide resin based on 100 parts by weight of a polyimide resin having a repeating unit represented by a specific formula ( For example, see Patent Document 2), 3) dissolving soluble polyimide in a volatile organic solvent to provide a polyimide solution, adding fluorocarbon resin particles to the polyimide solution and uniformly dispersing the fluorocarbon resin dispersed polyimide A method for producing an insulating material for high-frequency electronic components including a step of providing a solution, a step of applying the fluorocarbon resin-dispersed polyimide solution to a substrate, and a step of drying the same (for example, see Patent Document 3), 4) alone or a single layer substrate useful for electronic applications or electrical applications as a component of a multilayer structure, wherein the single layer substrate comprises a polymer blend of at least a polyimide component and a fluoropolymer component derived from a fluoropolymer fine powder having a specific average particle diameter. wherein the single-layer substrate has an outer surface and an inner core, the outer surface comprising a fluoropolymer component in an amount greater than the amount of the fluoropolymer component present in the inner core, and the inner core comprising a polyimide component present in the outer surface. The polymer blend, which contains a polyimide component in an amount greater than the amount of the mid component and has a total thickness within a specific range, is obtained by introducing the fluoropolymer fine powder into polyamic acid and treating the polyamic acid with an imidization process. A single-layer substrate characterized by producing (eg, see Patent Document 4), 5) a film in which a mixture containing polyimide and fluororesin particles is molded and cured by heat, at least a portion of which is present near the surface of the film A polyimide composite film characterized in that fluororesin particles are melt-flowed and precipitated on one side or both sides of the film, and a fluororesin film is formed partially or on the entire surface and a manufacturing method thereof (for example, see Patent Document 5) are known there is.

In the polyimide composition containing the fluororesin powder and the like described in Patent Documents 1 to 5 and the method for producing the same, conventionally, when dispersing the fluororesin, it is preferable to use a surfactant or dispersant containing fluorine such as alkyl fluoride. Common.

However, a polyimide material to which a fluorine-containing surfactant or a dispersant containing a fluorine-containing resin is added can lower the dielectric constant or dielectric loss tangent by the effect of the fluorine-based resin, but the surfactant or dispersant containing fluorine can lower the dielectric constant. In general, there are many cases in which the dielectric constant or the dielectric loss tangent is increased, and there is a problem that it is difficult to sufficiently improve the electrical characteristics.

In addition, the presence of such an additive presents a problem in terms of adhesion, adhesion, heat resistance, and the like of the polyimide material.

Furthermore, surfactants and dispersants containing fluorine may thermally decompose to form hydrogen fluoride when heat treatment in polyimide formation or waste liquid is incinerated, and adverse effects on the environment and the like are feared.

Therefore, there are still technical challenges or limitations in terms of sufficient improvement in electrical properties or physical properties and adverse effects on the environment, etc. A polyimide composition, a polyimide film, and the like are in demand.

The adhesive composition for circuit board production includes, for example, a cyanic acid (cyanate) ester resin, a fluorine-based resin powder dispersed in the cyanic acid (cyanate) ester resin, and a rubber component. A composition (eg, see Patent Document 6), an epoxy resin, a reactive diluent containing an epoxy compound represented by a specific formula as a main component, and a curing agent, and an adhesive epoxy resin composition (eg, see Patent Document 7) It is known.

However, in the adhesive resin composition for circuit board production 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 in improving the electrical properties sufficiently. In addition, the cyanate ester resin or epoxy resin itself described in Patent Documents 6 and 7, which are currently widely used as adhesive compositions for circuit boards, has a relatively high dielectric constant or dielectric loss tangent inherent to each resin, and it is technically necessary to improve electrical properties. There is a problem or limitation, and an adhesive composition for a circuit board with further improved electrical properties is required.

On the other hand, fluorine-based resins such as polytetrafluoroethylene (PTFE) are excellent materials such as heat resistance, electrical insulation, low dielectric properties, low friction properties, non-adhesiveness, and weather resistance, and are suitable for electronic devices, sliding materials, automobiles, and kitchens. Used for supplies, etc. Polytetrafluoroethylene having these characteristics is used as a micropowder for the purpose of improving product characteristics by being added to various resin materials (resist materials), rubber, adhesives, lubricants, greases, printing inks or paints.

Micropowders of fluorine-based resins such as polytetrafluoroethylene are prepared by polymerization of tetrafluoroethylene (TFE) monomers in the presence of stabilizers such as water, polymerization initiators, fluorine-containing emulsifiers, and paraffin wax, usually by emulsion polymerization. After obtaining as an aqueous dispersion containing fine polytetrafluoroethylene particles, it is produced through concentration, aggregation, drying and the like (see Patent Document 8, for example).

As a method of adding the fluororesin micropowder to a resin material or the like, for example, in addition to direct mixing, a method of dispersing in water or an oily solvent and mixing as a fluororesin dispersion is known. It can be mixed uniformly by adding after being once dispersed in water or an oil solvent.

However, fluorine-based resin micropowder has a strong cohesive force among the particles, and it is difficult to disperse in an oil-based solvent in a form with excellent storage stability and low viscosity in terms of particle size, especially in an oil-based solvent.

Furthermore, when adding to a water-insoluble resin or a resist material, an oil-based solvent-based polytetrafluoroethylene dispersion is required, and many inventions and the like related to aqueous polytetrafluoroethylene dispersions are known (e.g., patents). Reference Documents 9 and 10), there are few reports on oil-based solvent-based polytetrafluoroethylene dispersions compared to this aqueous dispersion (for example, see Patent Documents 11 and 12).

The technology described in Patent Document 11 consists of PTFE particles and at least one mono- or polyolefin-based unsaturated oil or oil mixture, wherein molecules of the olefin-based unsaturated oil are formed on the surface of the PTFE (primary) particles. It is covalently/chemically bonded by a radical reaction, and at that time, permanent charge separation between the surface of the PTFE particle and the bonded oil molecule, and long-term stable stability of the PTFE particle finely dispersed in oil or oil mixture exist. It is an oil-PTFE dispersion, the preparation of which is that a modified PTFE (emulsion) polymer having a persistent perfluoro (peroxy) radical is mixed with at least one olefinically unsaturated oil, and then the modified PTFE (emulsion) polymer It is obtained by a method in which mechanical stress is applied, etc., the production method is complicated, and general-purpose PTFE particles are not used, and the technical idea (configuration and its action and effect) is completely different from that of the present invention.

In addition, the technology described in Patent Document 12 is a nonaqueous medium and dispersion stabilizer such as a fluoropolymer such as PTFE, an organic solvent having a boiling point of 40 to 250 ° C, and a general formula: Rf ¹ -(X) _n -Y [ In the formula, Rf ¹ is a partially fluorinated or fully fluorinated alkyl group having 1 to 12 carbon atoms, n is 0 or 1, X is -O-, -COO- or -OCO-, and 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, and r is an integer from 0 to 12 an integer, and R ¹ and R ² are alkylene groups having 2 to 4 carbon atoms. However, R ¹ and R ² are different from each other.] and the like are described.

However, Patent Document 12 does not describe or suggest "polytetrafluoroethylene micropowder having a primary particle diameter of 1 µm or less". In paragraph [0041] of Patent Document 12, there is a description to the effect that "when a powdery fluoropolymer is dispersed, a dispersion that is difficult to re-aggregate can be obtained by dispersing in a size of 5 to 500 μm", which is an example. In the supports of Experimental Examples 1 to 12, “Lubron L-2 (PTFE)” (average particle diameter (50%) 3.5 μm by dry laser method in technical data) of “Daikingokyo Co., Ltd., as a fluoropolymer” was used. are doing Further, it is described that "when the aqueous dispersion is phase-inverted, the size is 0.05 to 5 μm." Thus, in Patent Document 12, when polytetrafluoroethylene micropowder powder is used, it is not assumed that particles of 1 μm or less are used, or it is difficult to implicitly disperse the powder.

In addition, in paragraph [0057] of Patent Document 12, it is described that "it may simply contain additives such as quartz sand, carbon black, diamond, tourmaline, germanium, alumina, silicon nitride, and extender pigments", but such The components are arbitrary components, and there is no description or suggestion as to what kind of action or effect these components exert in the fluoropolymer non-aqueous dispersion, and furthermore, in Patent Document 12, examples etc. have not demonstrated the effects, etc. not.

Accordingly, Patent Document 12 discloses the proximity technology of the present invention, but Patent Document 12 and the present invention are different in technical concept (configuration and operation and effect thereof).

Japanese Unexamined Patent Publication No. 2-286743 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 3-292365 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2002-203430 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2005-142572 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2007-30501 (claims, examples, etc.) Japanese Patent Publication No. 2015-509113 (claims, examples, etc.) Japanese Patent Laid-Open No. 2015-13950 (claims, examples, etc.) Japanese Patent Laid-Open No. 2012-92323 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2006-169448 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2009-179802 (claims, examples, etc.) Japanese Patent Publication No. 2011-509321 (claims, examples, etc.) Japanese Unexamined Patent Publication No. 2011-225710 (claims, examples, etc.)

The present invention is intended to solve the above conventional problems and realities, and a non-aqueous dispersion containing a fluorine-based resin, a polyimide precursor solution composition in which the dispersion state of the fluorine-based resin is uniformly controlled, heat resistance obtained by the composition, and mechanical Polyimide, polyimide film with excellent electrical properties and processability, such as sliding properties, insulating properties, low dielectric constant and low dielectric dissipation factor, and its manufacturing method, and circuit boards and coverlay films using the polyimide or polyimide film , Insulation film, correlation insulation film for wiring boards, surface protective layer, sliding layer, release layer, fiber, filter material, wire covering material, bearing, paint, insulation shaft, tray, various belts such as seamless belts, tapes, tubes, etc. is intended to provide

As a result of intensive examination of the above conventional problems, the inventors of the present invention have found a non-aqueous dispersion containing a fluorine-based resin, a polyimide precursor solution composition containing a fluorine-based resin for the above purpose, an adhesive composition containing a fluorine-based resin, and a polyimide using the same, a coverlay film, etc. I discovered what could be obtained and came to complete this invention.

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

(1) A non-aqueous dispersion of a fluorine-based resin comprising a micropowder of the fluorine-based resin and a fluorine-containing additive containing a fluorine-containing group and a lipophilic group.

(2) The non-aqueous dispersion of the fluororesin according to (1), characterized in that the average particle diameter of the micropowder of the fluororesin in the dispersed state is 1 µm or less in the fluororesin micropowder dispersion.

(3) The non-aqueous dispersion of the fluorine-based resin according to (1) or (2), characterized in that the water content according to the Karl Fischer method is 5,000 ppm or less.

(4) The micropowder of the fluorine-based resin is polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene- The ratio of the fluorine-based resin according to any one of (1) to (3), characterized in that it is a micropowder of at least one fluorine-based resin selected from the group consisting of chlorotrifluoroethylene copolymer and polychlorotrifluoroethylene. Aqueous Dispersion.

(5) The solvent used in the non-aqueous dispersion is γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane , Ethylcyclohexane, methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl 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 mono Ethyl ether acetate, cyclohexyl acetate, 3-ethoxyethylpropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, no Sol, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenethol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene , methanol, ethanol, 2-propanol, butanol, methyl monoglycidyl ether, ethyl monoglycidyl ether, butyl monoglycidyl ether, phenyl monoglycidyl ether, methyl diglycidyl ether, ethyl diglycidyl Dyl ether, butyl diglycidyl ether, phenyl diglycidyl ether, methylphenol monoglycidyl ether, ethyl phenol monoglycidyl ether, butyl phenol monoglycidyl ether, mineral spirits, 2-hydroxyethyl acrylate Rate, tetrahydrofurfuryl 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, perfluoropoly Ether, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl- 2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2-imida One solvent selected from the group consisting of zolidinone, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, γ-butyrolactone, sulfolane, halogenated phenols, and various silicone oils or two solvents thereof The non-aqueous dispersion of the fluorine-based resin according to any one of (1) to (4), characterized by containing more than one species.

(6) A fluorine-based resin-containing polyimide precursor solution composition characterized by comprising a polyimide precursor solution in the non-aqueous dispersion of the fluorine-based resin according to any one of (1) to (5).

(7) A polyimide characterized by being obtained using the fluorine-based resin-containing polyimide precursor solution composition described in (6).

(8) A polyimide film characterized by being obtained using the fluorine-based resin-containing polyimide precursor solution composition described in (6).

(9) a step of producing a non-aqueous dispersion of fluorine-based resin;

A step of preparing a polyimide precursor solution composition containing a fluorine-based resin by mixing the non-aqueous dispersion of the fluorine-based resin and a polyimide precursor solution;

A method for producing a polyimide, comprising a step of imidizing the polyimide precursor in the polyimide precursor solution composition to obtain a polyimide in which a fluorine-based resin is dispersed.

(10) A method for producing a polyimide film, characterized by including the step of obtaining the polyimide described in (9) and further including the step of obtaining a polyimide film.

(11) A circuit board characterized by using a polyimide film obtained by the production method described in (10).

(12) A coverlay film characterized by using a polyimide film obtained by the production method described in (10).

(13) An adhesive composition for a circuit board characterized by comprising a resin composition comprising a cyanate ester resin or an epoxy resin in the non-aqueous dispersion of the fluorine-based resin according to any one of (1) to (5).

(14) A laminate for a circuit board comprising at least a configuration of an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is the adhesive composition for a circuit board of claim 13. Laminate for circuit board, to be.

(15) The insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenyl (14) Laminates for circuit boards described.

(16) A coverlay film in which an insulating film and an adhesive layer are formed on at least one surface of the insulating film, wherein the adhesive layer is the adhesive composition for circuit boards described in (13).

(17) The insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenyl In (16), characterized in that it is at least one film selected from the group consisting of eneether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, and polyetheretherketone (PEEK) The described coverlay film.

(18) The adhesive composition for circuit boards described in (13) is impregnated into a structure formed of at least one type of fibers selected from the group consisting of carbon fibers, cellulose fibers, glass fibers and aramid fibers. Featured, prepreg.

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

(20) The polyimide precursor solution composition containing a fluorine-based resin according to (19), characterized in that the polyimide precursor solution contains tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound.

(21) The fluorine-based resin-containing polyimide precursor solution composition according to (20), characterized by containing a non-aqueous solvent.

(22) The fluorine-based resin-containing polyimide precursor solution composition according to (21), characterized in that the polyimide precursor solution contains tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound.

(23) The micropowder of the fluorine-based resin is polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene- The fluororesin-containing polyi according to any one of (19) to (22), characterized in that it is a micropowder of at least one fluorine-based resin selected from the group consisting of chlorotrifluoroethylene copolymers and polychlorotrifluoroethylene. Mead precursor solution composition.

(24) In the above fluorine-based resin micropowder dispersion, the average particle diameter of the dispersed fluorine-based resin micropowder is 10 µm or less, the fluorine-based resin according to any one of (19) to (22). Containing polyimide precursor solution composition.

(25) A fluorine-based resin-containing polyimide characterized by being obtained by using the fluorine-based resin-containing polyimide precursor solution composition according to any one of (19) to (24).

(26) A fluorine-based resin-containing polyimide film characterized by being obtained by using the fluorine-based resin-containing polyimide precursor solution composition according to any one of (19) to (24).

(27) A fluorine-based resin-containing polyimide insulating material characterized by being obtained by using the fluorine-based resin-containing polyimide precursor solution composition according to any one of (19) to (24).

(28) a step of preparing a micropowder dispersion of a fluorine-based resin containing a micropowder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent;

A step of preparing a polyimide precursor solution composition by mixing tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound;

A step of preparing a polyimide precursor solution composition containing a fluorine-based resin by mixing the micro-powder dispersion of the fluorine-based resin and the polyimide precursor solution composition;

A step of obtaining a fluorine-based resin-containing polyimide by curing the fluorine-based resin-containing polyimide precursor solution composition

A method for producing a polyimide containing a fluorine-based resin, comprising:

(29) A method for producing a fluorine-based resin-containing polyimide film, characterized by including the step of obtaining the fluorine-based resin-containing polyimide described in (28) and further comprising a step of obtaining the fluorine-based resin-containing polyimide film.

(30) A method for producing a fluorine-based resin-containing polyimide insulating film, characterized by including the step of obtaining the fluorine-based resin-containing polyimide described in (28) and further comprising a step of obtaining a fluorine-based resin-containing polyimide insulating film.

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

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

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

(34) The non-aqueous dispersion of the fluorine-based resin according to (1) or (2), characterized in that the fluorine-based resin is polytetrafluoroethylene, contains particle ceramics, and has a moisture content of 20,000 ppm or less by Karl Fischer method. .

(35) The non-aqueous dispersion according to (34), characterized in that the particulate ceramic contains any one of B, Na, Mg, Al, Si, P, K, Ca, and Ti.

(36) The particulate ceramic is Al ₂ O ₃ , SiO _{2 ,} CaCO ₃ , ZrO ₂ , SiC, The non-aqueous dispersion according to (34) or (35), characterized by comprising an inorganic compound of any one of Si ₃ N ₄ and ZnO.

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

According to the present invention, a non-aqueous dispersion of a fluorine-based resin such as polytetrafluoroethylene has a low viscosity in terms of particle size, excellent storage stability, and excellent redispersibility even after long-term storage. In addition, when it is added to various resin materials, rubbers, adhesives, lubricants, greases, printing inks, paints, etc., it is possible to mix them uniformly. In addition, a non-aqueous dispersion containing fluorine-based resin capable of uniformly dispersing fine particles of fluorine-based resin that improves electrical properties (low dielectric constant, low dielectric loss tangent) and physical properties, and a polyimide precursor that uniformly controls the dispersion state of fluorine-based resin A solution composition, polyimide excellent in electrical properties such as heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant and low dielectric loss tangent obtained by the composition, and processability, a polyimide film, a method for producing the same, and the polyimide; Circuit board using polyimide film, coverlay film, insulation film, correlation insulation film for wiring board, surface protection layer, sliding layer, release layer, fiber, filter material, wire covering material, bearing, paint, insulation shaft, tray, seamless belt, etc. Various belts, tapes, tubes, insulating materials, adhesive compositions for circuit boards, laminates for circuit boards, prepregs, and electronic devices using these are provided. In addition, although surfactants and dispersants containing fluorine may become hydrogen fluoride during heat treatment during polyimide conversion or incineration of wastewater, the practice of the present invention does not use surfactants or dispersants containing fluorine. Some of the shapes have the advantage of suppressing adverse effects on the environment and the like.

1 is a schematic view showing an example of an embodiment of a laminate for a circuit board according to the present invention in cross-sectional form.
2 is a schematic diagram showing an example of an embodiment of a laminate for a circuit board according to the present invention in cross-sectional form.
3 is a schematic view showing an example of an embodiment of the coverlay film of the present invention in cross-sectional form.

Next, embodiments of the present invention will be described in detail.

The polyimide precursor solution composition containing a fluorine-based resin of the present invention contains a micropowder of a fluorine-based resin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous dispersion of a fluorine-based resin having a moisture content of 20,000 ppm or less by Karl Fischer method. It is characterized by containing at least a sieve and a polyimide precursor solution.

[Non-aqueous dispersion of fluorine resin]

A non-aqueous dispersion of a fluorine-based resin such as polytetrafluoroethylene used in the present invention, comprising a micropowder of the fluorine-based resin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group. As a preferred embodiment, a non-aqueous dispersion having a moisture content of 20,000 ppm or less, preferably 5,000 ppm or less according to the Karl Fischer method is obtained. Although not particularly limited, for example, preparation can be performed by using micropowder of a fluorine-based resin having at least a primary particle size of 1 μm or less, a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, a solvent, or the like. Furthermore, as a particularly preferred embodiment, the polytetrafluoroethylene non-aqueous dispersion is characterized in that it contains at least polytetrafluoroethylene, particulate ceramics, and a fluorine-based additive containing a fluorine-containing group and a lipophilic group.

Examples of micropowders of fluorine-based resins that can be used in the present invention include polytetrafluoroethylene (PTFE), fluorinated ethylene-propylene copolymer (FEP), perfluoroalkoxy polymer (PFA), and chlorotrifluoroethylene (CTFE). , tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), at least one member selected from the group consisting of polychlorotrifluoroethylene (PCTFE) micropowder of a fluorine-based resin of the above, and these preferably have a primary particle diameter of 1 μm or less.

Among the fluorine-based resin micropowders, polytetrafluoroethylene (PTFE, dielectric constant 2.1), which has the most excellent properties among resin materials, is preferably used as a material having a low dielectric constant and a low dielectric loss tangent.

Such fluororesin micropowder is obtained by emulsion polymerization, and can be obtained by a commonly used method, such as a method described in a fluororesin handbook (edited by Kurokawa Takaomi, Nikkan Kogyo Shimbun). Further, the micropowder of the fluorine-based resin obtained by the emulsion polymerization is agglomerated and dried to be recovered as a fine powder of secondary particles in which the primary particles are aggregated, but various generally used methods for producing fine powders can be used. .

As the primary particle diameter of the fluorine-based resin micropowder, those with a volume-based average particle diameter (50% volume diameter, median diameter) of 1 μm or less measured by laser diffraction/scattering method, dynamic light scattering method, image imaging method, etc. are oily. It is preferable for stably dispersing in a solvent, and a more uniform dispersion is obtained by setting it preferably to 0.5 μm or less, and more preferably to 0.3 μm or less.

If the primary particle diameter of this fluorine-based resin micropowder exceeds 1 μm, it is not preferable because it tends to settle in an oil-based solvent and it becomes difficult to disperse stably. In addition, the lower the lower the lower limit of the average particle diameter, the better, but it is preferably 0.05 μm or more from the standpoint of manufacturability and cost.

The primary particle diameter of the fluorine-based resin in the present invention refers to a value obtained by a laser diffraction/scattering method or a dynamic light scattering method in the micropowder production step. Since the cohesive force between the primary particles is strong and it is difficult to easily measure the primary particle diameter by a laser diffraction/scattering method or a dynamic light scattering method, it may refer to a value obtained by an image imaging method. As the measuring device, for example, a dynamic light scattering method by FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction/scattering method by Microtrac (manufactured by Nikkiso Co., Ltd.), or an image imaging method by McView (manufactured by Mountec Co., Ltd.) etc. can be mentioned.

In the present invention, it is preferable to contain 5 to 70% by weight of fluororesin micropowder, more preferably 10 to 60% by weight, particularly preferably 10 to 50% by weight, based on the total amount of the non-aqueous dispersion. % is preferred.

When this content is less than 5% by weight, the amount of the solvent is large and the viscosity is extremely reduced, so that the micropowder particles of the fluororesin are easy to sediment, and when mixed with the polyimide precursor solution, the problem due to the large amount of solvent For example, undesirable situations such as extremely low viscosity of the fluorine-based resin-containing polyimide precursor solution composition and time consuming solvent removal may occur. On the other hand, when it is larger than 70% by weight, it is not preferable because the micropowder of the fluorine-based resin tends to agglomerate with each other and it becomes extremely difficult to stably maintain the state of the fine particles in a flowable state.

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 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 oil solvent serving as a dispersion medium is reduced and the wettability of the fluorine-based resin micropowder surface is improved, thereby improving the dispersibility of the micropowder of the fluorine-based resin. The fluorine group is adsorbed on the surface of the micropowder of the fluorine-based resin, the lipophilic group is extended in an oil-based solvent, and the steric hindrance of the lipophilic group prevents the aggregation of the micropowder of the fluorine-based resin, further improving the dispersion stability.

Examples of the fluorine-containing group include a perfluoroalkyl group and a perfluoroalkenyl group, and examples of the lipophilic group include one or two or more types such as an alkyl group, a phenyl group, and a siloxane group. Examples of the hydrophilic group include: For example, 1 type or 2 or more types, such as ethylene oxide, an amide group, a ketone group, a carboxyl group, and a sulfone group, are mentioned.

As the fluorine-based additives that can be specifically used, Suffron series such as perfluoroalkyl group-containing Suffron S-611 (manufactured by AGC Semichemical Co., Ltd.), Megafac F-555, Mecafac F-558, Megafac F-563 etc. Mekapack series (manufactured by DIC), Unidyne series such as Unidyne DS-403N (manufactured by Daikin Kogyo), etc. can be used.

These fluorine-based additives are appropriately selected according to the type of solvent and the micropowder of the fluorine-based resin to be used, but it is also possible to use one type or a combination of two or more types.

The content of the fluorine-based additive is 0.1 to 50% by weight based on the weight of the fluorine-based resin micropowder, but is preferably 5 to 35% by weight, more preferably 5 to 30% by weight, and particularly preferably 15 to 25% by weight. It is preferable to contain by weight %.

If this content is less than 0.1% by weight relative to the weight of the fluorine-based resin micropowder, the surface of the fluorine-based resin micropowder cannot be sufficiently wetted in a solvent such as an oil-based solvent. This is not preferable because the efficiency is lowered and problems may arise when handling the dispersion itself or mixing it with a resin material or the like thereafter.

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

Examples thereof include, but are not limited to, surfactants such as nonionic, anionic, and cationic surfactants, and polymeric surfactants such as nonionic, anionic, and cationic surfactants.

Examples of the solvent used in the non-aqueous dispersion of the present invention include γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, Methylcyclohexane, ethylcyclohexane, methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl 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, ethyl 3-ethoxypropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate , anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cyman , mesitylene, 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, mineral spirits, 2-Hyde hydroxyethyl acrylate, tetrahydrofurfuryl acrylate, 4-vinylpyridine, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, opentyl glycol Diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, methacrylate, methyl methacrylate, styrene, perfluorocarbon, hydrofluoroether, hydrochlorofluorocarbon, hydrofluorocarbon, purple Fluoropolyether, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N -Acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2- One solvent selected from the group consisting of imidazolidinone, methyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, γ-butyrolactone, sulfolane, halogenated phenols, and various silicone oils, or solvents thereof What contains 2 or more types of is mentioned.

Among these solvents, preference is given to formamide, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, although it varies depending on the use of the polyimide used. , N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane, halogenated phenols, xylene, and acetone. .

In the present invention, the above solvent is used, but it can be used in combination with other solvents or other solvents, and a suitable one is selected according to the purpose of the polyimide to be used (circuit board, coverlay film, etc.).

In addition, depending on the polarity of the solvent used, it is considered that the compatibility with water is high, but if the water content is high, the dispersibility of the fluorine-based resin micropowder in the solvent is impaired, and the viscosity may increase or the particles may agglomerate with each other. there is.

The solvent used in the present invention has a water content of 20,000 ppm or less according to the Karl Fischer method, preferably 5,000 ppm or less [0 ≤ water content ≤ 5,000 ppm]. In the present invention (including examples described later), the measurement of moisture content by the Karl Fischer method is based on JIS K 0068: 2001, and can be measured by, for example, MCU-610 (manufactured by Kyoto Electric Industry Co., Ltd.). By setting the water content in this solvent to 5,000 ppm or less, it is possible to obtain a non-aqueous dispersion of micropowder of a fluorine-based resin with excellent particle diameter, low viscosity and storage stability, more preferably 3,000 ppm or less, more preferably 2,500 ppm. It is preferably set to ppm or less, particularly 2,000 ppm or less. In addition, although it is possible to use the dehydration method of solvents, such as a generally used oil solvent, for adjusting below the said water content, for example, a molecular sieve etc. can be used.

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

In combination with one of the preferred embodiments of the present invention, the particulate ceramic used is contained in order to maintain a higher degree of dispersion stability of the non-aqueous dispersion of PTFE among fluorine resins in particular.

Particulate ceramics that can be used are not particularly limited, but preferably contain at least one or more of the elements of B, Na, Mg, Al, Si, P, K, Ca, and Ti, and are oxide-based containing these elements. , at least one type of particulate ceramic selected from a hydroxide type, a carbide type, a carbonate type, a nitride type, a halide type, and a phosphate type.

Particularly preferable particulate ceramics are Al ₂ O ₃ , SiO ₂ , CaCO ₃ , ZrO ₂ , SiC _, and Si from the viewpoints of further dispersion stability of the non-aqueous dispersion, compatibility with other components, availability, workability, and the like. It is preferably composed of at least one inorganic compound selected from among ₃ N ₄ and ZnO.

It is preferable that such fine particle ceramics have a primary particle diameter of 0.5 µm or less.

As the primary particle diameter of this particulate ceramic, 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. is 0.5 μm or less. , is stably dispersed in the non-aqueous system, and is preferable for maintaining the dispersion stability of the non-aqueous dispersion of PTFE at a higher level, preferably 0.3 μm or less, more preferably 0.1 μm or less, furthermore non-aqueous. The dispersion stability of the dispersion is excellent. In addition, the lower the lower limit of the primary particle diameter, the better, but it is preferably 0.02 μm or more from the viewpoints of manufacturability and cost.

In addition, in the measurement of primary particles of particulate ceramics in the present invention, when the cohesive force between ceramics is strong and it is difficult to easily measure primary particles by laser diffraction/scattering method or dynamic light scattering method, image imaging method It may indicate a value obtained by As the measuring device, for example, a dynamic light scattering method by FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), a laser diffraction/scattering method by Microtrac (manufactured by Nikkiso Co., Ltd.), an image imaging method by McView (manufactured by Mountec Co., Ltd.), etc. can be heard

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

If this content is less than 0.01% by weight, the effect of containing fine particle ceramics cannot be exhibited, and the dispersion stability of the non-aqueous dispersion of PTFE cannot be maintained at a higher level. On the other hand, if it exceeds 5% by weight, the characteristics of ceramic particles are strongly exhibited, and when the stability of the non-aqueous dispersion of PTFE is inhibited, or when added to various resin materials, rubber, adhesives, lubricants, grease, printing ink, or paint, etc. Rather, it is not desirable because it may degrade performance.

Such ceramic fine particles may be previously dispersed in a solvent (dispersion medium) used for the non-aqueous dispersion of PTFE, and then added before, during or after dispersion of PTFE. It could be.

Of the solvent (dispersion medium), it is preferable to vary depending on the use of the dispersion, etc., but methyl ethyl ketone, dimethylformamide, cyclohexanone, propylene glycol monomethyl ether acetate, N-methylpyrrolidone, γ-butyro Lactone, 2-propanol, etc. are mentioned.

The solvent of the present invention may further contain a silicone-based antifoaming agent. In particular, when the fluorine-based resin micropowder is 70% by weight or the fluorine-based additive is used at a high concentration of 50% by weight based on the weight of the fluorine-based resin micropowder, the foaming of the dispersion is affected by the manufacturing process and stability of the dispersion. , which may lead to problems when mixing resin materials and the like.

There are silicone emulsion type, self-emulsifying type, oil type, oil compound type, solution type, powder type, solid type, etc. as an antifoaming agent that can be used, but an optimal one is appropriately selected in combination with the oil solvent to be used. In particular, it is preferable to use a hydrophilic or water-soluble silicone-based antifoaming agent to be present at the interface between the oil-based solvent and air rather than at the interface between the oil-based solvent and PTFE, but it can be used without being limited thereto. The content of the antifoaming agent varies depending on the content (concentration) of the micropowder of the fluororesin, etc., but is preferably 1% by weight or less as an active ingredient relative to the total amount of the non-aqueous dispersion.

In the non-aqueous dispersion of the present invention, the average particle diameter of the fluorine-based resin micropowder by laser diffraction/scattering or dynamic light scattering in a dispersed state is 1 μm or less.

Even when micropowder of a fluorine-based resin having a primary particle diameter of 1 μm or less is used, the primary particles usually aggregate to form a micropowder with a particle diameter of 1 μm or more as secondary particles. By dispersing the secondary particles of this fluorine-based resin micropowder to a particle diameter of 1 μm or less, for example, using a disperser such as an ultrasonic disperser, 3 rolls, wet ball mill, bead mill, wet jet mill, high pressure homogenizer, etc. By dispersing, a stable dispersion can be obtained even when stored for a long time at low viscosity.

Further, in the present invention, the non-aqueous dispersion of the fluorine-based resin micropowder preferably has a water content of 5,000 ppm or less [0 ≤ water content ≤ 5,000 ppm] according to the Karl Fischer method. In addition to the amount of moisture contained in the oil-based solvent, water contained in the material itself such as fluorine-based resin micropowder or fluorine-based additive or in the manufacturing process of dispersing the fluorine-based resin micropowder in a solvent can also consider the incorporation of moisture, but ultimately By setting the moisture content of the non-aqueous dispersion of the resin to 5,000 ppm or less, a non-aqueous dispersion of the fluorine-based resin having more excellent storage stability can be obtained. It is more preferably 3,000 ppm or less, more preferably 2,500 ppm or less, and particularly preferably 2,000 ppm or less. In addition, as for adjusting the moisture content below, it is possible to use a dehydration method for an oil-based solvent that is generally used, but, for example, a molecular sieve or the like can be used. In addition, the non-aqueous dispersion of the fluorine-based resin can be used in a state in which the moisture content is sufficiently reduced by performing dehydration by heating or reduced pressure. Furthermore, after preparing the non-aqueous dispersion of the fluorine-based resin, it is possible to remove moisture using a molecular sieve or a membrane separation method. As long as it is, it can be used without particular limitation.

In a non-aqueous dispersion of fluorine-based resin micropowder, the smaller the average particle diameter or average particle diameter of the fluorine-based resin micropowder used in a dispersed state is, the easier it is to be affected by moisture. In particular, when it is 1 μm or less, not only the storage stability of the non-aqueous dispersion is significantly deteriorated, but also the micropowder of the fluorine-based resin easily aggregates and settles during mixing and addition with the polyimide precursor solution. , it becomes difficult to maintain a state in which the micropowder of the fluorine-based resin is uniformly dispersed, and problems such as an increase in viscosity during storage occur. In addition, aggregation of the fluorine-based resin micropowder tends to proceed in the step of removing the solvent, which adversely affects the physical properties and electrical properties of the finally obtained polyimide or polyimide film.

In addition, in the case of the non-aqueous PTFE dispersion, which is one of the preferred embodiments of the present invention, the moisture content according to the Karl Fischer method may be 20,000 ppm or less [0 moisture content 20,000 ppm]. In addition to the amount of water contained in the solvent (dispersion medium), water contained in the material itself, such as PTFE micropowder or fluorine-based additives, or water inclusion in the manufacturing process of dispersing PTFE in a solvent (dispersion medium) can be considered, but finally PTFE By setting the water content of the non-aqueous dispersion to 20,000 ppm or less, a PTFE non-aqueous dispersion having more excellent storage stability can be obtained. In addition, it is possible to use a dehydration method for an oil-based solvent that is generally used as the adjustment of the moisture content or less, but, for example, a molecular sieve or the like can be used. In addition, PTFE can be used in a state in which the moisture content is sufficiently lowered by performing dehydration by heating or reduced pressure. In addition, it is possible to remove water by using a molecular sieve or a membrane separation method after preparing the PTFE non-aqueous dispersion, but other than the above methods, as long as the water content of the non-aqueous dispersion can be lowered, it is not particularly limited. available.

The non-aqueous dispersion of PTFE of the present invention thus constituted contains at least PTFE, fine particle ceramics, and a fluorine-based additive containing a fluorine-containing group and a lipophilic group, thereby exhibiting low viscosity in terms of particle size, excellent filter liquid permeability, and preservation. It is excellent in stability and redispersibility after long-term storage, but the mechanism is estimated as follows.

That is, by using a fluorine-based additive having at least a fluorine-containing group and a lipophilic group, the surface tension of the non-aqueous solvent serving as a dispersion medium is lowered and the wettability to the surface of PTFE is improved to improve the PTFE dispersibility while the fluorine-containing group is adsorbed on the PTFE surface. The lipophilic group extends in a solvent serving as a dispersion medium, and steric hindrance of the lipophilic group prevents aggregation of PTFE, further improving dispersion stability. Furthermore, it is presumed that the inclusion of fine particle ceramics inhibits contact between PTFE particles and enhances fluidity, resulting in excellent filter permeability and storage stability, and excellent redispersibility even after long-term storage.

Therefore, the non-aqueous dispersion of PTFE of the present invention can be mixed uniformly even when added to various resin materials, rubber, adhesives, lubricants, grease, printing inks, paints, etc. For example, the non-aqueous PTFE dispersion of the present invention is added to resist materials such as photoresists such as color filters and black matrices and screen printing resists, and also among epoxy resin materials widely used as substrates and sealing materials for electronic devices. Since it is possible to achieve a further lower dielectric constant and lower dielectric dissipation factor by adding it, it can be suitably used for addition of resist materials and addition of epoxy resin materials.

The content of the micropowder of the fluorine-based resin used in the present invention having an average particle diameter of 1 μm or less in the dispersed state depends on the amount of the micropowder of the fluorine-based resin and the solvent contained in the dispersion, and also the amount of the polyimide precursor solution. It varies depending on each component, etc., and the solvent in the non-aqueous dispersion of fluorine-based resin or polyimide precursor solution is finally removed after preparing the fluorine-based resin-containing polyimide precursor solution composition, etc. during production of polyimide including polyimide film, etc. Therefore, the content of the micropowder of the fluororesin in the polyimide including the polyimide film or the like is finally preferably adjusted to 1 to 70% by weight, more preferably 5 to 50% by weight, and the dispersion is used. it is desirable

When the content of the micropowder of the fluorine-based resin is 1% by weight or more, the relative permittivity and dielectric loss tangent, which are electrical properties of polyimide including polyimide films, etc., can be lowered. The effects of the present invention can be exhibited without impairing the various properties and stability of the polyimide to be contained.

In addition, since the non-aqueous dispersion of the fluorine-based resin contains micropowder of the fluorine-based resin having an average particle diameter of 1 μm or less in a dispersed state, it has low viscosity and excellent storage stability in terms of particle diameter, and is subdivided even after long-term storage. Acidity becomes excellent. In addition, even when a large amount of fluorine-based additives are contained, the defoaming properties are excellent, and even when added to the polyimide precursor solution, they can be mixed uniformly.

[Polyimide precursor solution]

The polyimide precursor solution used in the present invention is obtained by reacting tetracarboxylic dianhydride and/or a derivative thereof with a diamine compound in the presence of a solvent. In addition, in this invention, "polyimide precursor solution" is a concept containing the solvent used in some cases.

For the preparation of this polyimide precursor solution, known methods, prescribed conditions, and the like can be suitably employed.

As tetracarboxylic dianhydride that can be used, for example, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2'- Bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, pyromellitic acid 2 Anhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) 2,3 ,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), 2,3,6,7-naphthalenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride , ethylene tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimellitate, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho[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. can

Preferably, the use of 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) is preferred.

Examples of usable diamine compounds include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5 -Dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiamine Phenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p- Phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylpropane, 2,4-diaminotoluene, bis(4-amino-3-carboxyphenyl)methane, 1,3-bis(4-aminophenoxy)benzene, 1,4- Bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,4-bis( β-amino-tert-butyl) toluene, bis(p-β-amino-tert-butylphenyl) ether, bis(p-β-methyl-6-aminophenyl)benzene, bis-p-(1,1-dimethyl -5-amino-pentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylenediamine, p-xylenediamine, di(p-aminocyclohexyl)methane, 2,17-diamino Eicosadecane, 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 individually or in mixture of 2 or more types.

Preferably, p-phenylenediamine (PPD), bis(4-amino-3-carboxyphenyl)methane (MBAA), 4,4'-diaminodiphenylether (ODA), 2,2-bis[4 Preference is given to using -(4-aminophenoxy)phenyl]propane (BAPP).

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

In the present invention, as the solvent used for preparing the polyimide precursor solution, an organic polar solvent capable of dissolving the polyimide precursor and having a boiling point of 300 ° C. or less at normal pressure is preferable, and furthermore, a non-aqueous dispersion of a fluorine-based resin Solvents that can be used on the sieve are preferred. For example, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclohexane, methyl-n-pentyl ketone, methyl isobutyl ketone, Methyl isopentyl 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-ethoxyethylpropionate, dioxane, Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether , phenetol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, 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, mineral spirits, 2-hydroxyethyl acrylate, tetrahydrofurfuryl 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, dimethylimidazoline, tetrahydrofuran, pyridine, formamide, acetanilide , dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N- Diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone , γ-butyrolactone, sulfolane, halogenated phenols, and the like, and these solvents may be used alone or in combination of two or more.

Preferably formamide, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylform It is preferable to use an amide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane, halogenated phenols, xylene, or acetone.

The polyimide precursor solution used in the present invention can be prepared by adding tetracarboxylic dianhydride and/or a derivative thereof and a diamine compound in a predetermined compositional ratio to a solvent, followed by stirring. The total concentration of tetracarboxylic dianhydride and/or derivatives thereof and the diamine compound in the solvent is set according to various conditions, but is usually preferably 5 to 30% by weight based on the total amount of the reaction solution. Although the reaction conditions at the time of stirring these are not specifically limited, It is preferable to set the reaction temperature to 80 degreeC or less, especially 5-50 degreeC. If the reaction temperature is too low, the reaction does not proceed or it takes too long for the reaction to proceed, and if the reaction temperature is too high, problems such as imidation proceed and discard occur. Moreover, it is preferable that reaction time is 1 to 100 hours.

<Compound represented by formula (I)>

The compound represented by formula (I) used in one of the embodiments of the present invention is a so-called butyral resin, which can uniformly and stably disperse fine particles of a fluorine-based resin micropowder in a polyimide precursor solution composition. The structure is a terpolymer composed of vinyl butyral/vinyl acetate/vinyl alcohol, polyvinyl alcohol (PVA) reacted with butyraldehyde (BA), and has a butyral group, an acetyl group, and a hydroxyl group. By changing the ratio of the structure (each ratio of l, m, n), solubility in non-aqueous solvents, compatibility with polyimide precursor solutions, etc., and chemical reactivity can be controlled.

As a compound represented by formula (I), commercially available products such as Sekisui Kagaku Kogyo S.L.B series, K (KS) series, SV series, and Kuraray Mobitar series can be used.

Specifically, the product name of Sekisui Kagaku Kogyo Co., Ltd.; SREC BM-1 (hydroxyl group content: 34 mol%, butyralization degree 65±3 mol%, molecular weight: 40,000), same BH-3 (hydroxyl group content: 34 mol%, butyralization degree 65±3 mol%, molecular weight : 110,000), copper BH-6 (hydroxyl group content: 30 mol%, butyralization degree 69 ± 3 mol%, molecular weight: 9.2 million), copper BX-1 (hydroxyl group content: 33 ± 3 mol%, acetalization degree 66 mol %, molecular weight: 100,000), copper BX-5 (hydroxyl group amount: 33 ± 3 mol%, acetalization degree 66 mol%, molecular weight: 130,000), copper BM-2 (hydroxyl group content: 31 mol%, butyralization degree 68 ± 3 mol%, molecular weight: 5.2 million), copper BM-5 (hydroxyl group content: 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight: 5.3 million), copper BL-1 (hydroxyl group content: 36 mol% butyral Crystallinity 63 ± 3 mol%, molecular weight: 1.9 million), copper BL-1H (hydroxyl group content: 30 mol%, butyralization degree 69 ± 3 mol%, molecular weight: 20,000), copper BL-2 (hydroxyl group content: 36 mol %, degree of butyralization 63 ± 3 mol%, molecular weight: 2.7 million), same BL-2H (amount of hydroxyl group: 29 mol%, degree of butyralization 70 ± 3 mol%, molecular weight: 2.8 million), BL-10 (amount of hydroxyl group : 28 mol%, butyralization degree 71 ± 3 mol%, molecular weight: 1.5 thousand), copper KS-10 (hydroxyl group amount: 25 mol%, acetalization degree 65 ± 3 mol%, molecular weight: 17 thousand), etc., or Kuraray Co., Ltd. product name; Mobitar B145 (hydroxyl group content: 21-26.5 mol%, acetalization degree 67.5-75.2 mol%), copper B16H (hydroxyl group content: 26.2-30.2 mol%, acetalization degree 66.9-73.1 mol%, molecular weight: 1-20,000), etc. can be heard

You may use these individually or in mixture of 2 or more types.

The content of the compound represented by formula (I) is preferably 0.01 to 30% by weight relative to the micropowder of the fluorine-based resin. When the content of this compound is less than 0.01% by weight, the dispersion stability deteriorates and the fluorine-based micropowder tends to precipitate, while when it exceeds 30% by weight, the viscosity of the fluorine-based resin-containing polyimide precursor solution increases, which is not preferable.

Furthermore, considering the characteristics of the obtained polyimide or the like, 0.01 to 5% by weight is more preferable, and particularly preferably 0.01 to 2% by weight is most preferable.

When the compound of formula (I) is included instead of the fluorine-based additive, the primary particle diameter of the micropowder of the fluorine-based resin is 10 μm or less, preferably 5 μm or less, and more preferably 1 μm or less. In addition, the lower the lower the lower limit of the primary particle diameter, the better, but from the standpoint of manufacturability and cost, 0.05 μm or more and 0.3 μm or less are preferable.

[Preparation of Fluorine-Based Resin-Containing Polyimide Precursor Solution Composition]

The polyimide precursor solution composition containing a fluorine-based resin of the present invention includes the micropowder of the fluorine-based resin, a fluorine-containing additive containing a fluorine-containing group and a lipophilic group, or a compound represented by Formula (I), and the water content according to the Karl Fischer method is It is characterized by containing at least a non-aqueous dispersion of a fluorine-based resin having a concentration of 20,000 ppm or less, preferably 5,000 ppm or less, and a polyimide precursor solution.

The polyimide precursor solution composition containing a fluorine-based resin of the present invention is a composition obtained by mixing a non-aqueous dispersion containing the fluorine-based resin with a polyimide precursor solution obtained by dissolving and polymerizing tetracarboxylic dianhydride and/or a derivative thereof and a diamine compound. However, tetracarboxylic dianhydride and/or a derivative thereof and a diamine compound may be added and dissolved in the non-aqueous dispersion containing the fluorine-based resin, and then polymerized to obtain a fluorine-based resin-containing polyimide precursor solution composition. . Further, a polyimide precursor solution composition containing a fluorine-based resin is obtained by adding and mixing the non-aqueous dispersion containing the fluorine-based resin in a polyimide precursor solution obtained by dissolving and polymerizing tetracarboxylic dianhydride and/or a derivative thereof and a diamine compound. It may be possible, and the order of addition and mixing is not limited as long as the fluorine-based resin in the non-aqueous dispersion of the fluorine-based resin can be mixed uniformly without aggregation or sedimentation.

The monomer concentration during the polymerization reaction in this preparation, that is, the total concentration of tetracarboxylic dianhydride and / or its derivative and diamine compound in the solvent is set according to various conditions, but is usually 5 to 30 in the total amount of the solution to be reacted. About % by weight is preferred.

If this concentration is less than 5% by weight, the reactivity of the tetracarboxylic dianhydride and/or its derivatives and the diamine compound deteriorates, the reaction takes time to progress, or the amount of solvent removed during film formation increases. It is not economical, and on the other hand, if the concentration exceeds 30% by weight, the viscosity at the time of polymerization becomes too high or problems such as precipitation occur. In addition, it is preferable to set the reaction temperature to 80°C or lower, particularly 5 to 50°C. If the reaction temperature is too lower than the temperature of 5 ° C, the reaction does not proceed or it takes too long to proceed, while if the reaction temperature is too high beyond 80 ° C, problems such as imidation proceed It happens. The reaction time is preferably about 1 to 100 hours.

[Preparation of polyimide and polyimide film obtained from the above fluorine-based resin-containing polyimide precursor solution composition, and method for producing the same]

In the polyimide and polyimide film of the present invention, the polyimide precursor in the polyimide precursor solution composition containing the fluorine-based resin prepared above is imidized to obtain a polyimide or polyimide film in which the fluorine-based resin is uniformly dispersed in fine particles.

In addition, each method for producing polyimide and polyimide film of the present invention includes a step of producing a non-aqueous dispersion of fluorine-based resin, and at least mixing the non-aqueous dispersion of fluorine-based resin and a polyimide precursor solution to form a polyimide containing fluorine-based resin. It is characterized by including a step of preparing a mid precursor solution composition and a step of obtaining a polyimide or polyimide film in which a fluorine-based resin is uniformly dispersed in fine particles by imidizing the polyimide precursor in the polyimide precursor solution composition. In addition, the imidation method is not particularly limited, and can be performed by a known method.

For example, in the case of producing a polyimide or polyimide film in which a fluorine-based resin is dispersed, the obtained fluorine-based resin-containing polyimide precursor solution composition is applied to the surface of the substrate for polyimide or the substrate for polyimide film to form a film. It can be obtained by forming a substance) (coating film), heat-treating the membranous substance, removing the solvent, and carrying out an imidation reaction.

As the substrate that can be used, for example, as long as it has a dense structure that does not substantially transmit liquid or gas, the shape or material is not particularly limited, and a belt known per se used when producing a normal film, a mold, Substrates for film formation such as rolls and drums, electronic components and wires such as circuit boards having a polyimide film formed on the surface as an insulating protective film, sliding parts or products having a film formed on the surface, and multilayered films or copper sheets formed by forming a polyimide film ( One film, copper foil, etc. at the time of forming a copper foil laminated board are mentioned suitably.

In addition, as a method of applying the polyimide precursor solution composition to such a substrate, for example, a method known per se such as a spray method, a roll coating method, a spin coating method, a bar-coating method, an inkjet method, a screen printing method, a slit coating method, and the like can be appropriately employed.

The film, film, etc. made of the polyimide precursor solution composition formed by applying to the base material may be degassed by heating at a relatively low temperature such as room temperature or lower under reduced pressure or normal pressure.

A film or the like formed of the polyimide precursor solution composition formed on the substrate is heated to remove the solvent and further imidized to form polyimide and a polyimide film. Heat treatment is preferably heat treatment in which the solvent is first removed at a relatively low temperature of 140° C. or less, and then the temperature is raised to the highest heat treatment temperature to imidize, rather than heat treatment at a high temperature suddenly. The highest heat treatment temperature can be employed in the temperature range of 200 to 600°C, but the heat treatment can be preferably performed in the temperature range of 300 to 500°C, more preferably 250 to 450°C. Instead of heat treatment or in combination with heat treatment, the imidation reaction may be promoted using a catalyst such as an amine compound. Moreover, carboxylic acid anhydride and the like can be used as a dehydrating agent for rapidly removing water generated in the imidization process.

The thickness of polyimide and polyimide film is appropriately adjusted depending on the application. For example, a polyimide film or film having a thickness of 0.1 to 200 μm, preferably 3 to 150 μm, more preferably 5 to 130 μm is suitable. it is used When the heating temperature is lower than 250°C, imidization does not proceed sufficiently, and when it exceeds 450°C, problems such as deterioration of mechanical properties due to thermal decomposition or the like occur. In addition, when the thickness exceeds 200 μm, the solvent cannot be sufficiently volatilized, and problems such as deterioration of mechanical properties or foaming during heat treatment may be caused.

The polyimide film obtained from the fluororesin-containing polyimide precursor solution composition and the micropowder concentration of the fluororesin in the polyimide film are not particularly limited, but are preferably 1 to 70% by weight, more preferably 1 to 70% by weight relative to the weight of the polyimide. 5 to 50% by weight, more preferably about 10 to 35% by weight. If the concentration of the micropowder of the fluorine-based resin is too small, there is no effect of adding the micropowder of the fluorine-based resin, and if the concentration of the micropowder of the fluorine-based resin is too large, the mechanical properties of the polyimide are deteriorated.

[Resin composition]

Examples of the resin composition used in the adhesive composition, which is one of the embodiments of the present invention, include cyanate ester resins and epoxy resins. This resin is to be the base resin of the adhesive composition for circuit boards, and can be used without particular limitation as long as it is suitable for use with respect to the adhesive resin.

Examples of cyanate ester resins that can be used include at least bifunctional aliphatic cyanate esters, at least bifunctional aromatic cyanate esters, and mixtures thereof, such as 1,3,5-tricyanatobenzene, 1,3- from dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene and 2,7-dicyanatonaphthalene Polymers of at least one selected polyfunctional cyanate ester, bisphenol A cyanate ester resins or those obtained by adding hydrogen thereto, bisphenol F-type cyanate ester resins or those obtained by adding hydrogen thereto, 6F bisphenol A dicyanate Ester resin, bisphenol E-type dicyanate ester resin, tetramethylbisphenol F dicyanate ester resin, bisphenol M dicyanate ester resin, dicyclopentadiene bisphenol dicyanate ester resin, or cyanate novolak resin. Moreover, commercial items of these cyanate ester resins can also be used.

Moreover, a cyanate ester hardening accelerator can be used for the said cyanate ester resin as needed.

As the cyanate ester hardening accelerator, organic acid metal salts and β-diketonato complexes are used, for example, organic acid metal salts and β-diketonato complexes such as iron, copper, zinc, cobalt, nickel, manganese, and tin. Specifically, the cyanate ester curing accelerator is an organic acid metal salt such as manganese naphthenate, iron naphthenate, copper naphthenate, zinc naphthenate, cobalt naphthenate, iron octanoate, copper octanoate, zinc octanoate, cobalt octanoate ; and β-diketonate complexes such as lead acetylacetonate and cobalt acetylacetonate.

The cyanate ester hardening accelerator is included in an amount of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on the metal concentration, based on 100 parts by weight of the cyanate ester resin in terms of reactivity, curability and moldability. can

As the usable epoxy resin, an epoxy resin containing an average of one or more epoxy groups (oxirane rings) can be used, and examples thereof include bisphenol F-type epoxy resins, bisphenol A-type epoxy resins, phenol novolac-type epoxy resins, and cresol no. Rockfish type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, dicyclopentadiene type epoxy resins, aralkyl type epoxy resins, biphenylaralkyl type epoxy resins, hydrogenated type epoxy resins obtained by hydrogenating the phenyl group of the above various epoxy resins , 1 or more types, such as an alicyclic epoxy resin, are mentioned.

Epoxy resins that can be used in the present invention are not limited to the above resins as long as one or more epoxy groups are present in one molecule, but bisphenol A, hydrogenated bisphenol A, cresol novolacs, and the like are suitable.

When using the said epoxy resin, it is preferable to use a hardening|curing agent from the point of reactivity, hardenability, and moldability. As the curing agent that can be used, for example, aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, isophoronediamine, metaphenylenediamine, paraphenylenediamine, Aromatic amines such as 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenolsulfone, 4,4'-diaminodiphenolmethane, and 4,4'-diaminodiphenol ether, mercapto Mercaptans such as propionic acid esters and terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromethane Mobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris(4-hydroxyphenyl)methane, 4,4-(1-(4-( Phenol resins such as 1-(4-hydroxyphenyl)-1-methylethyl)phenylethylidene)bisphenol, phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolak, and brominated bisphenol A novolak , polyols obtained by hydrogenating aromatic rings of these phenolic resins, polyazelaic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3 -dicarboxylic acid anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid Alicyclic acid anhydrides such as carboxylic anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2 - Imidazoles such as phenylimidazole and salts thereof, amine adducts obtained by reacting the aliphatic amines, aromatic amines and/or imidazoles with an epoxy resin, hydrazines such as adipic acid dihydrazide, and at least one of tertiary amines such as dimethylbenzylamine and 1,8-diazabicyclo[5.4.0]undecene-7, organic phosphines such as triphenylphosphine, and dicyandiamide.

Among these, alicyclic acid anhydrides and aromatic acid anhydrides are preferable, more preferably alicyclic acid anhydrides, and particularly preferably methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3- dicarboxylic acid anhydride, methyl-norbornane-2,3-dicarboxylic acid anhydride.

The amount of these curing agents is determined depending on the epoxy resin used and the type of curing agent used, but it is preferable to match the epoxy equivalent with the amine equivalent or active hydrogen equivalent. By mixing the same equivalent amount, the crosslinking reaction sufficiently proceeds, and a cured product of an adhesive for circuit board having excellent light resistance and heat resistance is obtained.

[Adhesive composition for circuit board]

The adhesive composition for a circuit board of the present invention includes a micropowder of a fluorine-based resin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group, and a non-aqueous dispersion of a fluorine-based resin having a water content of 5,000 ppm or less by the Karl Fischer method; , It includes at least a resin composition composed of a cyanate ester resin or an epoxy resin, and may further contain a rubber component dispersed in the cyanate ester resin or epoxy resin.

The adhesive composition for a circuit board of the present invention should also have sufficient flexibility (Flexible, hereinafter the same) in order to be used in the manufacture of a flexible printed circuit board capable of bending wiring or a substrate. It is preferable that the adhesive composition for a circuit board further contains a rubber component.

Examples of the rubber component that can be used include natural rubber (NR) and synthetic rubber, and preferably styrene butadiene rubber (SBR), isoprene rubber (IR), acrylonitrile butadiene rubber (NBR), ethylene propylene diene monomer ( EPDM) rubber, polybutadiene rubber, modified polybutadiene rubber, and the like, and preferably EPDM rubber having an ethylene content of 10 to 40% by weight, or SBR, NBR, etc. may be used. In particular, the resin composition An EPDM rubber capable of lowering the dielectric constant and dielectric dissipation factor values is preferred.

The content of these rubber components is 1 to 80 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the resin (cyanate ester resin or epoxy resin) in terms of further exhibiting the effect of the present invention, adhesive strength and heat resistance. 70 parts by weight, more preferably 20 to 60 parts by weight.

The adhesive composition for a circuit board of the present invention is a non-aqueous dispersion of a fluorine-based resin having a moisture content of 5,000 ppm or less according to the Karl Fischer method, including the micropowder of the fluorine-based resin and a fluorine-based additive containing at least a fluorine-containing group and a lipophilic group. and a resin composition comprising a cyanate ester resin or an epoxy resin. It can manufacture by the method of adding and mixing the containing resin composition.

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

In addition, the adhesive composition for a circuit board of the present invention may contain a curing accelerator, an antifoaming agent, a colorant, a phosphor, a denaturant, an anti-discoloration agent, an inorganic filler, a silane coupling agent, a light diffusing agent, a thermally conductive filler, etc. Conventionally known additives can be blended in an appropriate amount.

Examples of other curing (reaction) accelerators include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, and 1,8-diazabicyclo(5,4,0)undecene. Tertiary amines such as -7 and their salts, phosphines such as triphenylphosphine, phosphonium salts such as triphenylphosphonium bromide, aminotriazoles, tin-types such as tin octylate and dibutyltin dilaurate , zinc-based catalysts such as zinc octylate, metal catalysts such as acetylacetonates such as aluminum, chromium, cobalt, and zirconium. These hardening (reaction) accelerators may be used independently or may use 2 or more types together.

The adhesive composition for a circuit board of the present invention can be molded and cured by the same method as the known cyanate ester resin composition and epoxy resin composition to form a cured product. The molding method and the curing method may be the same methods as those of known cyanate ester resins and epoxy resin compositions, and the methods inherent in the adhesive composition for circuit boards of the present invention are unnecessary and are not particularly limited.

The adhesive composition for a circuit board of the present invention may further be in the form of a laminate, a molding, an adhesive, a coating, or a film.

Since the adhesive composition for a circuit board of the present invention is obtained by using a non-aqueous dispersion in which micropowder of a fluorine-based resin is stably and uniformly dispersed, the adhesive composition for a circuit board has a low relative permittivity and dielectric loss tangent, adhesiveness, Since it has excellent properties such as heat resistance, dimensional stability, and flame retardancy, it is suitable for adhesive materials for circuit boards, and can be used, for example, in the manufacture of laminates for circuit boards, coverlay films, prepregs, bonding sheets, etc. using the same. The coverlay film or prepreg, bonding sheet, etc. can be applied to a circuit board, for example, a flexible printed circuit board (FPCB) such as a flexible metal clad laminate, and the adhesive composition for circuit board of the present invention is used for their manufacture. In this case, an adhesive composition for a circuit board having a lower relative dielectric constant and a lower dielectric loss tangent, and excellent properties such as adhesiveness, heat resistance, dimensional stability, and flame retardancy can be realized.

[circuit board]

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

In the circuit board of the present invention, for example, in a flexible printed circuit board (FPC), an insulating fluorine-based resin-containing polyimide film obtained from the fluorine-based resin-containing polyimide precursor solution composition and a metal foil are formed by using an adhesive composition such as an epoxy resin or a cyanate ester resin. It can be manufactured by bonding together to produce a metal clad laminate (CCL) and applying a circuit to the metal foil.

The thickness of the polyimide film of the present invention, which is the insulating fluorine-based resin-containing film, can be selected from a suitable range in consideration of sufficient electrical insulation, thickness of the metal clad laminate, flexibility, etc., and is preferably 5 to 50 μm, Preferably, 7 to 45 μm is preferable.

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

As said metal foil, what has metal foil which has electroconductivity is mentioned, For example, gold, silver, copper, stainless steel, nickel, aluminum, these alloys etc. are illustrated. From the viewpoints of conductivity, ease of handling, cost and the like, copper foil or stainless foil is preferably used. As the copper foil, anything manufactured by a rolling method or an electrolytic method can be used.

The thickness of the metal foil is set within a suitable range in consideration of the electrical conductivity, interfacial adhesion of the insulating film, the flexibility of the laminate, the improvement of the bending resistance, the ease of forming a fine pattern in circuit processing, and the conductivity between wires. It may be, for example, preferably in the range of 1 to 35 μm, more preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.

In addition, the surface roughness Rz (10-point average roughness) of the metal foil used is preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and particularly preferably in the range of 0.2 to 2.0 μm. do.

The circuit board of the present invention configured as described above is an insulating film, and by using the polyimide film obtained from the fluorine-based resin-containing polyimide precursor solution composition of the present invention, the dielectric constant and dielectric loss tangent are low, and heat resistance, electrical insulation, and mechanical properties are improved. An excellent circuit board can be obtained.

[Laminate for circuit board]

The laminate for a circuit board of the present invention is a laminate for a circuit board comprising at least a configuration of an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is for a circuit board having the above configuration. It is characterized in that it is composed of an adhesive composition.

1 is a schematic diagram showing a metal clad laminate (FPCB), which is an example of an embodiment of a laminate for circuit board according to the present invention, in cross-sectional form.

In the laminate for circuit board (A) of the present embodiment, a metal foil 30 is laminated on an insulating film 10, and an adhesive resin layer 20 interposed between the insulating film 10 and the metal foil 30 It includes at least, and the adhesive resin layer 20 is composed (joined) of the above-described adhesive composition for circuit boards.

2 is a schematic view showing a metal clad laminate (FPCB), which is another example of an embodiment of a laminate for circuit board according to the present invention, in cross-sectional form.

As shown in FIG. 2 instead of the single-sided structure of FIG. 1, the laminated sheet (B) for circuit board of this embodiment employs a double-sided structure, and metal foils 30 and 30 are laminated on both sides of an insulating film 10. and includes at least adhesive resin layers (20, 20) interposed between the insulating film (10) and the metal foil (30, 30), respectively, and the adhesive resin layers (20, 20) have the above configuration. of the adhesive composition for circuit boards (joining).

In the laminate for circuit board according to the present invention, such as FIGS. 1 and 2, the insulating film 10 used is not particularly limited as long as it has electrical insulation, but has heat resistance, flexibility, mechanical strength, and a thermal expansion coefficient similar to that of metal. that can be used

As the insulating film 10 that can be used, for example, polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide ( PEI) at least one film selected from the group consisting of polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, and polyether ether ketone (PEEK), preferably Preferably it is a polyimide (PI) film.

In addition, in terms of further improving the interfacial adhesion with the adhesive resin layer 20, etc., a film formed from these materials may preferably be additionally surface-treated with a low-temperature plasma or the like.

The thickness of the insulating film 10 can be selected from an appropriate range, preferably 5 to 50 μm, more preferably 7 to 45 μm, in consideration of sufficient electrical insulation and the thickness and flexibility of the metal clad laminate. .

The adhesive resin layer 20 is composed (joined) of the above-described adhesive composition for circuit boards, and its thickness is preferably 1 to 50 in terms of interfacial adhesion of the insulating film, flexibility of the laminate, adhesive strength, and the like. μm, more preferably 3 to 30 μm.

Examples of the metal foil 30 include those having conductive metal foil, and examples thereof include gold, silver, copper, stainless steel, nickel, aluminum, and alloys thereof. From the viewpoints of conductivity, ease of handling, cost and the like, copper foil or stainless foil is preferably used. As the copper foil, anything manufactured by a rolling method or an electrolytic method can be used.

The thickness of the metal foil takes into account electrical conductivity, interfacial adhesion of the insulating film, flexibility of the laminate, improvement of bending resistance, ease of forming a fine pattern in circuit processing, and conductivity between wires. An appropriate range can be set. , For example, it is preferably in the range of 1 to 35 μm, more preferably in the range of 5 to 25 μm, and particularly preferably in the range of 8 to 20 μm.

In addition, the surface roughness Rz (10-point average roughness) of the metal foil used is preferably in the range of 0.1 to 4 μm, more preferably in the range of 0.1 to 2.5 μm, and particularly in the range of 0.2 to 2.0 μm. desirable.

The manufacture of the laminate for circuit board of the present invention (eg, FIG. 1 or 2) configured as described above is performed by applying the adhesive composition for circuit board of the present invention having the above configuration on the insulating film 10, for example, After forming the paper 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 bonded by thermal compression (thermal lamination) to obtain relative permittivity and A laminate for a circuit board having a low dielectric loss tangent and excellent properties such as adhesion, heat resistance, dimensional stability, and flame retardancy can be manufactured. At this time, the final flexible metal foil laminate can be obtained by completely curing the semi-cured adhesive resin layer 20 by post-curing the flexible metal foil laminate.

[Coverlay Film]

Next, the coverlay film of the present invention is a coverlay film in which an insulating film and an adhesive layer are formed on at least one side of the insulating film, and the adhesive layer is an adhesive composition for a circuit board having the above configuration.

3 is a schematic view showing an example of an embodiment of the coverlay film of the present invention in cross-sectional form.

The coverlay film (C) of the present embodiment is used as a surface protection film or the like for a flexible printed wiring board (FPC), and an adhesive resin layer 50 is formed on an insulating film 40, and the adhesive resin layer On 50, a separator (release film) 60 such as paper or PET film serving as a protective layer is bonded. In addition, this separator (release film) 60 is provided as needed in consideration of workability, storage stability, and the like.

The insulating film 40 used is the same as the insulating film 10 used in the above-described laminate for circuit board, and examples include polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate ( PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether (modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, polyetheretherketone (PEEK) One or more types of films selected from the group consisting of may be mentioned.

In addition, in that the film formed from these materials further improves the interfacial adhesion with the adhesive resin layer 50, it is preferable to use a film additionally surface-treated with low-temperature plasma or the like.

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

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

The adhesive resin layer 50 is composed (joined) of the above-described adhesive composition for circuit boards, and its thickness is preferably 1 to 50 μm, in terms of interfacial adhesion and adhesive strength of the insulating film, Preferably, 3 to 30 μm is preferable.

The coverlay film of the present invention configured as described above is coated on the insulating film 40 by using a comma roll coater, a reverse roll coater, etc. to form an adhesive layer, The relative permittivity and dielectric loss tangent are reduced by drying to a semi-cured state (the composition is in a dried state or a state in which a curing reaction is progressing partially), and then laminating the separator (release film) 60 serving as the above-described protective layer. A coverlay film having low adhesiveness, excellent heat resistance, dimensional stability, flame retardancy and the like can be manufactured.

In the present invention, polyimide or polyimide film having excellent electrical properties such as heat resistance, mechanical properties, sliding properties, insulation, low dielectric constant and low dielectric dissipation obtained by the above-described polyimide precursor solution composition and processability, or a polyimide film is used. In addition to circuit boards and coverlay films, such polyimide or polyimide films can be used to make insulation films, correlation insulation films for wiring boards, surface protection layers, sliding layers, release layers, fibers, filter materials, wire covering materials, bearings, paints, and insulation. It can be suitably used for applications such as various belts such as shafts, trays, and seamless belts, tapes, and tubes.

Example

Next, the present invention will be further described in detail with reference to Examples and Comparative Examples. In addition, the present invention is not limited to the following examples.

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

According to the compounding formula shown in Table 1 below, after sufficiently stirring and mixing and dissolving the fluorine-based additive in the solvent, PTFE micro-powder was added as a micro-powder of the fluorine-based resin, and further stirring and mixing were performed. Thereafter, the obtained PTFE mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to obtain dispersions 1 to 5.

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

Table 1 below shows the blending formulations of the dispersions 1 to 5, the average particle diameter of PTFE and the moisture content of the obtained dispersions.

[Table 1]

[Examples 1 to 3 and Comparative Examples 1 to 3: Preparation of fluorine-based resin-containing polyimide precursor solution composition]

<Example 1>

(1-a) Preparation of polyimide precursor solution

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

(1-b) Dispersion 1 in Table 1 was used as the non-aqueous dispersion of fluorine-based resin.

(1-c) Method for producing fluorine-based resin-containing polyimide precursor solution composition

18 parts by weight of Dispersion 1 (PTFE content: 30% by weight) was added to the polyimide precursor solution prepared in 1-a, stirred and mixed for 10 minutes, and containing a fluororesin containing 30% by weight of PTFE based on the resin component. A polyimide precursor solution composition was obtained.

(1-d) Method for producing a polyimide film containing a fluorine-based resin

The fluorine-based resin-containing polyimide precursor solution composition obtained in 1-c was applied onto a glass plate as a substrate by a bar coater, degassed and preliminarily dried at 25°C for 50 minutes under reduced pressure, and then held at 120°C for 45 minutes under a nitrogen atmosphere at normal pressure. , Heat treatment was performed at 150°C for 30 minutes, 200°C for 15 minutes, 250°C for 10 minutes, and 400°C for 10 minutes to form a polyimide film having a thickness of 50 μm.

<Example 2>

In the same manner as in Example 1, using Dispersion 2, a fluorine-based resin-containing polyimide precursor solution composition (2-b) was obtained with the formulation shown in Table 2 below. Further, a polyimide film (2-d) was formed by the same method as in Example 1.

<Example 3>

In the same manner as in Example 1, a fluorine-based resin-containing polyimide precursor solution composition (3-b) was obtained using Dispersion 3 and the formulation shown in Table 2 below. Further, a polyimide film (3-d) was formed by the same method as in Example 1.

<Comparative Example 1>

In the same manner as in Example 1, a fluorine-based resin-containing polyimide precursor solution composition (4-b) was obtained using Dispersion 4 and the formulation shown in Table 2 below. Further, a polyimide film (4-d) was formed by the same method as in Example 1.

<Comparative Example 2>

In the same manner as in Example 1, a fluorine-based resin-containing polyimide precursor solution composition (5-b) was obtained using Dispersion 5 and the formulation shown in Table 2 below. Further, a polyimide film (5-d) was formed by the same method as in Example 1.

<Comparative Example 3>

A polyimide film (6-d) was formed in the same manner as in Example 1 using the polyimide precursor obtained in Example 1 (without using a dispersion: without PTFE).

[Table 2]

[evaluation]

The fluorine-based resin-containing polyimide precursor solution composition (1-5-c) obtained in Examples 1 to 3 and Comparative Examples 1 to 2 and the polyimide films obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated for each of the following. method.

(Average particle diameter of fluororesin particles in fluororesin-containing polyimide precursor solution composition)

A polyimide precursor solution composition containing a fluorine-based resin was diluted with N,N-dimethylacetamide, and the average particle diameter of PTFE was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) to evaluate the state of aggregation. did

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

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

In addition, the sedimentation state of the PTFE particles after being left still at 25°C for 30 days was visually confirmed, and the sedimentation and redispersibility states were sensory evaluated according to the following evaluation criteria.

Criteria for evaluation of viscosity change:

A: The viscosity change of the liquid is in the range of ± 10%

B: The change in viscosity of the liquid exceeds the range of ±10%

Criteria for evaluating sedimentation:

A: What sedimentation layer is not seen in the lower part

B: What the sedimentation layer is visible in the lower part

Criteria for evaluation of redispersibility:

A: What the precipitate easily redispersed when stirred

B: Difficult to redisperse when the sediment is stirred

(Evaluation method of state of polyimide film)

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

Condition Evaluation Criteria for Polyimide Films

A: There is no foreign material such as PTFE agglomerates, and a smooth surface is formed.

B: Foreign matter such as agglomerates of PTFE was confirmed.

(Relative dielectric constant and dielectric loss tangent of polyimide film)

The polyimide film obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was removed from the glass plate, and the relative permittivity and dielectric constant were measured at 25° C. and a frequency of 1 kHz using an impedance analyzer according to the test standard of JIS C6481-1996. The tangent was measured.

[Table 3]

Looking at the results of Tables 2 and 3, the fluorine-based resin-containing polyimide precursor solution compositions of Examples 1 to 3 within the scope of the present invention showed little change in the particle diameter or viscosity of the fluorine-based resin and were very stable. In addition, it was confirmed that the relative permittivity and dielectric loss tangent of the polyimide film were reduced compared to Comparative Example 3 not containing a fluorine-based resin. In addition, the mechanical properties and the like of the polyimide films obtained in Examples 1 to 3 exhibited performance substantially equivalent to that of the polyimide film of Comparative Example 3. In addition, the performances of both polyimide and PTFE are fused, and performance specific to PTFE, such as sliding properties, insulating properties, and releasability, is improved.

On the other hand, in Comparative Example 1 using Dispersion 4 having a water content outside the scope of the present invention, the stability of the fluorine-based resin-containing polyimide precursor solution composition was low, the state of the polyimide film deteriorated, and no effect was seen on the electrical properties. . Further, in Comparative Example 2 of Dispersion 5 using a fluorine-based resin having a large particle diameter, the stability of the polyimide precursor solution composition containing the fluorine-based resin was also low, and the state of the polyimide film was deteriorated. In addition, the condition of the polyimide film of Comparative Example 2 was worse than that of Comparative Example 1, and electrical properties could not be measured.

[Preparation of micropowder dispersion of fluorine resin: Dispersion 6-12]

According to the formulation shown in Table 4 below, after sufficiently stirring and mixing and dissolving the compound represented by formula (I) in a solvent, PTFE micropowder was added as a fluorine-based resin micropowder, followed by further stirring and mixing. Thereafter, the resulting PTFE mixture was dispersed with zirconia beads having a diameter of 0.3 mm using a horizontal bead mill to obtain dispersions 6 to 12.

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

Table 4 below shows the formulation of the dispersions 6 to 12, the average particle diameter of PTFE and the viscosity of the obtained dispersions. In addition, as a result of measuring the moisture content of the obtained dispersions 6 to 12, each moisture content by the Karl Fischer method was within the range of 700 to 3,000 ppm, respectively.

[Table 4]

*1: Primary particle average particle diameter

*3: ESREC BL-10 (butyral (PVB) resin, manufactured by Sekisui Kagaku Kogyo Co., Ltd., hydroxyl group 28 mol%, butyralization degree 71±3 mol%, molecular weight 150,000)

*4: SRECK BM-1 (butyral (PVB) resin, manufactured by Sekisui Kagaku Kogyo Co., Ltd. hydroxyl group 34 mol%, butyralization degree 65 ± 3 mol%, molecular weight 40,000)

*5: SRECK BH-3 (butyral (PVB) resin, manufactured by Sekisui Kagaku Kogyo Co., Ltd. 34 mol% hydroxyl group, degree of butyralization 65 ± 3 mol%, molecular weight 110,000)

*6: SRECK KS-10 (butyral (PVB) resin, manufactured by Sekisui Kagaku Kogyo Co., Ltd. hydroxyl group 25 mol%, acetalization degree 74 ± 3 mol%, molecular weight 170,000)

*2: Megafac F-563: Oligomer containing fluorine-containing and lipophilic groups from DIC, active ingredient 100 wt%

[Examples 4 to 10 and Comparative Example 4: Preparation of Fluorine-Based Resin-Containing Polyimide Precursor Solution Composition]

<Example 4>

(a) Preparation of polyimide precursor solution

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

(b) Dispersion 6 of Table 4 was used as the micropowder dispersion of fluorine-based resin.

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

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

(d) Preparation of a polyimide film containing a fluorine-based resin

The fluorine-based resin-containing polyimide precursor solution composition obtained in (c) above was applied onto a glass plate as a base material by a bar coater, degassed and pre-dried at 25° C. for 50 minutes under reduced pressure, and then dried at 120° C. for 45 minutes under normal pressure nitrogen atmosphere. , Heat treatment was performed at 150°C 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 having a thickness of 50 µm.

<Example 5>

A polyimide film (2) was formed in the same manner as in Example 4, except that Dispersion 7 in Table 4 was used as the fluorine-based resin micropowder dispersion.

<Example 6>

A polyimide film (3) was formed in the same manner as in Example 4, except that Dispersion 8 in Table 4 was used as the micropowder dispersion of the fluorine-based resin.

<Example 7>

A polyimide film 4 was formed in the same manner as in Example 4, except that Dispersion 9 in Table 4 was used as the fluorine-based resin micropowder dispersion.

<Example 8>

A polyimide film 5 was formed in the same manner as in Example 4, except that Dispersion 10 in Table 4 was used as the micropowder dispersion of the fluorine-based resin.

<Example 9>

A polyimide film 6 was formed in the same manner as in Example 4, except that the dispersion 11 of Table 4 was used as the micropowder dispersion of the fluorine-based resin.

<Example 10>

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

5.4 parts by weight of PTFE micropowder (primary particle diameter: 3㎛) and 1.5% by weight of S-REC BL-10 were added to the polyimide precursor solution, stirred and mixed for 2 hours, and 30% by weight of PTFE was contained with respect to the resin component. A polyimide precursor solution composition containing a fluorine-based resin was obtained.

The above fluorine-based resin-containing polyimide precursor solution composition was applied onto a glass plate as a base material by a bar coater, degassed and pre-dried at 25°C for 50 minutes under reduced pressure, and then dried at 120°C for 45 minutes and 150°C for 30 minutes under normal pressure nitrogen atmosphere. Heat treatment was performed at 200° C. for 15 minutes, 250° C. for 10 minutes, and 400° C. for 10 minutes to form a polyimide film 7 having a thickness of 50 μm.

<Comparative Example 4>

A polyimide film 8 was formed in the same manner as in Example 4, except that the dispersion 12 of Table 4 was used as the micropowder dispersion of the fluorine-based resin.

[evaluation]

Each state of viscosity change, sedimentation, and redispersibility of the fluorine-based resin-containing polyimide precursor solution composition obtained in Examples 4 to 10 and Comparative Example 4, and the polyimide film (1) obtained in Examples 4 to 10 and Comparative Example 4 Each evaluation of the state of (8), relative permittivity and dielectric loss tangent, and adhesiveness was performed by each of the following methods. These results are shown in Table 5 below.

In addition, as a result of measuring the water content of each of the fluorine-based resin-containing polyimide precursor solution compositions obtained in Examples 4 to 10 and Comparative Example 4, the water content by the Karl Fischer method was in the range of 700 to 3,000 ppm, respectively.

(Method for Measuring Average Particle Diameter of Fluororesin Particles in Fluororesin-Containing Polyimide Precursor Solution Composition)

A polyimide precursor solution composition containing a fluorine-based resin was diluted with N,N-dimethylformamide (DMF), and the average particle diameter of PTFE was measured by a dynamic light scattering method using FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.), and agglutination was performed. status was evaluated.

(Evaluation method of viscosity change sedimentation/redispersion state of fluorine-based resin-containing polyimide precursor solution composition)

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

In addition, the sedimentation state of the PTFE particles after being left still at 25°C for 30 days was visually confirmed, and the sedimentation and redispersibility states were sensory evaluated according to the following evaluation criteria.

Criteria for evaluation of viscosity change:

A: The change in viscosity of the liquid is in the range of ± 10%

B: The change in viscosity of the liquid exceeds the range of ± 10%

Criteria for evaluating sedimentation:

A: What sedimentation layer is not seen in the lower part

B: sedimentation layer visible at the bottom (re-dispersion is easy)

C: Showing a sedimentation layer at the bottom (difficulty in redispersion)

Criteria for evaluation of redispersibility:

A: What the precipitate easily redispersed when stirred

B: Difficult to redisperse when the sediment is stirred

(Evaluation method of state of polyimide film)

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

Condition Evaluation Criteria for Polyimide Films

A: There is no foreign material such as PTFE agglomerates, and a smooth surface is formed.

B: Foreign matter such as agglomerates of PTFE was confirmed.

(Measurement method of dielectric constant and dielectric loss tangent of polyimide film)

The polyimide film obtained in Examples 4 to 9 and Comparative Example 4 was separated from the glass plate, and the relative dielectric constant and dielectric loss tangent were measured at a frequency of 25 ° C. and 1 kHz using an impedance analyzer according to the test standard of JIS C6481-1996. did

(Method for Evaluating Adhesion of Polyimide Film)

Polyimide films (1) to (8) obtained in Examples 4 to 10 and Comparative Example 4 and polyimide films (without PTFE) produced by the same method as in Example 1 without using a dispersion were prepared, respectively. Bonding was performed using a two-component curing type epoxy adhesive, and a peeling test was performed by a method specified in JIS K6854-, and adhesiveness was evaluated according to the following evaluation criteria.

Criteria for evaluation of adhesion:

A: When the adhesive portion is destroyed without peeling at the interface between the polyimide film and the epoxy adhesive

B: In the case of peeling at the interface between the polyimide film and the epoxy adhesive

[Table 5]

As is clear from the results of Table 5 above, in any of Examples 4 to 10 and Comparative Example 4, the average particle diameter, viscosity change, sedimentation, redispersibility, and state of the polyimide film were not particularly changed. On the other hand, the fluorine-based resin-containing polyimide precursor solution composition of Example 10 using PTFE micropowder having a large particle diameter of 3 μm was evaluated as B in sedimentation property, but it was easily redispersible and was at a level without problems in use. .

Compared with Examples 4-10, the relative permittivity and dielectric loss tangent of the polyimide film were higher in Comparative Example 4. This is because Comparative Example 4 uses a fluorine-based dispersant, and it has been confirmed that the electrical properties are inferior to those of Examples 4 to 10.

Further, the adhesiveness of the polyimide film was peeled off at the interface between the polyimide film and the adhesive in the case of Comparative Example 4, and the adhesion of the polyimide film was poor due to the influence of the fluorine-based dispersant present on the surface of the polyimide film. guessed On the other hand, in the polyimide films of Examples 4 to 10 within the scope of the present invention, destruction occurred at the adhesive portion without peeling at the interface between the polyimide film and the adhesive, and it was found that there was no decrease in the adhesiveness or adhesiveness of the polyimide. lost.

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

After stirring, mixing and dissolving the fluorine-based additive sufficiently in a solvent according to the formulation shown in Table 6 below, PTFE micro-powder was added as a micro-powder of the fluorine-based resin, and further stirring and mixing were performed. Thereafter, the obtained PTFE mixture was dispersed into zirconia beads having a diameter of 0.3 mm using a horizontal bead mill, and dispersions 13 to 17 were obtained.

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

Table 6 below shows the compounding formulation of the dispersions 13 to 17, the average particle diameter of PTFE and the moisture content of the obtained dispersions.

[Table 6]

[Examples 11 to 13 and Comparative Examples 5 to 6: Preparation of adhesive composition for circuit board]

Using the obtained dispersions 13 to 17, adhesive compositions for circuit boards were prepared according to the formulation shown in Table 7 below.

After mixing in the mixing ratio shown in Examples 11 to 13 and Comparative Examples 5 to 6, the PTFE dispersion and the resin were stirred to uniformly mix using a disper to obtain adhesive compositions for circuit boards.

Here, the adhesive compositions I to III according to Examples 11 to 13, which are the adhesive compositions for circuit boards prepared using the dispersions 11 to 13, showed a very uniform state, but the circuit prepared using the dispersion 16 In the adhesive composition IV of Comparative Example 5, which is the adhesive composition for a substrate, a granular substance that appeared to be an aggregation of PTFE particles was observed on the wall surface. Further, in the adhesive composition V according to Comparative Example 6, which is an adhesive composition for a circuit board prepared using the dispersion 17, sedimentation and separation of particles were observed when stored for a long period of time.

[Table 7]

(Examples 14-16, Comparative Examples 7-8: Preparation of coverlay film)

On one entire surface of a polyimide film (thickness: 25 μm), the adhesive compositions IV obtained in Examples 11 to 13 and Comparative Examples 5 to 6 were applied uniformly using a coater so that the thickness after drying was about 25 μm. After coating to a thickness and drying at about 120° C. for about 10 minutes, a release coated release paper having a thickness of 125 μm was laminated to prepare a coverlay film.

(Examples 17 to 19, Comparative Examples 9 to 10: Preparation of prepregs)

A NE glass cloth having a thickness of about 100 μm was impregnated with the adhesive compositions I to V obtained in Examples 11 to 13 and Comparative Examples 5 to 6, and then dried at about 120 ° C. for about 10 minutes to obtain a total thickness of about 125 μm. A thermosetting prepreg was prepared.

(Examples 20-22, Comparative Examples 11-12: Manufacture of laminated board for circuit board)

On one entire surface of a polyimide film (thickness: 25 μm), the adhesive composition obtained in Examples 11 to 13 and Comparative Examples 5 to 6 was applied to a uniform thickness using a coater so that the thickness after drying was about 10 μm. After coating to form an adhesive resin layer, it was dried to a semi-cured state. Then, the same adhesive resin layer was formed on the opposite side of the polyimide film to prepare an adhesive sheet.

Subsequently, copper foil (thickness: about 12 μm, mat surface roughness (Rz): 1.6 μm) is laminated on both sides of the adhesive sheet, and then compressed at 170 ° C. at a pressure of 40 kgf / cm ² , 5 at 170 ° C. After curing for a period of time, a laminate for a circuit board was prepared.

(Preparation of evaluation sample of coverlay film)

After laminating the coverlays of Examples 14 to 16 and Comparative Examples 7 to 8 in the order of polyimide film of the coverlay / adhesive surface of the coverlay / copper foil (12 μm), this is 180 ° C., 40 kgf / cm ² It hot-pressed for 60 minutes at the pressure of, and produced the evaluation sample.

(Production of prepreg evaluation sample)

After laminating the prepregs of Examples 17 to 19 and Comparative Examples 9 to 10 in the order of polyimide film (12.5 μm) / prepreg / polyimide (12.5 μm), this was 180 ° C., 40 kgf / cm ² of It hot-pressed for 60 minutes by pressure, and produced the evaluation sample.

(Production of Evaluation Samples for Laminates for Circuit Boards)

Laminates for circuit boards of Examples 20 to 22 and Comparative Examples 11 to 12 were used as evaluation samples.

(physical property evaluation)

The following physical property evaluation was performed using the evaluation samples of Examples 14 to 22 and Comparative Examples 7 to 12 obtained above.

(Evaluation method of electrical characteristics)

Relative permittivity and dielectric loss tangent were measured at 1 MHz using an impedance analyzer according to the test standard of JIS C6481-1996.

(Evaluation method of heat resistance)

A sample having a size of 50 mm × 50 mm was prepared, subjected to moisture absorption treatment at 120° C. and 0.22 MPa for 12 hours, and then floated in a solder bath at 260° C. for 1 minute, and the state of the sample was visually observed.

Evaluation standard:

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

B: Abnormalities such as peeling, deformation, and swelling

(Evaluation method of adhesive strength)

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

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

[Table 8]

[Table 9]

[Table 10]

As shown in Tables 8 to 10, since the adhesive compositions I to V in Examples 14 to 22 have a low dielectric constant and a low dielectric loss tangent, the coverlay film, prepreg, and laminate for circuit board prepared using the same are compared Compared to Examples 7 to 12, it was confirmed that heat resistance and adhesive strength were equivalent, but exhibited more improved electrical properties.

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

In the formulation shown in Table 11 below (calcium carbonate fine particles and silicon oxide fine particles as various PTFE micropowder fine particle ceramics, fluorine-containing and lipophilic group-containing oligomers as fluorine-based additives, methyl ethyl ketone and dimethylformamide as non-aqueous dispersion media) A non-aqueous dispersion of PTFE was prepared by In production, after sufficiently stirring and dissolving the fluorine-based additive in a non-aqueous solvent, PTFE and fine particle ceramics (only PTFE in the comparative example) were added, and further stirring and mixing were performed.

The mixed solution of PTFE obtained as described above was dispersed with 0.3 mm diameter zirconia beads using a horizontal bead mill to obtain non-aqueous PTFE dispersions of Examples 23 to 27 and Comparative Examples 13 to 14. . In addition, as a result of measuring the moisture content of each non-aqueous dispersion of Examples 23 to 27 and Comparative Examples 13 to 14 by the Karl Fischer method, it was confirmed that it was 20,000 ppm or less.

[Evaluation of dispersion]

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

[Evaluation method of sediment]

The presence or absence of sediment in the non-aqueous PTFE dispersion after storage was visually evaluated for sensory evaluation.

Evaluation standard:

A: no sediment

B: There is a little sediment

C: there is a lot of sediment

[Evaluation method of redispersibility]

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

Evaluation standard:

A: easily redispersed

B: redistribution

C: Some agitation is required for redispersion

D: Sufficient agitation is required to redisperse

In addition, as an evaluation of the dispersion, evaluation of the liquid permeability of the filter was performed.

As an evaluation method, for Examples 23 to 25 and Comparative Example 13, when a pressure of 100 kPa was applied to a φ25 mm membrane filter (pore diameter of 5 μm) for 1 minute, the flow weight of the non-aqueous PTFE dispersion was measured. In Examples 26 and 27 and Comparative Example 14, the weight of the non-aqueous PTFE dispersion was measured when a pressure of 100 kPa was applied to a φ13 mm membrane filter (pore diameter of 5 μm) and pressurized for 1 minute. These results are shown in Table 12 below.

[Table 11]

*8: Primary particle diameter

*2: Mecapac F-563 (DIC), fluorine-containing/lipophilic group-containing oligomer, active ingredient 100 wt%

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

*10: Average particle diameter in a dispersed state

[Table 12]

As is clear from Table 11 above, it was confirmed that Examples 23 to 27 in the range of the present invention had an average particle diameter of about 300 nm or less and were finely dispersed.

Looking at each Example and Comparative Example individually, although the viscosity of Examples 23 to 25 was higher than that of Comparative Example 13, they became highly stable dispersions. Further, in Examples 24 and 25, dispersions with good stability and filter permeability were obtained despite the reduction in the amount of the fluorine-based additive. Further, Examples 26 and 27 were dispersions having substantially the same viscosity as Comparative Example 14 and high stability.

Subsequently, as is clear from Table 12 above, it was confirmed that the filter passing weight of Examples 23 to 25 was larger than that of Comparative Example 13, and the fluidity was good, making the filter difficult to clog. In addition, it was confirmed that Examples 26 and 27 also had an increased weight of filter passing through compared to Comparative Example 14, improved fluidity, and less clogging of the filter.

Taking all of these into consideration, the non-aqueous PTFE dispersion of the present invention has low viscosity and excellent storage stability in terms of particle diameter, excellent redispersibility and good fluidity even after long-term storage, so there is no clogging of the filter, and various resins. It has been found that even when added to materials, rubbers, adhesives, lubricants, greases, printing inks, paints, etc., they can be mixed uniformly.

Polyimide with excellent heat resistance, mechanical properties, sliding properties, insulation properties, electrical properties such as low dielectric constant and low dielectric constant, processability, dimensional stability, and flame retardancy, polyimide film, and circuit boards using the polyimide or polyimide film , laminated board for circuit board, adhesive composition for circuit board, coverlay film, prepreg, insulating film, correlative insulating film for wiring board, surface protection layer, sliding layer, peeling layer, fiber, filter material, wire covering material, bearing, resist material and It is suitably used for various belts, tapes, tubes, etc., such as resin materials, paints, printing inks, additives thereof, heat insulation shafts, trays, and seamless belts.

10 insulating film
20 layer of adhesive composition for circuit board
30 metal foil

Claims (36)

A micropowder of a fluorine-based resin and a fluorine-based additive containing a fluorine-containing group and a lipophilic group, wherein the micropowder of the fluorine-based resin in the dispersion has an average particle diameter of 1 µm or less by laser diffraction/scattering method or dynamic light scattering method; , A non-aqueous dispersion of a fluorine-based resin, characterized in that the moisture content is 5,000 ppm or less according to the Karl Fischer method. Laser diffraction/scattering method or dynamic light scattering method of micropowder of polytetrafluoroethylene as a fluorine-based resin, ceramic particles, and a fluorine-based additive containing a fluorine-containing group and a lipophilic group, in a dispersion. The average particle diameter by is 1 μm or less,
A non-aqueous dispersion of a fluorine-based resin characterized by having a water content of 20,000 ppm or less according to the Karl Fischer method. The method of claim 1,
The micropowder of the fluorine-based resin is polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoro A non-aqueous dispersion of a fluorine-based resin, characterized in that it is a micropowder of at least one fluorine-based resin selected from the group consisting of a ethylene copolymer and polychlorotrifluoroethylene. According to claim 1 or claim 2,
The solvent used in the non-aqueous dispersion is γ-butyrolactone, acetone, methyl ethyl ketone, hexane, heptane, octane, 2-heptanone, cycloheptanone, cyclohexanone, cyclohexane, methylcyclohexane, ethylcyclo Hexane, methyl-n-pentyl ketone, methyl isobutyl ketone, methyl isopentyl 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-ethoxy ethylpropionate, dioxane, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, anisole, ethyl Benzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, benzene, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, 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, mineral spirits, 2-hydroxyethyl acrylate, tetra Hydrofurfuryl 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, acetanilide, dioxolane, o-cresol, m-cresol, p-cresol, phenol, N-methyl-2-pyrrolidone, N-acetyl-2-p Rolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, 1,3-dimethyl-2-imidazolidinone, One solvent selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, γ-butyrolactone, sulfolane, halogenated phenols, and various silicone oils, or containing two or more of these solvents A non-aqueous dispersion of a fluorine-based resin, characterized in that: A polyimide precursor solution composition containing a fluorine-based resin, characterized by comprising a polyimide precursor solution in the non-aqueous dispersion of the fluorine-based resin of claim 1 or 2. A polyimide characterized in that it is obtained by using the fluorine-based resin-containing polyimide precursor solution composition of claim 5. A polyimide film obtained by using the fluorine-based resin-containing polyimide precursor solution composition of claim 5. A step of producing the non-aqueous dispersion of the fluorine-based resin of claim 1 or claim 2;
A step of preparing a polyimide precursor solution composition containing a fluorine-based resin by mixing the non-aqueous dispersion of the fluorine-based resin and a polyimide precursor solution;
A method for producing a polyimide, comprising a step of imidizing the polyimide precursor in the polyimide precursor solution composition to obtain a polyimide in which a fluorine-based resin is dispersed. A method for producing a polyimide film, comprising the step of obtaining the polyimide of claim 8 and further comprising the step of obtaining a polyimide film. A circuit board characterized by using the polyimide film obtained by the manufacturing method of claim 9. A coverlay film characterized by using the polyimide film obtained by the manufacturing method of claim 9. An adhesive composition for a circuit board comprising a resin composition comprising a cyanate ester resin or an epoxy resin in the non-aqueous dispersion of the fluorine-based resin of claim 1 or claim 2. A circuit board laminate comprising at least a configuration of an insulating film, a metal foil, and an adhesive layer interposed between the insulating film and the metal foil, wherein the adhesive layer is the adhesive composition for a circuit board of claim 12, Laminate for substrate. The method of claim 13,
The insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether ( Modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, polyether ether ketone (PEEK) characterized in that at least one film selected from the group consisting of, a laminate for circuit board. A coverlay film comprising an insulating film and an adhesive layer formed on at least one side of the insulating film, wherein the adhesive layer is the adhesive composition for a circuit board of claim 12. The method of claim 15
The insulating film is polyimide (PI), liquid crystal polymer (LCP), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS), polyetherimide (PEI), polyphenylene ether ( A coverlay film, characterized in that it is at least one film selected from the group consisting of modified PPE), polyester, para-aramid, polylactic acid, nylon, polyparabanic acid, and polyetheretherketone (PEEK). Prepreg, characterized in that the adhesive composition for a circuit board of claim 12 is impregnated into a structure formed of at least one type of fiber selected from the group consisting of carbon-based fibers, cellulose-based fiberglass-based fibers, and aramid-based fibers . A polyimide precursor solution composition containing a fluorine-based resin, comprising a micropowder of a fluorine-based resin, a compound represented by the following formula (I), and a polyimide precursor solution.
The method of claim 18
A polyimide precursor solution composition containing a fluorine-based resin, characterized in that the polyimide precursor solution contains tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound. The method of claim 19
A polyimide precursor solution composition containing a fluorine-based resin, characterized in that it contains a non-aqueous solvent. The method of claim 20
A polyimide precursor solution composition containing a fluorine-based resin, characterized in that the polyimide precursor solution contains tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound. The method of claim 18
The micropowder of the fluorine-based resin is polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy polymer, chlorotrifluoroethylene, tetrafluoroethylene-chlorotrifluoroethylene copolymer, ethylene-chlorotrifluoro A polyimide precursor solution composition containing a fluorine-based resin, characterized in that it is a micropowder of at least one fluorine-based resin selected from the group consisting of a ethylene copolymer and polychlorotrifluoroethylene. The method of claim 18
A polyimide precursor solution composition containing a fluorine-based resin, characterized in that in the micro-powder dispersion of the fluorine-based resin, the average particle diameter of the micro-powder of the fluorine-based resin in a dispersed state is 10 μm or less. A fluorine-based resin-containing polyimide obtained by using the fluorine-based resin-containing polyimide precursor solution composition of claim 18. A polyimide film containing a fluorine-based resin, characterized in that it is obtained by using the fluorine-based resin-containing polyimide precursor solution composition of claim 18. A polyimide insulating material containing a fluorine-based resin, characterized in that it is obtained by using the fluorine-based resin-containing polyimide precursor solution composition of claim 18. A step of preparing a micropowder dispersion of a fluorine-based resin containing a micropowder of a fluorine-based resin, a compound represented by the following formula (I), and a non-aqueous solvent;
A step of preparing a polyimide precursor solution composition by mixing tetracarboxylic dihydrate and/or a derivative thereof and a diamine compound;
A step of preparing a polyimide precursor solution composition containing a fluorine-based resin by mixing the micro-powder dispersion of the fluorine-based resin and the polyimide precursor solution composition;
A step of obtaining a fluorine-based resin-containing polyimide by curing the fluorine-based resin-containing polyimide precursor solution composition
A method for producing a polyimide containing a fluorine-based resin, comprising:
A method for producing a fluorine-based resin-containing polyimide film, comprising the step of obtaining the fluorine-based resin-containing polyimide according to claim 27 and further comprising a step of obtaining the fluorine-based resin-containing polyimide film. A method for producing a fluorine-based resin-containing polyimide insulating film, comprising the step of obtaining the fluorine-based resin-containing polyimide of claim 27 and further comprising a step of obtaining a fluorine-based resin-containing polyimide insulating film. A circuit board characterized by using the fluorine-based resin-containing polyimide film of claim 25. A coverlay film characterized by using the fluorine-based resin-containing polyimide film of claim 25. An electronic device characterized by using the fluorine-based resin-containing polyimide insulating material of claim 26. delete The method of claim 2,
The non-aqueous dispersion, characterized in that the ceramic particles contain one of B, Na, Mg, Al, Si, P, K, Ca, and Ti. According to claim 2 or claim 34,
The ceramic particles are Al ₂ O ₃ , SiO _{2 ,} CaCO ₃ , ZrO ₂ , SiC, A non-aqueous dispersion characterized by being composed of an inorganic compound of one of Si ₃ N ₄ and ZnO. The method of claim 2,
A non-aqueous dispersion characterized in that the ceramic particles are surface-treated.