JP5765448B2 - Fluoropolymer non-aqueous dispersion - Google Patents

Description

The present invention relates to a fluoropolymer non-aqueous dispersion.

Fluoropolymers are used in many applications in terms of non-adhesiveness, heat resistance, low friction, unique electrical characteristics, and charging characteristics. However, dispersibility in organic solvents and other resins is poor. Improvement is desired. As a means for improving the dispersibility, a dispersion liquid uniformly dispersed in an organic solvent or the like in advance is desired.

A composition (organosol) in which a fluoropolymer is dispersed in an organic solvent obtained by solvent substitution from an aqueous dispersion of a fluoropolymer polymerized in an aqueous medium is known (for example, Patent Document 1). And 2). However, in these compositions, compositions having a high polymer concentration are not known. Furthermore, when the polymer solid content is high, there are problems such as high viscosity and insufficient stability.

In order to solve this problem, it has been proposed to add a dispersibility improver. As a dispersion improver, for example, Patent Document 3 discloses a silicon resin-based dispersibility improver. However, a high concentration non-aqueous dispersion of fluoropolymer is not substantially disclosed, and it is necessary to add a dispersibility improver of about 10% to the fluoropolymer.

Patent Document 4 discloses a surface protective layer in which fluororesin fine particles are dispersed (this is a coating obtained by irradiating ultrasonic waves after dispersing fluororesin fine particles having a volume average particle size of 10 [μm] or less. An image bearing member having (obtained by applying a liquid) is disclosed. Furthermore, a non-aqueous dispersion of PFA using a fluorine-based block polymer as a dispersibility improver is described. However, the solid content concentration was about 18%, and it was necessary to add 9% of the addition amount of the fluorine-based block polymer to the polymer.

Patent Document 5 discloses a charge transport coating for an electrophotographic photoreceptor, and fluorine-containing polyorganosiloxane is used as a dispersibility improver. However, the content of PTFE in the paint was about 18%, and the dispersibility improver was required to be 20% based on the resin.

Patent Document 6 discloses a fluorine-based comb-type graft polymer as a dispersibility improver, but the solid content concentration of the fluororesin is about 1%, and the dispersibility improver needs to be added by 250%. there were.

Patent Document 7 describes that a fluorosurfactant is effective in improving the dispersibility of PTFE, and specifically comprises a fluorinated alkyl group-containing polymer segment and an acrylic polymer-containing segment. The use of block copolymers as dispersibility improvers is disclosed. However, the solid content concentration of PTFE was 3% or less, and the addition amount was also required 10% with respect to PTFE.

In Patent Document 8, PTFE particles treated with polyorganosiloxane are dispersed in an organic solvent. However, the obtained solid content concentration is low, and a dispersibility improver is required to be 10% of PTFE.

Patent Document 9 discloses reverse micelles in a non-aqueous medium using a block polymer having a vinyl ether unit as a dispersant. However, there is no description that PTFE particles can be stably dispersed as a functional substance, and there is no description that suggests that.

Patent Document 10 also attempts to use a material that improves the dispersibility of the fluororesin particles in the photosensitive layer.

JP 60-104164 A Japanese Patent Publication No. 47-31096 JP 2000-080232 A JP 2009-300751 A JP 2008-224851 A JP 2008-46197 A JP 2005-181396 A JP 2005-156653 A JP 2004-35735 A JP 2000-81715 A

Conventionally, when a fluoropolymer is dispersed in an organic solvent at a high concentration, a precipitate that cannot be easily phase-separated or redispersed is generated. Even when a stable dispersion state is realized, it is necessary to keep the polymer concentration low and to add a large amount of a dispersibility improver. On the other hand, the present invention provides a fluoropolymer non-aqueous dispersion which has high dispersibility and storage stability and can be easily redispersed even if part of the fluoropolymer settles during storage.

The present invention is a fluoropolymer non-aqueous dispersion characterized by containing a fluoropolymer, a non-aqueous medium, and a dispersion stabilizer.

The dispersion stabilizer is
(1) General _{^{formula: Rf 1 - (X) n}} -Y
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, n is 0 or 1, and 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 1 R is an integer of 0 to 12, and R ¹ and R ² are alkylene groups having ² to 4 carbon atoms, provided that R ¹ and R ² are different from each other. A compound represented by
(2) General formula: H (OR ⁶ ) _u (OR ⁷ ) _v OH
(Wherein R ⁶ and R ⁷ are alkylene groups having 1 to 4 carbon atoms, and u and v are integers of 1 to 5, provided that R ⁶ and R ⁷ are different from each other.) (3) a nonionic polymer having a hydrophobic group consisting of a hydrocarbon group having 8 to 20 carbon atoms and a hydrophilic group consisting of a polyalkylene oxide in the molecule, and
(4) General ^{_{formula: R 3 m -Si- (OR 4}} ) 4-m
(Wherein R ³ is an alkyl group having 1 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3). Silicon compounds,
It is preferably at least one selected from the group consisting of

Compound (1) is
The general ^{_{formula: Rf 1 - (CH 2)}} s OH
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, and s is an integer of 1 to 12, and
General _{^{formula: Rf 1 -O- (R 5 O}} ) t H
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, R ⁵ is an alkylene group having 2 to 4 carbon atoms, and t is 1 A compound represented by the following formula:
It is preferably at least one selected from the group consisting of

Nonionic polymer (3)
General formula: R ⁸ O (CH ₂ CH ₂ O) _w H
In the formula, R ⁸ is an alkyl group having 10 to 15 carbon atoms, and w represents an average addition mole number and is an integer of 1 to 15.

The dispersion stabilizer is preferably a block polymer (2).

The content of the dispersion stabilizer is preferably 0.01 to 50% by mass.

The non-aqueous medium is preferably an organic solvent having a boiling point of 40 to 250 ° C.

The fluoropolymer content is preferably 1 to 60% by mass.

It is preferable that the water content is 1% or less.

The fluoropolymer non-aqueous dispersion of the present invention has high dispersibility and storage stability. Moreover, even if a part of the fluoropolymer settles during storage, the precipitate can be easily redispersed.

The fluoropolymer non-aqueous dispersion of the present invention is characterized by containing a fluoropolymer, a non-aqueous medium, and a dispersion stabilizer.

<Dispersion stabilizer>
The dispersion stabilizer may have a segment having an affinity for a non-aqueous medium and a segment having an affinity for a fluoropolymer. The dispersion stabilizer contained in the fluoropolymer non-aqueous dispersion of the present invention is presumed to have two or more segments having affinity for each of the non-aqueous medium and the fluoropolymer, thereby dispersibility and storage stability. It is presumed that a non-aqueous dispersion having excellent properties and redispersibility can be obtained.

The dispersion stabilizer is
(1) General _{^{formula: Rf 1 - (X) n}} -Y
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, n is 0 or 1, and 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 1 R is an integer of -12, r is an integer of 0 to 12, and R ¹ and R ² are alkylene groups having ² to 4 carbon atoms, provided that R ¹ and R ² are different from each other. ) A compound represented by
(2) General formula: H (OR ⁶ ) _u (OR ⁷ ) _v OH
(Wherein R ⁶ and R ⁷ are alkylene groups having 1 to 4 carbon atoms, and u and v are integers of 1 to 5, provided that R ⁶ and R ⁷ are different from each other.) A block polymer represented by
(3) a nonionic polymer having a hydrophobic group composed of a hydrocarbon group having 8 to 20 carbon atoms and a hydrophilic group composed of a polyalkylene oxide in the molecule; and
(4) General ^{_{formula: R 3 m -Si- (OR 4}} ) 4-m
(Wherein R ³ is an alkyl group having 1 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3). Silicon compounds,
It is preferably at least one selected from the group consisting of

Compound (1) is
The general ^{_{formula: Rf 1 - (CH 2)}} s OH
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, and s is an integer of 1 to 12, and
General _{^{formula: Rf 1 -O- (R 5 O}} ) t H
Wherein Rf ¹ is a partially fluorinated alkyl group or a fully fluorinated alkyl group having ¹ to 12 carbon atoms, R ⁵ is an alkylene group having 2 to 4 carbon atoms, and t is 1 It is more preferable that it is at least one selected from the group consisting of compounds represented by:

Rf ¹ is preferably an alkyl group having 3 to 6 carbon atoms. If the number of carbon atoms is smaller than 3, the dispersibility of the fluoropolymer may not be sufficient, and it is preferably 6 or less from the environmental viewpoint. Rf ¹ is preferably a fully fluorinated alkyl group.

As the compound (1), an ester obtained from Rf ¹ COOH and a hydrocarbon alcohol, an ester obtained from Rf ¹ CH ₂ OH and a hydrocarbon carboxylic acid, or an ester obtained from Rf ¹ CH ₂ OH and a hydrocarbon alcohol Ether and the like are preferably exemplified. Further, in a manner known to the Rf 1 ^CH 2 _OH, compounds obtained by adding an alkylene oxide are also preferably exemplified. More _{^{specifically, Rf 1 - (CH 2)}} x -OH, Rf 1 -COO- (CH 2) x -OH, Rf 1 -O- (CH 2) x -CH 3, Rf 1 -O- ( RO) _x H and the like (x is an integer of 1 to 12, and R represents an alkylene group having 2 to 4 carbon atoms).

Block polymer (2)
General formula: H (OR ⁶ ) _u (OR ⁷ ) _v OH
(Wherein R ⁶ and R ⁷ are alkylene groups having 1 to 4 carbon atoms, and u and v are integers of 1 to 5, provided that R ⁶ and R ⁷ are different from each other.) It is preferable that it is a block polymer represented by these.

Specific examples of the block polymer that can be used in the present invention include a block polymer composed of at least two types of segments selected from the group of polyoxyethylene, polyoxypropylene, and polyoxybutylene. Among them, polyoxyethylene-polyoxypropylene block polymers and polyoxyethylene-polyoxybutylene block polymers are exemplified, and not only AB type but also ABA type block polymers are preferably exemplified. More preferably, by using a polyoxyethylene-polyoxypropylene block polymer, a highly stable dispersion of a fluoropolymer can be prepared. Furthermore, it is preferable that the content of the polyoxyethylene segment is 10 to 50% because there is little generation of aggregates that may be caused by reaggregation, and when the content is 20 to 40%, the dispersion of the low-viscosity fluoropolymer is preferable. Since a liquid can be prepared, it is preferable. The molecular weight is not particularly limited, but if the molecular weight is 1000 to 7000 g / mol, the dispersion of the present invention can be prepared. In particular, when the molecular weight is 2500 to 6500 g / mol, a dispersion having a low viscosity and excellent dispersibility is prepared. be able to.

The nonionic polymer (3) is a nonionic polymer having in its molecule a hydrophobic group comprising a hydrocarbon group having 8 to 20 carbon atoms and a hydrophilic group comprising a polyalkylene oxide. Further, the hydrophilic group is preferably polyoxyethylene, and can optionally contain an alkylene oxide unit having a higher carbon number within the scope of the object of the present invention. The nonionic polymer (3) is preferably a nonfluorinated nonionic polymer. Either an ester type or an ether type can be used, but the ether type is preferred from the viewpoint of chemical stability. Further, the hydrophobic group preferably has 10 to 20 carbons from the viewpoint of dispersibility, and more preferably has a branched structure from the viewpoint of stability. Furthermore, since a low-viscosity dispersion liquid is obtained, those having an HLB of 10 or less are preferable.

In particular, the nonionic polymer (3)
General formula: R ⁸ O (CH ₂ CH ₂ O) _w H
(Wherein R ⁸ is an alkyl group having 10 to 15 carbon atoms, w represents the average number of added moles, and is an integer of 1 to 15 and is an average value), and C More preferably, it is ₁₃ H ₂₇ O (CH ₂ CH ₂ O) _w H. A more preferable range of w is 10 or less because dispersibility is particularly good, and more preferably 7 or less from the viewpoint of viscosity, storage stability, and redispersibility of the dispersion.

The silicon compound (4) is represented by the general formula: R ³ _m -Si- (OR ⁴ ) _4-m
(Wherein R ³ is an alkyl group having 1 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3). In particular, R ³ is preferably an alkyl group having 3 to 8 carbon atoms, and m is preferably 1 to 2. R ⁴ is preferably a methyl group or an ethyl group.

The dispersion stabilizer is preferably a block polymer (2) because it is particularly excellent in dispersibility, storage stability, and redispersibility.

In the fluoropolymer non-aqueous dispersion, the content of the dispersion stabilizer is preferably 0.01 to 50% by mass, more preferably 0.05 to 10% by mass, and even 5% by mass or less. Sufficient dispersibility can be obtained.

Further, a fluorinated anionic surfactant may be added as a dispersant for promoting the dispersion of the fluoropolymer. By adding a fluorinated anionic surfactant, reaggregation of the fluoropolymer can be suppressed. As such a fluorinated anionic surfactant, a compound having a fluorine-substituted alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a carboxylic acid, or a sulfonic acid, or a salt thereof in the molecule. Preferably, fluorinated carboxylic acids can be used. From the environmental aspect, compounds having 4 to 6 carbon atoms are preferred. Specific examples include perfluorooctanoic acid, perfluoroheptanoic acid, perfluorohexanoic acid and salts thereof.

<Fluoropolymer>
The fluoropolymer is preferably a fluoropolymer that does not dissolve in a non-aqueous medium, such as polytetrafluoroethylene [PTFE], tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer. And at least one polymer selected from the group consisting of polychlorotrifluoroethylene, polyvinylidene fluoride, ethylene / tetrafluoroethylene copolymer, and ethylene / chlorotetrafluoroethylene copolymer. Further, among these, perflopolymer is more preferable because it is difficult to dissolve in a non-aqueous medium. Polytetrafluoroethylene [PTFE], tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer Coalescence is exemplified. Among these, PTFE is still more preferable. The PTFE may be a TFE homopolymer, a slightly modified PTFE, or a PTFE having a core / shell structure. In the case of PTFE, since there is no solvent solubility, it is difficult to measure the molecular weight by GPC or the like. Usually, SSG (standard specific gravity) as described in ASTM D4895-89 is used as an index of molecular weight. In the PTFE of the present invention, PTFE having an SSG of 2.13 to 2.20 is preferably used.

Moreover, as PTFE, it is also preferable that it is low molecular weight PTFE whose melt viscosity in 380 degreeC is 700,000 Pa.s or less. The melt viscosity is in accordance with ASTM D 1238, and a 2 g sample heated at 380 ° C. for 5 minutes in advance using a flow tester (manufactured by Shimadzu Corporation) and a 2φ-8L die at a load of 0.7 MPa. And measured at the above temperature.

Further, PTFE subjected to special treatment can also be preferably used. Product: KTL-610, KTL-450, KTL-350, KTL-8N, KTL-400H, etc. can be exemplified.

Regarding the dispersed particle size of the fluoropolymer in the non-aqueous medium, for example, when a powdered fluoropolymer is dispersed, by dispersing it in a size of 5 to 500 μm, it is possible to obtain a dispersion liquid that hardly reaggregates. For example, when an aqueous dispersion obtained by polymerization in an aqueous medium is phase-converted, it is dispersed in a size of 0.05 to 5 μm from other materials. In the case of compounding, it is convenient because uniform mixing is possible, and it is preferable from the viewpoint of sedimentation stability of the dispersion that it is dispersed in a size of 0.1 to 0.5 μm.

<Non-aqueous medium>
The dispersion of the present invention is a non-aqueous dispersion. Examples of non-aqueous media that can be used include organic solvents and polymers.

Specific examples of the organic solvent include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-dimethylformamide, acetone, acetonitrile, methyl ethyl ketone, methyl isopropyl ketone, and methyl. Isobutyl ketone, methyl-normal-butyl ketone, cyclohexanone, methylcyclohexanone, methylcyclohexanol, benzene, o-dichlorobenzene, toluene, styrene, xylene, cresol, chlorobenzene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2 -Dichloroethylene, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-trichloroethane, trichloro Tylene, tetrachloromethane, tetrachloroethylene, tetrachloroethane, tetrahydrofuran, dioxolane, dioxane, methanol, ethanol, butanol, isobutyl alcohol, 1-propanol, isopropanol, isopentyl alcohol, cyclohexanol, cyclohexanone, 1,4-dioxane, dichloromethane , N, N-dimethylformamide, normal hexane, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, normal-pentyl acetate, isopentyl acetate, dimethyl sulfoxide, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Ethylene glycol monoethyl ether acetate, ethylene glycol mono-normal Ether, carbon disulfide, gasoline, coal tar naphtha, petroleum ether, petroleum benzine, turpentine, mineral spirits and the like. Natural oils such as olive oil, soybean oil, beef tallow, and pork fat can also be used. Silicon oil, fluorine-based oil, and fluorine-based alcohol can also be used.

As the non-aqueous medium, a solvent containing a fluorine atom in the molecule can be preferably used. For example, a fluorine-based solvent such as propanol pentafluoride may be used, but a solvent that does not dissolve the fluoropolymer is preferable.

As said organic solvent, it is preferable that a boiling point is 40-250 degreeC, a more preferable minimum is 50 degreeC and a more preferable upper limit is 200 degreeC. If the boiling point is too low, volatilization may occur during the work and control of the composition change may be difficult, and safety measures such as ignition by steam are required. If it is too high, it takes time for drying, and there is a concern about the influence of heat on the dispersion during drying.

The above organic solvents can be used alone or as a mixed solvent of two or more.

<Content of fluoropolymer>
The fluoropolymer non-aqueous dispersion of the present invention preferably has a fluoropolymer content of 1 to 60% by mass, for example, sufficient dispersion even at a high concentration of 5, more preferably 10, 20% by mass or more. Showing gender.

<Moisture content>
It is preferable that the water content is 1% or less, preferably 0.1% or even 0.01% or less.

For example, when the dispersion of the present invention is mixed with a component that dislikes moisture, such as an electrode active material, control of the amount of moisture is important. The amount of water can be quantified by Karl Fischer.

The moisture content can be controlled by the method described in Japanese Patent Publication No. 48-17548. That is, it can be obtained by adding an organic solvent capable of forming an azeotropic state with water and then azeotropically removing the azeotropic mixture of water and the organic solvent.

Organic solvents that can form an azeotropic state with water include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, propylbenzene, and cumene; methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone Examples thereof include ketone solvents such as methyl isobutyl ketone; ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate. After azeotropic removal, the concentration may be adjusted with the same or different organic solvent as the solvent used for azeotropic removal.

<Method for preparing dispersion>
There is a method of dispersing a fluoropolymer powder in an organic solvent in the presence of a dispersion stabilizer. It is preferable to prepare an organic solvent in which a dispersion stabilizer is dissolved or dispersed in advance and disperse the powdery fluoropolymer therein. Also preferred is a method in which a dispersant and a powdery fluoropolymer are mixed and dispersed in advance (if necessary, in the presence of a dispersion auxiliary medium) and then dispersed in an organic solvent (after removing the dispersion auxiliary medium if necessary).

Moreover, the method of adding a dispersion stabilizer to the organosol obtained by phase inversion from an aqueous dispersion according to a conventional method is also included. A dispersion stabilizer can be added to the aqueous dispersion in advance, and it is also preferable to add it after phase inversion. Further, it is also preferable to add an aqueous dispersion to an organic solvent in which a dispersion stabilizer is dissolved (dispersed) in advance to perform phase inversion.

Another example is a method in which a fluoropolymer powder is dispersed in an organic solvent in the presence of a dispersion stabilizer by a high-speed liquid collision dispersion device. The high-speed liquid collision dispersion device is a general term for a device having a function of dispersing and emulsifying fine particles contained by generating a high-speed flow by an arbitrary method and causing liquids or liquids to collide with a vessel wall. Fluoropolymer powder is considered to be dispersed and emulsified by the effects of shearing force generated by high pressure and high flow velocity, cavitation, high frequency, and ultrasonic waves. Examples of the high-speed liquid collision dispersion device include a high-pressure homogenizer, a microfluidizer, a nanomizer, and an optimizer.

It is also suitable to disperse the dispersion media in combination with the fluoropolymer powder. Examples of the material of the dispersion medium include zirconia balls. The diameter of the dispersion medium is preferably φ0.3 to 10 [mm]. When a dispersion medium having a diameter of less than 0.3 mm is used, it takes time to separate the dispersion medium after dispersion. When a dispersion medium exceeding φ10 [mm] is used, the dispersion force is reduced and fine dispersion may not be performed.

You may irradiate an ultrasonic wave to the obtained dispersion liquid. The frequency of the irradiated ultrasonic wave is preferably 10 to 100 [kHz]. When the frequency is lower than 10 [kHz], the cavitation strength is weakened, the dispersion ability of the fluoropolymer is lowered, and the ultrasonic effect may not be sufficiently obtained. On the other hand, when the frequency is higher than 100 [kHz], the aggregation effect is strongly expressed, and thus the fluoropolymer dispersion effect may not be sufficiently obtained.

<Additives>
The dispersion of the present invention comprises a leveling agent, solid lubricant, wood powder, quartz sand, carbon black, diamond, tourmaline, germanium, alumina, silicon nitride, fluorite, clay, talc, extender pigments, various extenders, conductivity Filler, glitter material, pigment, filler, pigment dispersant, anti-settling agent, moisture absorbent, surface conditioner, thixotropy imparting agent, viscosity modifier, anti-gelling agent, ultraviolet absorber, light stabilizer, plasticizer , Anti-coloring agent, anti-skinning agent, anti-scratch agent, anti-fungal agent, antibacterial agent, antioxidant, anti-static agent, silane coupling agent, antifoaming agent, desiccant, anti-repellent agent There may be.

<Application>
The non-aqueous dispersion liquid of the present invention is suitably used as a coating material for fixing members used in electrophotographic equipment and the like. The fixing member has at least a base material and a film formed by the fixing member coating material of the present invention. As long as the fixing member has a film formed of at least a base material and a coating material for the fixing member, another layer (for example, an elastic layer provided between the base material and the coating film) is provided as necessary. You may have. Examples of the fixing member include, but are not particularly limited to, a fixing roll, a fixing belt, or a fixing film for an electrophotographic apparatus, a pressing roll, a pressing belt, or a pressing film. For example, it may be a fixing member in general office automation equipment (hereinafter also referred to as “OA equipment”). Examples of the OA equipment include image forming apparatuses such as a printing machine and a copying machine. Examples of the fixing member include a roll for OA equipment, a belt for OA equipment, or a film for OA equipment.
Examples of the roll for OA equipment, the belt for OA equipment or the film for OA equipment include a fixing roll, a fixing belt or a fixing film, a pressing roll, a pressing belt or a pressing film.

The non-aqueous dispersion of the present invention is also suitably used as a material for forming members of image forming apparatuses such as copying machines, printers and facsimile machines. After being dispersed in a binder resin such as an acrylic resin, a polyester resin, a polyurethane resin, or a polycarbonate resin, the film is used as a surface layer or a protective layer of the photoreceptor. For example, it can be suitably used as a photosensitive layer forming coating solution for forming an electrophotographic photoreceptor. The electrophotographic photoreceptor is used for an image forming apparatus provided with the electrophotographic photoreceptor, a process cartridge for the image forming apparatus, and the like.

The non-aqueous dispersion of the present invention is suitably used as a material for forming a photosensitive layer of an electrophotographic photoreceptor. By using the dispersion according to the present invention, a surface layer containing a relatively large amount of fluororesin fine particles can be formed, and a low coefficient of friction can be maintained over a long period of time.

The non-aqueous dispersion liquid of the present invention is suitable as a coating material for imparting water-repellent conductivity to the gas diffusion electrode of the membrane electrode assembly in fuel cell applications.
Moreover, in non-aqueous electrolyte batteries, for example, lithium secondary battery applications, it is suitable for a positive electrode mixture paste of a non-aqueous electrolyte battery comprising a positive electrode active material, a conductive material, a binder, a thickener, and an organic solvent. Used.

The non-aqueous dispersion liquid of the present invention may be used for a coating composition, a grease composition, a cosmetic composition, a plating solution composition, or a toner composition.

The non-aqueous dispersion of the present invention may be used for impregnation comprising impregnating and drying a porous support such as a nonwoven fabric or a resin molded article, and then preferably firing; coating on a substrate such as glass. After drying, it is immersed in water as necessary, and cast film formation consisting of obtaining a thin film by peeling off the substrate, examples of these applications include aqueous dispersion paints, binders for electrodes, Examples thereof include a water repellent for electrodes.

The non-aqueous dispersion of the present invention is also preferably used as a processing aid. When used as a processing aid, mixing the fluoropolymer aqueous dispersion of the present invention with a host polymer, etc. improves the melt strength during the host polymer melt processing, and the mechanical strength, electrical properties, and difficulty of the resulting polymer. It is possible to improve the flammability, the dripping prevention property, and the slidability.

Next, the present invention will be described with reference to experimental examples, but the present invention is not limited to such experimental examples.

Each numerical value of the experimental example was measured by the following method.

(Dispersibility)
When filtration was performed with a 120 mesh SUS wire mesh, mesh up was 5% or less of the initial resin amount, ○, 5 to 10% was over Δ, and x was over.

(viscosity)
A filtration time of less than 1 minute was marked as ◯, 1 to 5 minutes as Δ, and those that could not be filtered in 5 minutes as x.

(Storage stability)
When allowed to stand at room temperature for 5 days, the percentage of the transparent supernatant was 5% or less, over 5%, over 10%, over 10%, and x.

(Redispersibility)
After the storage stability test, the mixture was stirred at 500 rpm for 5 minutes and evaluated in the same manner as the dispersibility.

(Comparative example)
In a 200 ml glass container, 100 g of isopropanol is weighed and stirred at 500 rpm using an overhead explosion-proof stirrer (manufactured by Shinto Kagaku Co., Ltd., Three-One Motor) equipped with a disperser-type stirring blade. 30 g of Lubron L-2 was added and stirred and dispersed for 5 minutes, and then dispersed in a water bath for 30 minutes in an ultrasonic cleaner having an oscillation frequency of 40 kHz and a high frequency output of 600 W.
The evaluation results are shown in Table 1.

(Experimental example 1)
In a 200 ml glass container, 100 g of isopropanol was weighed. To this, 1.5 g of Pluronic PE6100 (EO / PO block polymer, EO content 10%, molecular weight about 2000) manufactured by BASF was added as a dispersion stabilizer, and an overhead explosion-proof stirrer equipped with a disperser-type stirring blade (Shinto Kagaku Co., Ltd., Three-One Motor) was stirred at 500 rpm for 5 minutes to obtain a uniform solution. Further, 30 g of Lubron L-2 manufactured by Daikin Industries, Ltd. was added under stirring, and the mixture was stirred and dispersed for 5 minutes, and then dispersed in a water bath for 30 minutes in an ultrasonic cleaner with an oscillation frequency of 40 kHz and a high frequency output of 600 W. The above “EO” means ethylene oxide, and “PO” means “propylene oxide”.
The evaluation results are shown in Table 1.

(Experimental Examples 2 to 12)
The same operation as in Experimental Example 1 was performed except that the substances shown in Table 1 were used as the dispersion stabilizer. The amount of the dispersion stabilizer added is 1.5 g in all cases. The evaluation results are shown in Table 1.

The fluoropolymer non-aqueous dispersion of the present invention is used for forming a coating material for a fixing member used in an electrophotographic apparatus or the like, or an electrophotographic photosensitive member for forming a member of an image forming apparatus such as a copying machine, a printer, or a facsimile machine. It can be suitably used for various applications such as a coating solution for forming a photosensitive layer.

Claims (6)

Containing a fluoropolymer, a non-aqueous medium, and a dispersion stabilizer,
Dispersion stabilizer,
(3) hydrophobic group carbon atoms consisting of 8-20 hydrocarbon groups and a fluoropolymer nonaqueous dispersion, wherein the hydrophilic group consisting of a polyalkylene oxide nonionic polymer over having in the molecule . Nonionic polymer (3)
General formula: R ⁸ O (CH ₂ CH ₂ O) _w H
(Wherein R ⁸ represents an alkyl group having 10 to 15 carbon atoms, w represents an average number of added moles, and an integer of 1 to 15 is an average value). Item 4. The fluoropolymer non-aqueous dispersion according to Item 1. The fluoropolymer non-aqueous dispersion according to claim 1 or 2, wherein the content of the dispersion stabilizer is 0.01 to 50% by mass. The fluoropolymer non-aqueous dispersion according to claim 1, 2 or 3, wherein the non-aqueous medium is an organic solvent having a boiling point of 40 to 250 ° C. The fluoropolymer non-aqueous dispersion according to claim 1, wherein the content of the fluoropolymer is 1 to 60% by mass. The fluoropolymer non-aqueous dispersion according to claim 1, wherein the water content is 1% or less.