JP2012188514A - Fluorine-containing resin particle dispersion, method for preparing fluorine-containing resin particle dispersion, coating liquid which contains fluorine-containing resin particles, method for preparing coating film which contains fluorine-containing resin particles, coating film which contains fluorine-containing resin particles, and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve dispersion of fluorine-containing resin particles in a solvent in the group of the hydroxyl group-containing solvents.SOLUTION: Provided is a fluorine-containing resin particle dispersion including: fluorine-containing resin particles; a resin which is not dissolved in at least one solvent in a group of hydroxyl group-containing solvents including an alcohol-based solvent having 1 to 10 carbon atoms, containing no aromatic ring in the molecule structure, and a water-based medium, and which is adhered on the surface of the fluorine-containing resin particles; and at least one solvent, in which the resin is not dissolved, in the group of hydroxyl group-containing solvents, in which the fluorine-containing resin particles having the resin adhered on the surface thereof are dispersed.

Description

  The present invention relates to a fluorine-containing resin particle dispersion, a method for producing a fluorine-containing resin particle dispersion, a fluorine-containing resin particle-containing coating solution, a method for producing a fluorine-containing resin particle-containing coating film, a fluorine-containing resin particle-containing coating film, and It relates to a molded body.

  A coating solution in which fluorine-containing resin particles are mixed in a coating solution and the fluorine-containing resin particles are dispersed in a coating material is used. In general, the fluorine-containing resin particles have a small surface energy and are not compatible with any solvent such as water, alcohol, and organic solvent and cannot maintain a stable dispersion state. Therefore, the fluorine-containing resin particles are dispersed using a large amount of a surfactant. In recent years, water or alcohol solvents are often used in order to reduce the environmental load of organic solvents.

As a method for dispersing the fluorine-containing resin particles in these solvents, for example, a method using a nonionic surfactant composed of alkyl and oxyalkylene (see, for example, Patent Document 1), a perfluoroalkyl group, or a perfluoropolyester. A method of dispersing using a nonionic surfactant having an ether group (for example, see Patent Document 2), a method of adding a nonionic surfactant and a nonionic water-soluble polymer (for example, see Patent Document 3), fluorine A method for introducing a functional group into the resin particle itself (for example, see Patent Document 4) is disclosed.
In addition, alcohol dispersions are commercially available (for example, KD-500AS, isopropanol dispersion, Kitamura Co., Ltd.) and electrophotographic photoreceptors in which fluorine-containing resin particles are dispersed (for example, patents). Reference 5).

JP-A-7-233345 Japanese Patent Laid-Open No. 11-130927 JP 2008-13669 A Special table 2007-511657 gazette JP 2005-181396 A

  An object of the present invention is to attach a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium not containing an aromatic ring in the molecular structure to the surface. The object is to improve the dispersibility of the fluorine-containing resin particles in the solvent of the hydroxyl group-containing solvent group as compared with the case where it is not.

The above object is achieved by the present invention described below.
That is, the invention according to claim 1
Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin and
A solvent that disperses the fluorine-containing resin particles having at least one selected from those that do not dissolve the resin in the hydroxyl group-containing solvent group;
Is a fluorine-containing resin particle dispersion.

The invention according to claim 2
The fluororesin particle dispersion according to claim 1, wherein the resin is adsorbed on the surface of the fluororesin particles.

The invention according to claim 3
The fluorine-containing resin particle dispersion according to claim 1 or 2, wherein the hydroxyl group-containing solvent group comprises an aliphatic alcohol and a fluorine-containing alcohol.

The invention according to claim 4
A resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. A dissolution step of dissolving in a solvent;
An adsorption step of contacting the resin with the fluorine-containing resin particles to adsorb the resin on the surface of the fluorine-containing resin particles;
A separation step of separating the fluorine-containing resin particles having the resin adsorbed on the surface thereof from the other solvent;
Dispersing the separated fluorine-containing resin particles in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group;
It is a manufacturing method of the fluorine-containing resin particle dispersion which has this.

The invention according to claim 5
Reactive monomer that is a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure Dissolving step in another solvent capable of dissolving the resin,
An adsorption step of bringing the fluorine-containing resin particles into contact with the monomer and adsorbing the monomer on the surface of the fluorine-containing resin particles;
A polymerization step of polymerizing the monomer to form a resin on the surface of the fluorine-containing resin particles;
A separation step of separating the fluororesin particles having the resin formed on the surface thereof from the other solvent;
Dispersing the separated fluorine-containing resin particles in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group;
It is a manufacturing method of the fluorine-containing resin particle dispersion which has this.

The invention according to claim 6
Reactive monomer that is a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure Dissolving in at least one solvent selected from those capable of dissolving the resin without dissolving the resin in the hydroxyl group-containing solvent group;
An adsorption step of bringing the fluorine-containing resin particles into contact with the monomer and adsorbing the monomer on the surface of the fluorine-containing resin particles;
A polymerization step of polymerizing the monomer to form a resin on the surface of the fluorine-containing resin particles;
It is a manufacturing method of the fluorine-containing resin particle dispersion which has this.

The invention according to claim 7 provides:
Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin
A polymer that can be dissolved in at least one solvent in the hydroxyl group-containing solvent group that does not dissolve the resin;
A solvent that disperses the fluororesin particles and the polymer with the resin adhering to the surface, which is at least one selected from those capable of dissolving the resin and not dissolving the resin in the hydroxyl group-containing solvent group When,
Is a coating solution containing fluorine-containing resin particles.

The invention according to claim 8 provides:
Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin
A reactive monomer that can be dissolved in at least one solvent in the hydroxyl group-containing solvent group that does not dissolve the resin;
The fluorine-containing resin particles having at least one selected from those capable of dissolving the reactive monomer and not dissolving the resin in the hydroxyl group-containing solvent group, and the reactivity A solvent in which the monomer is dispersed;
Is a coating solution containing fluorine-containing resin particles.

The invention according to claim 9 is:
An application step of applying the fluorine-containing resin particle-containing coating solution according to claim 7 to a substrate surface to form a coating film;
A drying step of drying the coating film to form a coating film;
It is a manufacturing method of the fluorine-containing resin particle containing coating film which has this.

The invention according to claim 10 is:
A fluorine-containing resin particle-containing coating film produced by drying a coating film formed by applying the fluorine-containing resin particle-containing coating solution according to claim 7.

The invention according to claim 11 is:
An application step of applying the fluorine-containing resin particle-containing coating solution according to claim 8 to a substrate surface to form a coating film;
A polymerization step of drying the coating film and polymerizing the reactive monomer to form a coating film;
It is a manufacturing method of the fluorine-containing resin particle containing coating film which has this.

The invention according to claim 12
A fluorine-containing resin particle-containing coating film produced by drying a coating film formed by applying the fluorine-containing resin particle-containing coating solution according to claim 8 and polymerizing the reactive monomer.

The invention according to claim 13 is:
A molded body comprising a substrate and the fluororesin particle-containing coating film according to claim 10 or 12 on the substrate.

  According to the invention of claim 1, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where is not attached to the surface, the dispersibility of the fluororesin particles in the solvent of the hydroxyl group-containing solvent group is improved.

  According to the invention which concerns on Claim 2, the dispersibility of the fluorine-containing resin particle to the solvent of the said hydroxyl-containing solvent group improves compared with the case where resin is not adsorb | sucking on the surface of a fluorine-containing resin particle.

  According to the invention of claim 3, the fluorine-containing resin to the aliphatic alcohol and the fluorine-containing alcohol is compared with the case where the resin that does not dissolve in at least one of the aliphatic alcohol and the fluorine-containing alcohol does not adhere to the surface. The dispersibility of the particles is improved.

  According to the invention of claim 4, it is possible to produce a fluorine-containing resin particle dispersion in which the dispersibility of the hydroxyl group-containing solvent group in the solvent is improved and the long-term weather resistance is excellent as compared with the case without this configuration. .

  According to the invention which concerns on Claim 5, compared with the case where it does not have this structure, the dispersibility to the solvent of a hydroxyl-containing solvent group can be improved, and the fluorine-containing resin particle dispersion liquid excellent in long-term weather resistance can be manufactured. .

  According to the invention which concerns on Claim 6, compared with the case where it does not have this structure, the fluorine-containing resin particle dispersion liquid by which the dispersibility to the solvent of a hydroxyl-containing solvent group was improved can be manufactured.

  According to the invention of claim 7, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where is not attached to the surface, the dispersibility of the fluororesin particles in the solvent of the hydroxyl group-containing solvent group is improved.

  According to the invention of claim 8, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where is not attached to the surface, the dispersibility of the fluororesin particles in the solvent of the hydroxyl group-containing solvent group is improved.

  According to the invention of claim 9, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having an aromatic ring and having no aromatic ring in the molecular structure and an aqueous medium. Compared with the case where no is attached to the surface, a coating film containing the fluorine-containing resin particles uniformly can be produced.

  According to the invention of claim 10, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where no is attached to the surface, a coating film containing the fluorine-containing resin particles evenly is provided.

  According to the invention of claim 11, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where no is attached to the surface, a coating film containing the fluorine-containing resin particles uniformly can be produced.

  According to the invention of claim 12, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where no is attached to the surface, a coating film containing the fluorine-containing resin particles evenly is provided.

  According to the invention of claim 13, a resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. Compared with the case where no is adhered to the surface, a molded body provided with a coating film containing the fluorine-containing resin particles uniformly is provided.

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

<Fluorine-containing resin particle dispersion>
The fluorine-containing resin particle dispersion according to the present embodiment includes a fluorine-containing resin particle, a hydroxyl group-containing solvent group composed of an alcohol solvent having 1 to 10 carbon atoms and having no aromatic ring in the molecular structure, and an aqueous medium. It is at least one selected from a resin that does not dissolve in at least one solvent and adheres to the surface of the fluorine-containing resin particles, and a resin that does not dissolve the resin in the hydroxyl group-containing solvent group, and the resin on the surface And a solvent for dispersing the fluorine-containing resin particles to which is adhered.

When the fluorine-containing resin particles are dispersed in the solvent of the hydroxyl group-containing solvent group for stabilization, basically, a dispersant is added and dissolved in the solvent to be dispersed. Therefore, a large amount of the alcohol solvent is used. Or it was necessary to use what has a polar group which can be melt | dissolved in an aqueous medium. On the other hand, when a resin that does not dissolve in the solvent of the hydroxyl group-containing solvent group (hereinafter referred to as “specific resin”) is used as a dispersant, each of the above-mentioned specific resins is not dissolved in a solvent that does not adhere to the surface of the fluororesin particles. Even if it is attempted to disperse, the specific resin does not disperse because it is insoluble in the solvent.
However, in this embodiment, since the specific resin is attached to the surface of the fluorine-containing resin particles, it is presumed that the affinity for the solvent is increased, and as a result, excellent dispersibility can be obtained.

Here, whether or not the specific resin is dissolved in the solvent of the hydroxyl group-containing solvent group (solubility) is confirmed by the following test method.
-Test method for confirming solubility-
The solubility is measured in advance by measuring the surface tension of the solvent of the hydroxyl group-containing solvent group, and further measuring the surface tension after adding 5 mass% of the specific resin to the solvent of the hydroxyl group-containing solvent group and stirring for 5 hours. A case where the rate of change in surface tension before and after the addition of a specific resin is less than 10% is defined as “not dissolved”.
Further, in the case of producing by (Production Method 2) described later, the fluororesin particles having a resin formed on the surface are separated from other solvents, and the dried fluororesin particles are used as a solvent of the hydroxyl group-containing solvent group. Measures the surface tension after adding 5% by mass and stirring for 5 hours, and “does not dissolve” those with a surface tension change rate of less than 10% before and after the addition of fluororesin particles with a resin formed on the surface It is defined as
In addition, as a surface tension meter, the Kyowa Interface Science Co., Ltd. product: surface tension meter DY-700 is used, for example.

The term “adhesion” means that the specific resin is chemically or physically bonded to the surface of the fluorine-containing resin particles. Specifically, the specific resin is adsorbed on the surface of the fluorine-containing resin particles. It is a concept that includes the case of being bonded and the case of being chemically bonded.
In addition, adsorption | suction represents the physical adsorption | suction by van der Waals force, and represents the state where specific resin contacts the surface of a fluorine-containing resin particle and the density | concentration of specific resin in this surface is large.

  Hereinafter, each composition and manufacturing method which comprise the fluorine-containing resin particle dispersion which concerns on this embodiment are demonstrated in detail.

-Fluorine-containing resin particles-
As the fluorine-containing resin particles, a homopolymer of fluoroolefin or a copolymer of two or more kinds, which is a copolymer of one or more kinds of fluoroolefin and a non-fluorinated monomer is used.

  Examples of the fluoroolefin include perhaloolefin such as tetrafluoroethylene (TFE), perfluorovinyl ether, hexafluoropropylene (HFP), and chlorotrifluoroethylene (CTFE), vinylidene fluoride (VdF), trifluoroethylene, and fluoride. Non-perfluoroolefins such as vinyl can be mentioned, and VdF, TFE, CTFE, HFP and the like are preferable.

  Examples of the non-fluorine monomer include hydrocarbon olefins such as ethylene, propylene and butene, alkyl vinyl ethers such as cyclohexyl vinyl ether (CHVE), ethyl vinyl ether (EVE), butyl vinyl ether and methyl vinyl ether, and polyoxyethylene allyl ether. (POEAE), alkenyl vinyl ethers such as ethyl allyl ether, organosilicon compounds having reactive α, β-unsaturated groups such as vinyltrimethoxysilane (VSi), vinyltriethoxysilane, vinyltris (methoxyethoxy) silane, and acrylic acid Acrylic esters such as methyl and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, vinyl acetate, vinyl benzoate, Examples include vinyl esters such as “BEOVA” (trade name, vinyl ester manufactured by Shell), and alkyl vinyl ethers, allyl vinyl ethers, vinyl esters, and organosilicon compounds having a reactive α, β-unsaturated group are preferable.

  Among these, those having a high fluorination rate are preferable, such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA). ), Ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and the like are preferable. Among these, PTFE, FEP, and PFA are particularly preferable.

As the fluorine-containing resin particles, for example, particles (fluorine resin aqueous dispersion) produced by a method such as emulsion polymerization of a fluorine-based monomer may be used as they are, or may be used after thoroughly washing with water and drying. Good.
The average particle diameter of the fluororesin particles is preferably 0.01 μm or more and 100 μm or less, and particularly preferably 0.03 μm or more and 5 μm or less.

  Commercially available fluorine-containing resin particles may be used. For example, PTFE particles include Fullon L173JE (Asahi Glass Co., Ltd.), Taniion THV-221AZ, Taniion 9205 (Sumitomo 3M), Lubron L2, and Lubron. And L5 (manufactured by Daikin).

-Resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group-
In the fluorine-containing resin particle dispersion of this embodiment, a resin (specific resin) that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group adheres to the surface of the fluorine-containing resin particles. Whether or not the specific resin is not dissolved in the solvent of the hydroxyl group-containing solvent group (solubility) is confirmed by the test method described above.

  The specific resin preferably has a surface active action, that is, a substance having a hydrophilic group and a hydrophobic group in the molecule.

Examples of the resin (specific resin) that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group include resins obtained by polymerizing the following reactive monomers.
Specifically, a random or block copolymer of a acrylate having a perfluoroalkyl group and a monomer having no fluorine, a methacrylate homopolymer, and an acrylate having the perfluoroalkyl group, and not having the fluorine A random or block copolymer of a monomer, a methacrylate, and a random or block copolymer of the monomer having no fluorine.
Examples of the acrylate having a perfluoroalkyl group include 2,2,2-trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 3 -(Perfluorobutyl) -2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 1H, 1H, 3H-tetrafluoropropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 7H-dodecafluoroheptyl methacrylate, 1H-1- (trifluoromethyl) trifluoroethyl methacrylate, 1H, 1H, 3H-hexafluorobutyl Tacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2- (perfluorobutyl) ethyl acrylate, 3- (perfluorobutyl) -2-hydroxypropyl Acrylate, 2- (perfluorohexyl) ethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 1H, 1H, 3H-tetrafluoropropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 7H-dodecafluoroheptyl acrylate, 1H-1- (trifluoromethyl) trifluoroethyl acrylate, and 1H, 1H, 3H-hexafluorobutyl acrylate.
Moreover, as a monomer which does not have fluorine, for example, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate Phenoxypolyethyleneglycol Acrylate, phenoxy polyethylene glycol methacrylate, hydroxyethyl o-phenylphenol acrylate, o-phenylphenol glycidyl ether acrylate, ethylene glycol monoacrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, hexaethylene glycol monoacrylate, ethylene glycol monomethacrylate, Examples include diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, and hexaethylene glycol monomethacrylate.
Other examples include block or branch polymers disclosed in US Pat. No. 5,637,142, US Pat. No. 4,251,662, and US Pat. No. 4,251,662.

  In addition, as a method of attaching the specific resin to the surface of the fluorine-containing resin particles, the specific resin may be directly attached to the surface of the fluorine-containing resin particles (physical bonding), or first, the monomer described above May be adsorbed on the surface of the fluorine-containing resin particles, followed by polymerization to form the specific resin on the surface of the fluorine-containing resin particles (chemical bonding).

-Hydroxyl-containing solvent group-
In the fluorine-containing resin particle dispersion according to the present embodiment, as a solvent for dispersing the fluorine-containing resin particles having the specific resin attached to the surface, the molecular structure does not contain an aromatic ring and has 1 to 10 carbon atoms. At least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent and an aqueous medium is used.
Examples of the solvent belonging to the hydroxyl group-containing solvent group include an aqueous medium such as water, unbranched, branched and cyclic aliphatic alcohols such as methanol, ethanol, propanol, t-butanol, cyclohexanol, and furfuryl alcohol, ethylene glycol. And glycols such as propylene glycol, cellosolves such as methyl cellosolve, and aromatics such as phenol and benzyl alcohol.
Examples of the fluorine-containing alcohol include 2,2,2-trifluoroethanol, 2-fluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,3-trihydrotetrafluoropentanol, -Hydro-hexafluoro-2-propanol, 1,1,3-trihydrohexafluorobutanol, 1,1,5-trihydrotetrafluoropentanol, 2,2-bis (trifluoromethyl) propanol, 2- ( Perfluorobutyl) ethanol, 2-perfluoropropoxy-2,3,3,3-tetrafluoropropanol, 3-perfluorobutyl-2-iodopropanol, 2- (perfluoro-3-methylbutyl) ethanol, 1,1 , 7-Trihydrododecafluoroheptanol, 6- (perfluoroethyl) Hexanol, 1,1-dihydroheptafluorobutanol, 2- (perfluorohexyl) ethanol, 3- (perfluorohexyl) propanol, 3-perfluorohexyl-2-iodopropanol, 6- (perfluoro-1-methylethyl) ) Hexanol, 2- (perfluoro-5-methylhexyl) ethanol, 1,1,9 trihydrohexadecafluorononanol, 6- (perfluorobutyl) hexanol, 2- (perfluorooctyl) ethanol, 3- ( Perfluoro-5-methylhexyl) -2-iodopropanol, 3- (perfluorooctyl) propanol, 3-perfluorooctyl-2-iodopropanol, 6- (perfluoro-3-methylbutyl) hexanol, 2- (per Fluoro-7-methylo Chill) ethanol, 6- (perfluorohexyl) hexanol, 2- (perfluorodecyl) ethanol, 3- (perfluoro-7-methyloctyl) -2-iodopropanol, 6- (perfluoro-5-methylhexyl) Examples thereof include fluorinated alcohols such as hexanol, 2- (perfluoro-9-methyldecyl) ethanol, 6- (perfluorooctyl) hexanol, and 6- (perfluoro-7-methyldecyl) ethanol.
In addition, the thing whose boiling point is 150 degrees C or less is preferable from the point of drying time.

-Surfactant-
In the fluorine-containing resin particle dispersion according to this embodiment, a surfactant may be added. However, the amount is preferably as small as possible, preferably 0 parts by weight or more and 0.1 parts by weight or less, more preferably 0 parts by weight or more and 0.05 parts by weight or less, with respect to 1 part by weight of the fluororesin particles. 0 parts by mass or more and 0.03 parts by mass or less are particularly preferable.

  As the surfactant, nonionic surfactants are preferable. For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters And glycerin esters and derivatives thereof.

  Surfactants containing fluorine may also be used. For example, Surflon S-611, Surflon S-385 (manufactured by AGC Seimi Chemical Co., Ltd.), Aftergent 730FL, Aftergent 750FL (manufactured by Neos), PF-636, PF-6520 ( Kitamura Chemical Co., Ltd.), Mega-Fac EXP, TF-1507, Mega-Fac EXP, TF-1535 (Dic), FC-4430, FC-4432 (3M).

<Method for producing fluororesin particle dispersion>
Although it does not specifically limit as a manufacturing method of the fluorine-containing resin particle dispersion which concerns on this embodiment, For example, the following three methods are mentioned.

(Manufacturing method 1)
The manufacturing method which has the following each process.
-Dissolution process Resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium not containing an aromatic ring in the molecular structure is dissolved in the resin. Dissolving in other solvent to obtain / adsorption step Contacting the resin with fluorine-containing resin particles to adsorb the resin on the surface of the fluorine-containing resin particles-Separation step The fluorine-containing resin particles having the resin adsorbed on the surface Separation / dispersion step from the other solvent The separated fluorine-containing resin particles are dispersed in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group. A dispersion liquid in which fluorine-containing resin particles having a resin physically adsorbed on the surface is dispersed is obtained.

(Manufacturing method 2)
The manufacturing method which has the following each process.
・ Solubility step Reactivity that becomes a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. The monomer is dissolved in another solvent that can dissolve the resin. Adsorption step The fluorine-containing resin particles are brought into contact with the monomer to adsorb the monomer on the surface of the fluorine-containing resin particles. Step: Polymerizing the monomer to form a resin on the surface of the fluorine-containing resin particles / separation step Separating the fluorine-containing resin particles having the resin formed on the surface from the other solvent / dispersing step In addition, the fluorine-containing resin particles are dispersed in at least one solvent selected from the group of hydroxyl group-containing solvents that do not dissolve the resin. Chemically polymerizing a reactive monomer, dispersion fluorine resin particles obtained by chemically bonding resin is dispersed is obtained.

(Manufacturing method 3)
The manufacturing method which has the following each process.
・ Solubility step Reactivity that becomes a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. A monomer is dissolved in at least one solvent selected from those capable of dissolving the monomer without dissolving the resin in the hydroxyl group-containing solvent group. Adsorption step Fluorine-containing resin in the monomer The monomer is adsorbed on the surface of the fluorine-containing resin particles by bringing the particles into contact. Polymerization step The resin is polymerized to form a resin on the surface of the fluorine-containing resin particles.

The fluororesin particle dispersion obtained by the above (Production Method 1) and (Production Method 2) is once again adsorbed with a specific resin on the surface of the fluororesin particles and separated from the other solvent. Dispersion in which the specific resin not adhering to the fluorine-containing resin particles (hereinafter referred to as “free resin”) does not exist or the presence of the free resin is extremely suppressed because it is dispersed in the solvent of the hydroxyl group-containing solvent group Become a liquid.
When the liberated resin is present in the fluorine-containing resin particle dispersion, the liberated resin is particularly susceptible to humidity, and the characteristics of the dispersion are likely to vary. However, according to the above method, since the presence of free resin that is particularly susceptible to humidity is suppressed, it is presumed that the fluororesin particle dispersion is excellent in long-term weather resistance and dispersibility. The

  Here, the method for confirming the presence of the liberated resin (presence / absence of resin detachment) can be easily determined by measuring the surface tension of the solvent. That is, the surface tension (STs (mN / m)) in the state of only the solvent and the surface tension (STp (mN / m)) of the solvent after dispersing the fluorine-containing resin particles to which the specific resin is adhered are commercially available. Surface tension meter (in this specification, manufactured by Kyowa Interface Science Co., Ltd., surface tension meter: DY-700 is used), and is free if | STs-STp | /STs≦0.05. It is judged that there is no.

-Manufacturing by Manufacturing Method 1-
-Dissolution Step and Adsorption Step As the other solvent capable of dissolving the specific resin, any solvent can be used as long as the solubility of the specific resin is 10% by mass or more. The solubility is determined by adding the specific resin to the other solvent, weighing the entire mass of the specific resin and the other solvent, and then filtering after stirring for a sufficient time, weighing the mass of the filtrate, It is calculated by measuring the mass of the undissolved resin from the total mass before stirring and the mass of the filtrate after filtration.

  Suitable other solvents vary depending on the resin, for example, aromatics such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, tetrahydrofuran, dioxane and the like Examples include solvents such as ethers, hydrocarbons such as hexane, octane and cyclohexane, amides such as N, N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide. In addition, what can be mixed with the solvent of a hydroxyl-containing solvent group in arbitrary ratios is preferable, The thing whose boiling point is 180 degrees C or less is preferable, Furthermore, the thing of 150 degrees C or less is more preferable.

  The other solvent is preferably 1 part by mass or more and 1000 parts by mass or less, more preferably 2 parts by mass or more and 800 parts by mass or less, and particularly preferably 5 parts by mass or more and 700 parts by mass or less with respect to 1 part by mass of the specific resin.

  The amount of the specific resin depends on the adsorptivity to the surface of the fluorine-containing resin particles, but is preferably 0.001 parts by mass or more and 10 parts by mass or less, and 0.005 parts by mass or more and 8 parts by mass with respect to 1 part by mass of the fluorine-containing resin particles. Is more preferably 0.01 parts by mass or more and 5 parts by mass or less.

  As the treatment method, the fluororesin particles are added to the other solvent in which the specific resin is dissolved, and preferably 0 ° C. or higher and the boiling point of the other solvent, more preferably 10 ° C. or higher and 100 ° C. or lower, particularly preferably 10 ° C. or higher. It is preferable to make the contact at 50 ° C. or lower while stirring, ultrasonic irradiation, shaking with a paint shaker or the like, and dispersing with a homogenizer or the like.

  The contact time is preferably 5 minutes to 48 hours, more preferably 10 minutes to 24 hours. It is preferable to end the adsorption state when the change in the surface tension of the solvent is observed while observing the change in the surface tension of the solvent with a surface tension meter or the like.

Separation process and dispersion process Examples of the method for separating the fluororesin particles adsorbed with the specific resin from other solvents after the adsorption process include decantation, filtration, and centrifugation. Excess specific resin that has not been adsorbed is separated. The fluorine-containing resin particles may be dried, but it is more preferable that the fluorine-containing resin particles be added to and dispersed in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group. In this way, a fluororesin particle dispersion in which the presence of free resin is suppressed is obtained.

-Manufacturing by Manufacturing Method 2-
-Dissolution process and adsorption process As another solvent which can melt | dissolve resin (specific resin), what was used for the said manufacturing method 1 is used. Moreover, as the reactive monomer, the reactive monomers listed in the above-mentioned section of “-resin not soluble in at least one solvent in the hydroxyl group-containing solvent group” are used.

The specific resin (I) synthesized by the reactive monomer used in the production method 2, the solvent (II) of the hydroxyl group-containing solvent group that does not dissolve the specific resin, and the specific resin can be dissolved. Specific combinations with other solvents (III) include, for example, the following combinations (described in the order of (I) (II) (III)).
Copolymer of hydroxyethyl methacrylate and 2- (perfluorohexyl) ethyl methacrylate, cyclopentanol, toluene Copolymer of 2- (perfluorohexyl) ethyl acrylate and hexaethylene glycol monoacrylate, n-butanol , A copolymer of tetrahydrofuran, 2- (perfluorobutyl) ethyl methacrylate, styrene and hexaethylene glycol monoacrylate, n-propanol, tetrahydrofuran

  The amount of the other solvent is preferably 1 part by mass or more and 1000 parts by mass or less, more preferably 2 parts by mass or more and 800 parts by mass or less, with respect to the reactive monomer used as a raw material for 1 part by mass of the specific resin. The amount is particularly preferably not less than 700 parts by mass.

  The amount of the reactive monomer depends on the adsorptivity to the surface of the fluorine-containing resin particles, but is 0.001 part by mass or more and 10 parts by mass or less of the specific resin raw material with respect to 1 part by mass of the fluorine-containing resin particles. The amount of the reactive monomer is preferably 0.005 parts by mass or more and more preferably 8 parts by mass or less of the reactive monomer used as the raw material for the specific resin. It is particularly preferable that the amount of the reactive monomer used as a raw material for the specific resin is from 5 parts by mass to 5 parts by mass.

Polymerization process Thermal radical polymerization is preferred as the reaction method, and the fluororesin particles and the polymerization initiator are added to the other solvent in which the reactive monomer is dissolved, and the mixture is preferably stirred at 50 ° C to 150 ° C. While reacting. The reaction is preferably performed in an inert gas atmosphere such as nitrogen.

  The reaction time is preferably from 30 minutes to 24 hours, and more preferably from 1 hour to 10 hours.

As the polymerization initiator, for example, the following commercially available catalysts are used.
For example, V-30, V-40, V-59, V601, V65, V-70, VF-096, Vam-110, Vam-111 (manufactured by Wako Pure Chemical Industries), OTazo-15, OTazo-30, AIBM, Azo initiators such as AMBN, ADVN and ACVA (Otsuka Chemical). Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Park Mill H, Park Mill P, Permenta H, Per Octa H, Perbutyl C, Perbutyl D, Perhexyl D, Parroyl IB, Parroyl 355, Parroyl L , Parroyl SA, Niper BW, Niper BMT-K40 / M, Parroyl IPP, Parroyl NPP, Parroyl TCP, Parroyl OPP, Parroyl SBP, Parkmill ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 2 5Z, perbutyl A, perhexyl Z, perbutyl ZT, perbutyl Z (manufactured by NOF Chemical Co., Ltd.) and the like.

-Separation process and dispersion process Examples of the method for separating the fluororesin particles adsorbed with the specific resin from the solvent after the adsorption process include decantation, filtration, and centrifugation, and these operations adsorb to the fluororesin particles. Any excess specific resin that did not exist is separated. The fluorine-containing resin particles may be dried, but it is more preferable that the fluorine-containing resin particles be added to and dispersed in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group without drying. In this way, a fluororesin particle dispersion in which the presence of free resin is suppressed is obtained.

-Production by Production Method 3-
-Dissolution step and adsorption step As the reactive monomer, the reactive monomers listed in the above-mentioned "-resin not soluble in at least one solvent in the hydroxyl group-containing solvent group" section. Used.

  The amount of the solvent in the hydroxyl group-containing solvent group is preferably 1 part by mass or more and 1000 parts by mass or less, and more preferably 2 parts by mass or more and 800 parts by mass or less with respect to the reactive monomer used as a raw material for 1 part by mass of the specific resin. 5 parts by mass or more and 700 parts by mass or less are particularly preferable.

  The amount of the reactive monomer depends on the adsorptivity to the surface of the fluorine-containing resin particles, but is 0.001 part by mass or more and 10 parts by mass or less of the specific resin raw material with respect to 1 part by mass of the fluorine-containing resin particles. The amount of the reactive monomer is preferably 0.005 parts by mass or more and more preferably 8 parts by mass or less of the reactive monomer used as the raw material for the specific resin. It is particularly preferable that the amount of the reactive monomer used as a raw material for the specific resin is from 5 parts by mass to 5 parts by mass.

Polymerization process Thermal radical polymerization is preferred as the reaction method, and the fluororesin particles and the polymerization initiator are added to the solvent in which the reactive monomer is dissolved, and the reaction is preferably performed at 50 ° C to 150 ° C with stirring. Let The reaction is preferably performed in an inert gas atmosphere such as nitrogen.

  As the reaction time and the polymerization initiator to be used, the reaction time and the polymerization initiator in the production method 2 are applied.

<Fluorine-containing resin particle-containing coating solution, fluorine-containing resin particle-containing coating film, molded article>
When preparing a fluorine-containing resin particle-containing coating liquid (hereinafter also simply referred to as “coating material”), the solvent used in the dispersion (that is, of the hydroxyl group-containing solvent group) is used with respect to the fluorine-containing resin particle dispersion. A polymer that can be dissolved in at least one solvent that does not dissolve the specific resin, or a reactive monomer that is a raw material of the polymer, and does not dissolve the specific resin in the solvent (that is, the hydroxyl group-containing solvent group) Monomers that can be dissolved in at least one solvent among them. Further, for example, additives generally used in paints such as pigments, thickeners, dispersants, antifoaming agents, antifreezing agents, film forming aids, ultraviolet absorbers and antioxidants may be blended.
This paint is used as a surface protective coating agent for inorganic substrates such as concrete, slate, ALC plate, and metal substrates, and further as a coating agent for coated paper. In addition, it is also used as a design coating agent by blending synthetic resin beads for matting, natural stones, and the like. Furthermore, it is also used for exterior and / or interior water-based paints for low-rise buildings.

  The blending ratio of the solid component in the fluorine-containing resin particle dispersion according to this embodiment in the fluorine-containing resin particle-containing coating liquid varies depending on the form of the coating liquid and the coating method, but is 5% by mass or more of the coating liquid. It may be 95% by mass or less, preferably 20% by mass or more and 90% by mass or less.

  Conventionally known coating methods are employed as the coating method of the paint. For coating, conventionally known coating tools such as brushes, rollers, roll coaters, air sprays, airless sprays, electrostatic coating machines, immersion coating machines, and electrodeposition coating machines are used.

  The paint is not limited to metals such as iron, aluminum, copper or alloys thereof, but inorganic materials such as glass, cement and concrete, resins such as FRP, acrylic resin, vinyl chloride resin, polycarbonate resin and polyurethane resin, It can be applied to various substrates such as wood and fiber. In addition, a preliminary treatment such as applying a primer such as a known water-based resin emulsion paint or solvent-type paint to the base material or a surface treatment may be performed, and after applying an undercoat or precoat, the paint is applied. Also good.

  The coating of the paint may be performed as a clear paint or an enamel paint on a base material having a design such as various known unevenness and color patterns. After coating, the coating is usually dried at 5 to 300 ° C. for 30 seconds to 1 week and cured. The film thickness of the coating film is not particularly limited, but is usually preferably 1 μm to 200 μm, more preferably 5 μm to 100 μm, and particularly preferably 10 μm to 50 μm.

  The coated product thus obtained can be used in a wide range of applications. For example, interior and exterior of electrical products (microwave oven, toaster, refrigerator, washing machine, hair dryer, TV, video, amplifier, radio, electric kettle, rice cooker, radio cassette, cassette deck, compact disc player, video camera, etc.) Air conditioner indoor units, outdoor units, air outlets and ducts, air conditioners such as air purifiers and heaters, lighting fixtures such as fluorescent lamps, chandeliers, reflectors, furniture, machine parts, ornaments, combs, Glasses frames, natural fibers, synthetic fibers (threads and fabrics obtained from them), office equipment (telephones, facsimiles, copiers (including rolls), cameras, overhead projectors, actual projectors, watches, slide projectors, Desk, bookshelf, locker, document shelf, chair, bookend, electric Interior and exterior of white boards, etc., automobiles (wheels, door mirrors, moldings, door knobs, license plates, handles, instrumental panels, etc.) (For faucets, gas ranges, ventilation fans, etc.), for interior painting of partitions, bath units, shutters, blinds, curtain rails, accordion curtains, walls, ceilings, floors, etc. General housing exteriors such as shutters, ceramic exterior sizing materials, foamed concrete panels, concrete panels, aluminum curtain walls, steel sheets, galvanized steel sheets, stainless steel sheets, PVC sheets, window glass, etc. Have a wide range of uses.

  EXAMPLES Examples and comparative examples will be described below, but the present invention is not limited to the following examples. In the following, “part” is based on mass unless otherwise specified.

[Resin synthesis example A]
In a 1 liter pressure-resistant reaction vessel equipped with a stirrer, 50 parts of a macromonomer represented by the following formula (1) (m is 80), 30 parts of 2- (perfluorohexyl) ethyl methacrylate, 300 parts of trifluorotoluene, azoisobutyro 0.5 parts of nitrile was added and reacted at 90 ° C. for 5 hours under a nitrogen atmosphere. This reaction solution was dropped into 5000 parts of methanol to precipitate a resin, which was filtered and dried to obtain 65 parts of a resin (surfactant) (A).
When the molecular weight was measured by GPC, Mw was 30000 in terms of styrene. When the solubility of this resin (A) in methanol, ethanol, cyclopentanol, and 1H, 1H-pentafluoropropanol was measured by the above-described method, the rate of decrease in surface tension was 0 for methanol, ethanol, and cyclopentanol. .1% or less, 1H, 1H-pentafluoropropanol was 0.5%, and was insoluble in any solvent.

[Resin synthesis example B]
Resin (interface) was prepared by the method described in Resin Synthesis Example A except that 30 parts of 2- (perfluorohexyl) ethyl methacrylate in Resin Synthesis Example A was changed to 30 parts of monomer represented by the following formula (2). 60 parts of activator (B) were obtained.
When molecular weight was measured by GPC, Mw was 35000 in terms of styrene. When the solubility of this resin (B) in methanol, ethanol, cyclopentanol, and 1H, 1H-trifluoroethanol was measured by the above-described method, the rate of decrease in surface tension was 0 for methanol, ethanol, and cyclopentanol. .1% or less, 1H, 1H-pentafluoropropanol was 0.5%, and was insoluble in any solvent.

[Resin synthesis example C]
To a 1 liter pressure-resistant reaction vessel equipped with a stirrer, 20 parts of hydroxyethyl methacrylate, 60 parts of 2- (perfluorohexyl) ethyl methacrylate, 300 parts of trifluorotoluene and 0.5 part of azoisobutyronitrile are added, and the mixture is stirred under a nitrogen atmosphere. The reaction was carried out at 5 ° C. for 5 hours. This reaction solution was dropped into 5000 parts of methanol to precipitate a resin, which was filtered and dried to obtain 60 parts of a resin (surfactant) (C).
When the molecular weight was measured by GPC, Mw was 20000 in terms of styrene. When the solubility of this resin (C) in methanol, ethanol, and cyclopentanol was measured by the above-described method, the rate of decrease in surface tension was 0.2% or less for methanol, ethanol, and cyclopentanol. -Pentafluoropropanol was 0.6%, and although some swelling was seen, it was insoluble in any solvent.

[Resin D]
“Aron GF300” manufactured by Toa Gosei Co., Ltd. was used as the resin (D).
When the solubility of this resin (D) in methanol, ethanol, and cyclopentanol was measured by the above-described method, the rate of decrease in surface tension was 0.1% or less for methanol, ethanol, and cyclopentanol. -It was 0.2% in pentafluoropropanol, and was insoluble in any solvent.

<Example 1>
In a 500 ml glass bottle, 300 parts of toluene and 3 parts of resin (surfactant) (A) were added and dissolved (dissolution step).
After dissolution, add 30 parts of PTFE particles (Daikin: Lubron L-2), stir at room temperature (25 ° C) for 1 day, and centrifuge to adsorb resin insoluble in methanol, ethanol, and cyclopentanol PTFE particles were obtained (adsorption process and separation process). When the supernatant was centrifuged and the solvent was removed with an evaporator and weighed, 1.2 parts of unadsorbed resin (A) was recovered and it was confirmed that 6% by mass / 1 g-PTFE was adsorbed. .
The PTFE after the adsorption treatment of the resin (A) was separated, washed with tetrahydrofuran, and the resin (A) recovered by concentrating the washing liquid was 6% by mass / 1 g-PTFE. It was confirmed that the resin (A) was adsorbed on the surface.
Next, when the PTFE particles after centrifugation were dispersed in 300 parts of cyclopentanol (dispersing step), it easily became a dispersion and hardly settled even after standing for one day. This is designated as dispersion (1).

  The surface tension (STs) of cyclopentanol at room temperature (25 ° C.) is 33.50 mN / m, the surface tension after dispersion of PTFE particles (STp) is 33.45 mN / m, and | STs−STp | When /STs=0.001, it is judged that the resin (A) is not released from the surface of the PTFE particles.

<Examples 2 to 4>
The resin (A) in Example 1 was treated by the method described in Example 1 except that the resin (B), the resin (C), and the resin (D) (Aron GF300, manufactured by Toagosei Co., Ltd.) were used. Liquids (2) to (4) were obtained.
In the dispersions (2) to (4), almost no settling was observed after standing for one day after dispersion. The measurement results of the adsorption amount and the calculation result of | STs−STp | / STs are shown in Table 1 below.

<Example 5>
In a 1 liter pressure-resistant reaction vessel with a stirrer, 1 part of hydroxyethyl methacrylate, 6 parts of 2- (perfluorohexyl) ethyl methacrylate, 300 parts of toluene, 30 parts of PTFE particles (manufactured by Daikin: Lubron L-2) are placed at room temperature. For 1 day (dissolution step and adsorption step).
Subsequently, 0.1 part of azoisobutyronitrile was added and reacted at 90 ° C. for 5 hours under a nitrogen atmosphere (polymerization step).
After cooling the reaction solution, it was centrifuged and then redispersed in 300 parts of toluene again and centrifuged to obtain PTFE particles adsorbed with the resin (separation step). When all the supernatant liquids after centrifugation were weighed after removing the solvent with an evaporator, it was confirmed that 3.9 parts of unadsorbed resin was recovered and 7 mass% / 1 g-PTFE was adsorbed.
Next, when the PTFE particles after centrifugation were dispersed in 300 parts of cyclopentanol (dispersing step), it easily became a dispersion and hardly settled even after standing for one day. This is designated as Dispersion Liquid (5).

  A resin obtained by polymerizing 1 part of hydroxyethyl methacrylate and 6 parts of 2- (perfluorohexyl) ethyl methacrylate was separately synthesized, and the solubility of this resin in methanol, ethanol, and cyclopentanol was determined by the method described above. As a result, it was insoluble in any solvent.

  Further, the surface tension (STs) of cyclopentanol at room temperature (25 ° C.) is 33.50 mN / m, the surface tension after dispersion of PTFE particles (STp) is 33.25 mN / m, and | STs−STp | / When STs = 0.007, it is judged that no resin is released from the surface of the PTFE particles.

<Examples 6 and 7>
PTFE particles in Example 1 (Daikin: Lubron L-2), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) (Mitsui DuPont Fluorochemicals: MP102), and tetrafluoroethylene-hexafluoro Dispersions (6) and (7) were obtained by the same treatment as described in Example 1 except that the propylene copolymer (FEP) (Mitsui DuPont Fluorochemical Co., Ltd .: MPE056) was used.
In the dispersions (6) and (7), a small amount of sediment was observed after standing for one day after dispersion. The measurement results of the adsorption amount and the calculation result of | STs−STp | / STs are shown in Table 1 below.

<Examples 8 and 9>
Except for changing 300 parts of cyclopentanol in Examples 6 and 7 to a mixed solvent of 240 parts of cyclopentanol and 60 parts of 1H, 1H-pentafluoropropanol, the treatment was carried out by the method described in Examples 6 and 7, Dispersions (8) and (9) were obtained.
In the dispersions (8) and (9), almost no settling was observed after standing for one day after dispersion. The measurement results of the adsorption amount and the calculation result of | STs−STp | / STs are shown in Table 1 below.

<Examples 10 and 11>
Dispersions (10) and (11) were treated by the method described in Example 1 except that the amount of the resin (surfactant) (A) in Example 1 was changed from 3 parts to 10 parts and 15 parts. Got.
In the dispersions (10) and (11), almost no sedimentation was observed after standing for one day after dispersion. The measurement results of the adsorption amount and the calculation result of | STs−STp | / STs are shown in Table 1 below.

<Example 12>
The dispersion solvent in Example 5 was treated by the method described in Example 5 except that cyclopentanol was changed to a mixed solvent of water and methanol 1: 1 (volume ratio) to obtain a dispersion liquid (12). It was.
A small amount of sediment was observed in the dispersion (12) after standing for one day after dispersion. The measurement results of the adsorption amount and the calculation result of | STs−STp | / STs are shown in Table 1 below.

<Comparative Example 1>
A 500 ml glass bottle was charged with 300 parts of cyclopentanol and 3 parts of resin (surfactant) (A) and stirred at room temperature (25 ° C.), but it did not dissolve at all.
30 parts of PTFE particles (manufactured by Daikin: Lubron L-2) were added to this mixed solution and stirred for 1 day at room temperature (25 ° C.). However, the dispersibility was extremely poor and sedimentation occurred immediately.
The calculation result of | STs−STp | / STs is shown in Table 1 below.

<Comparative Examples 2-4>
The resin (A) in Comparative Example 1 was treated by the method described in Comparative Example 1 except that the resin (B), the resin (C), and the resin (D) (Aron GF300, manufactured by Toagosei Co., Ltd.) were used.
However, the dispersibility was extremely poor and sedimentation occurred immediately. The calculation result of | STs−STp | / STs is shown in Table 1 below.

<Comparative Examples 5 and 6>
PTFE particles in Comparative Example 1 (Daikin: Lubron L-2), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) (Mitsui DuPont Fluorochemicals: MP102), and tetrafluoroethylene-hexafluoro It processed by the method of the comparative example 1 except having changed into the propylene copolymer (FEP) (the Mitsui DuPont fluorochemical company make: MPE056).
However, the dispersibility was extremely poor and sedimentation occurred immediately. The calculation result of | STs−STp | / STs is shown in Table 1 below.

<Example 13>
10 parts of dispersion (1), 5 parts of phenol resin (PL-4852: manufactured by Gunei Chemical Co., Ltd.) and 0.01 part of FT 730FL (manufactured by NEOS) were mixed to obtain a coating solution.
The solubility of the phenol resin in cyclopentanol was tested by the method described in Resin Synthesis Example A and was soluble.
The coating solution was applied on a polycarbonate resin plate with a wire bar and cured at 130 ° C. for 20 minutes to form a 10 μm surface film. When the surface film was formed, the polycarbonate resin was not altered or cracked, and a good film was obtained. Further, the obtained surface film was very difficult to be scratched by a simple rubbing test with Bencott.

<Examples 14 to 19>
A coating solution was obtained by the method described in Example 13 except that the dispersions (2) to (5), (10), and (11) were used instead of the dispersion (1) to form a surface film.
In any case, no deterioration or cracking of the polycarbonate resin was observed during the formation of the surface film, and a good film was obtained. Further, the obtained surface film was very difficult to be scratched by a simple rubbing test with Bencott.

<Example 20>
10 parts of the dispersion (1), 5 parts of dipropylene glycol diacrylate (DPGDA: manufactured by Daicel Cytec), 0.01 part of FT 730FL (manufactured by NEOS), 0.2 part of Irgacure 819 (manufactured by BASF) are mixed. A coating solution was obtained.
The solubility of dipropylene glycol diacrylate in cyclopentanol was tested and found to be soluble.
The above coating solution is coated on a polycarbonate resin plate with a wire bar, dried, and then photocured for 60 seconds at 160 W / cm with an ultraviolet irradiation device (Unicure: manufactured by USHIO INC.) Under nitrogen to form a surface film. did. When the surface film was formed, the polycarbonate resin was not altered or cracked, and a good film was obtained. Further, the obtained surface film was very difficult to be scratched by a simple rubbing test with Bencott.

Claims (13)

Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin
A solvent that disperses the fluorine-containing resin particles having at least one selected from those that do not dissolve the resin in the hydroxyl group-containing solvent group;
Fluorine-containing resin particle dispersion containing   The fluororesin particle dispersion according to claim 1, wherein the resin is adsorbed on the surface of the fluororesin particles.   The fluorine-containing resin particle dispersion according to claim 1 or 2, wherein the hydroxyl group-containing solvent group comprises an aliphatic alcohol and a fluorine-containing alcohol. A resin that does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure. A dissolution step of dissolving in a solvent;
An adsorption step of contacting the resin with the fluorine-containing resin particles to adsorb the resin on the surface of the fluorine-containing resin particles;
A separation step of separating the fluorine-containing resin particles having the resin adsorbed on the surface thereof from the other solvent;
Dispersing the separated fluorine-containing resin particles in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group;
The manufacturing method of the fluorine-containing resin particle dispersion which has this. Reactive monomer that is a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure Dissolving step in another solvent capable of dissolving the resin,
An adsorption step of bringing the fluorine-containing resin particles into contact with the monomer and adsorbing the monomer on the surface of the fluorine-containing resin particles;
A polymerization step of polymerizing the monomer to form a resin on the surface of the fluorine-containing resin particles;
A separation step of separating the fluororesin particles having the resin formed on the surface thereof from the other solvent;
Dispersing the separated fluorine-containing resin particles in at least one solvent selected from those not dissolving the resin in the hydroxyl group-containing solvent group;
The manufacturing method of the fluorine-containing resin particle dispersion which has this. Reactive monomer that is a raw material for a resin that does not dissolve in at least one solvent in a hydroxyl group-containing solvent group consisting of an alcoholic solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure Dissolving in at least one solvent selected from those capable of dissolving the resin without dissolving the resin in the hydroxyl group-containing solvent group;
An adsorption step of bringing the fluorine-containing resin particles into contact with the monomer and adsorbing the monomer on the surface of the fluorine-containing resin particles;
A polymerization step of polymerizing the monomer to form a resin on the surface of the fluorine-containing resin particles;
The manufacturing method of the fluorine-containing resin particle dispersion which has this. Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin and
A polymer that can be dissolved in at least one solvent in the hydroxyl group-containing solvent group that does not dissolve the resin;
A solvent that disperses the fluororesin particles and the polymer with the resin adhering to the surface, which is at least one selected from those capable of dissolving the resin and not dissolving the resin in the hydroxyl group-containing solvent group When,
A coating solution containing fluorine-containing resin particles. Fluorine-containing resin particles;
It does not dissolve in at least one solvent in the hydroxyl group-containing solvent group consisting of an alcohol solvent having 1 to 10 carbon atoms and an aqueous medium that does not contain an aromatic ring in the molecular structure, and adheres to the surface of the fluororesin particles. Resin and
A reactive monomer that can be dissolved in at least one solvent in the hydroxyl group-containing solvent group that does not dissolve the resin;
The fluorine-containing resin particles having at least one selected from those capable of dissolving the reactive monomer and not dissolving the resin in the hydroxyl group-containing solvent group, and the reactivity A solvent in which the monomer is dispersed;
A coating solution containing fluorine-containing resin particles. An application step of applying the fluorine-containing resin particle-containing coating solution according to claim 7 to a substrate surface to form a coating film;
A drying step of drying the coating film to form a coating film;
The manufacturing method of the coating film containing a fluorine-containing resin particle which has this.   A fluorine-containing resin particle-containing coating film produced by drying a coating film formed by applying the fluorine-containing resin particle-containing coating solution according to claim 7. An application step of applying the fluorine-containing resin particle-containing coating solution according to claim 8 to a substrate surface to form a coating film;
A polymerization step of drying the coating film and polymerizing the reactive monomer to form a coating film;
The manufacturing method of the coating film containing a fluorine-containing resin particle which has this.   A fluorine-containing resin particle-containing coating film produced by drying a coating film formed by applying the fluorine-containing resin particle-containing coating solution according to claim 8 and polymerizing the reactive monomer.   The molded object provided with the base material and the fluorine-containing resin particle containing coating film of Claim 10 or Claim 12 on this base material.