WO2013058333A1

WO2013058333A1 - Surface treatment agent composition, and use thereof

Info

Publication number: WO2013058333A1
Application number: PCT/JP2012/076991
Authority: WO
Inventors: 三木　淳; 剣吾伊藤; 田中　義人; 浩治久保田
Original assignee: ダイキン工業株式会社
Priority date: 2011-10-19
Filing date: 2012-10-18
Publication date: 2013-04-25
Also published as: TW201321440A; JP2013100493A

Abstract

Disclosed is a surface treatment agent composition containing a fluorine-containing polymer having a repeating unit (i) derived from a fluorine-containing olefin and a repeating unit (ii) derived from a hydrocarbon-based vinyl. The surface treatment agent composition does not contain a perfluoroalkyl group having 8 or more carbon atoms and uses a fluorine-containing monomer that is easily obtained. Preferably, the fluorine-containing olefin is represented by CR¹R²=CR³R⁴. (In the formula, R¹, R², R³, and R⁴ are the same or different from one another and each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a C_1-10 alkoxy group, a C_1-10 perfluoroalkyl group, a C_1-10 polyfluoroalkyl group represented by C_mH_nF_p (in the formula, m represents an integer between 1 and 10, n represents an integer between 1 and 2m, and p represents a number obtained from 2m+1-n), a C_6-18 perfluoroaryl group, or a C_6-18 polyfluoroaryl group.)

Description

Surface treatment agent composition and use thereof

The present invention relates to a surface treating agent composition and its use. The surface treating agent composition can be favorably used as a surface treating agent, for example, a water / oil repellent, an antifouling agent and a release agent.

Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere. For example, US Pat. No. 5,247,008 discloses an aqueous copolymer of a perfluoroalkyl ester of (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, and an aminoalkyl ester of (meth) acrylic acid. Finishing agents for textiles, leather, paper and mineral substrates, which are dispersions, are described.

The surface function as a water / oil repellent and antifouling agent is manifested by a heavy monomer composed of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms on which the perfluoroalkyl group is stably oriented. Copolymers or copolymers have been considered effective.
However, in recent years, it has been pointed out by the EPA (United States Environmental Protection Agency) that the decomposition product of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms is a compound having a high environmental load. There is a demand for a water / oil repellent or antifouling agent of a compound containing no perfluoroalkyl group having 8 or more carbon atoms.

Also, (per) fluoroalkyl esters of (meth) acrylic acid are produced through several steps using tetrafluoroethylene or the like. That is, the (per) fluoroalkyl ester of (meth) acrylic acid has the disadvantage that it is not easy to obtain because it is complicated to manufacture. There is a demand for producing a surface treatment agent using a fluorine-containing monomer that is easily available.

Polymers using fluoroolefins are disclosed in, for example, JP-A-49-11915, JP-A-61-113607, and JP-A-2009-126990. It does not give sufficient performance as a surface treatment agent.

US Pat. No. 5,247,008 JP 49-11915 A JP 61-113607 A JP 2009-126990 A

One object of the present invention is to provide a surface treating agent using a fluorine-containing monomer that does not contain a perfluoroalkyl group having 8 or more carbon atoms and is easily available. Other objects of the present invention include performance required as a surface treatment agent, such as water / oil repellency, antifouling properties, mold release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, and the like. A fluorine-containing composition having durability in performance is provided.

The present invention
A surface treating agent composition (fluorinated composition) comprising (i) a repeating unit derived from a fluorine-containing olefin, and (ii) a fluorine-containing polymer having a repeating unit derived from a hydrocarbon-based vinyl. )I will provide a.

According to the present invention, a surface treating agent composition (fluorine-containing composition) is obtained using a monomer that does not contain a perfluoroalkyl group having 8 or more carbon atoms and is easily available. The fluorine-containing composition has performance required as a surface treatment agent, for example, good water and oil repellency, antifouling properties, release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, these Durable performance.

In the present invention, the fluorine-containing composition can be used as a surface treatment agent (for example, a water / oil repellent, an antifouling agent and a release agent).
The fluorine-containing composition contains a fluorine-containing polymer. The fluorine-containing polymer has a repeating unit derived from a fluorine-containing olefin and a repeating unit derived from a hydrocarbon-based vinyl.

In the present invention, fluorine-containing olefin (i) and hydrocarbon-based vinyl (ii) are used as monomers constituting the fluorine-containing polymer. If necessary, non-fluorine non-crosslinkable monomer (iii) and / or non-fluorine crosslinkable monomer (iv) may be used.

(I) Fluorine- containing olefin The fluorine- containing olefin (i) is preferably an olefin having 2 to 20 carbon atoms (particularly a monoolefin) containing a fluorine atom. Fluorine-containing olefin is a combination of carbon atom and fluorine atom, or a combination of carbon atom, fluorine atom and hydrogen atom, or a combination of carbon atom, fluorine atom and chlorine atom, a combination of carbon atom, fluorine atom, hydrogen atom and chlorine atom. It may consist of

The fluorine-containing olefin (i) has the general formula:
CR ¹ R ² = CR ³ R ⁴
[Wherein, R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. A carbon number represented by the general formula: C _m H _n F _p , wherein m is an integer of 1 to 10, n is an integer of 1 to 2 m, and p is 2m + 1-n. A 1-10 polyfluoroalkyl group, a C6-C18 perfluoroaryl group or a C6-C18 polyfluoroaryl group,
At least one of R ¹ , R ² , R ³ and R ⁴ is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms, a general formula: C _m H _n F _p (wherein m is 1 to 10 An integer, n is an integer of 1 to 2 m, and p is 2m + 1-n), a polyfluoroalkyl group having 1 to 10 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or 6 to 18 carbon atoms Of the polyfluoroaryl group. ]
It is preferable that it is a compound shown by these.

The R ¹ group, R ² group, R ³ group and R ⁴ group may be either linear or branched. The perfluoroalkyl group and the polyfluoroalkyl group preferably have 1 to 7, for example, 1 to 6, carbon atoms.

Examples of R ¹ , R ² , R ³ and R ⁴ groups (not atoms) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, trifluoromethyl Group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, difluoromethyl group, 2H-perfluoroethyl group, 3H-perfluoropropyl group, 4H-perfluorobutyl Group, 5H-perfluoropentyl group, 6H-perfluorohexyl group, pentafluorophenyl group, perfluoronaphthyl group, fluoroanthranyl group and the like.
R ¹ group and R ² group are fluorine atoms, and each of R ³ group and R ⁴ group is independently a hydrogen atom, a chlorine atom, a fluorine atom or a polyfluoroalkyl group (preferably a perfluoroalkyl group). Is preferred.

Preferred examples of the fluorinated olefin (i) include tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, CH ₂ = CFCF ₃ (1234yf), CH ₂ = CHCF ₃ (1243zf), CH ₂ = CFCHF ₂ (1243yf), CH ₂ = CClCF ₃ , and perfluorohexylethylene. Tetrafluoroethylene and hexafluoropropylene are particularly preferred.

(ii) Hydrocarbon vinyl Hydrocarbon vinyl (ii) is an olefin (particularly a monoolefin) containing no fluorine atom (generally having 2 to 32 carbon atoms, particularly 2 to 22 carbon atoms). The hydrocarbon vinyl (ii) has a carbon atom and a hydrogen atom, and may have an oxygen atom. A preferred example of the hydrocarbon vinyl (ii) is a vinyl ester of a carboxylic acid. The carboxylic acid is preferably a (generally saturated) aliphatic, aromatic, (generally saturated) alicyclic or araliphatic carboxylic acid having 1 to 30, especially 2 to 22 carbon atoms. The hydrocarbon vinyl (ii) preferably has one double bond and does not have a crosslinkable reactive group.

Hydrocarbon vinyl (ii) has the formula:
CH ₂ ═CH—O—C (═O) R ⁰
[Wherein, R ⁰ represents an aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group having 1 to 22 carbon atoms. ]
It is preferable that it is carboxylic acid vinyl ester shown by these.
The aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group is a linear or branched aliphatic group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, or 4 to 22 carbon atoms. Of these, an alicyclic group or an araliphatic group having 7 to 22 carbon atoms is preferable.

Preferable specific examples of the hydrocarbon vinyl (ii) include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl caprylate, vinyl decanoate, vinyl laurate. , Vinyl myristate, vinyl palmitate, vinyl stearate, vinyl behenate, vinyl cyclohexanecarboxylate, vinyl benzoate. Vinyl stearate is particularly preferred.

(iii) Non-fluorine non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (iii) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (iii) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (iii) is non-crosslinkable unlike the crosslinkable monomer (iv). The non-fluorine non-crosslinkable monomer (iii) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (iii) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (iii) is generally a compound having one carbon-carbon double bond.

Preferred non-fluorine non-crosslinkable monomers (iii) have the formula:
CH ₂ = CA ⁰ -T
[In the formula, A ⁰ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a chlorine atom, a chain or cyclic hydrocarbon group having 1 to 22 carbon atoms, or a chain or cyclic organic group having 1 to 22 carbon atoms having an ester bond. ]
It may be a compound shown by these.

Examples of the linear or cyclic hydrocarbon group having 1 to 22 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, a cyclic aliphatic group having 4 to 22 carbon atoms, and 6 to 6 carbon atoms. 22 aromatic hydrocarbon groups and aromatic aliphatic hydrocarbon groups having 7 to 22 carbon atoms.

Examples of the linear or cyclic organic group having 1 to 22 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 22 carbon atoms). Straight chain or branched aliphatic hydrocarbon group, cyclic aliphatic group having 4 to 22 carbon atoms, aromatic hydrocarbon group having 6 to 22 carbon atoms, and araliphatic hydrocarbon group having 7 to 22 carbon atoms). .

Preferred examples of the non-fluorine non-crosslinkable monomer (iii) include, for example, vinyl halides such as ethylene and vinyl chloride, vinylidene halides such as vinylidene chloride, acrylonitrile, styrene, polyethylene glycol (meth) acrylate, and polypropylene glycol. (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl alkyl ether are included. Non-fluorine non-crosslinkable monomer (iii) is not limited to these examples.

The non-fluorine non-crosslinkable monomer (iii) may be a (meth) acrylate ester having an alkyl group. The number of carbon atoms in the alkyl group may be 1-30, for example, 6-30 (eg 10-30). For example, the non-fluorine non-crosslinkable monomer (iii) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
An acrylate represented by For example, stearyl (meth) acrylate and behenyl (meth) acrylate may be used.

The non-fluorine non-crosslinkable monomer (iii) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is preferably 4-20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, but is preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, And cyclopentenyl acrylate.

(iv) Non-fluorine crosslinkable monomer The fluorine-containing polymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (iv). The non-fluorine crosslinkable monomer (iv) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (iv) may be a compound having at least two reactive groups and / or a carbon-carbon double bond and not containing fluorine. The non-fluorine crosslinkable monomer (iv) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
The non-fluorine crosslinkable monomer (iv) may be mono (meth) acrylate, (meth) diacrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (iv) may be di (meth) acrylate.
One example of the non-fluorine crosslinkable monomer (iv) is a vinyl monomer having a hydroxyl group.

Non-fluorine crosslinkable monomers (iv) include, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxy Propyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Examples include glycol di (meth) acrylate, but are not limited thereto.
In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

By copolymerizing the non-fluorine non-crosslinkable monomer (iii) and / or the non-fluorine crosslinkable monomer (iv), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.

In the fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing olefin (i),
The amount of hydrocarbon-based vinyl (ii) is 2 to 500 parts by weight, for example 5 to 200 parts by weight, in particular 20 to 150 parts by weight;
The amount of the non-fluorine non-crosslinkable monomer (iii) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,
The amount of the non-fluorine crosslinkable monomer (iv) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.
Alternatively, in the fluorine-containing polymer, the ratio of the repeating unit (i) derived from the fluorine-containing olefin / the repeating unit (ii) derived from the hydrocarbon vinyl is 1 to 80 mol% / 20 to 99 mol%, preferably 10 It may be ˜60 mol% / 40 to 90 mol%, for example 15 to 40 mol% / 60 to 85 mol%.

The number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 2,000 to 500,000, especially from 3,000 to 200,000. The number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).

The fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and is purged with nitrogen as necessary, followed by heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

Examples of the organic solvent are those which are inert to the monomer and dissolve them, such as acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total monomer.

In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and is purged with nitrogen if necessary, and stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Is done. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

In order to obtain an aqueous copolymer dispersion with excellent storage stability, the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, it may be used in the range of 10 to 40 parts by weight. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers. For example, it may be used in the range of 10 to 40 parts by weight.

The fluoropolymer can be used for surface treatment of various substrates such as fibers.
The fluoropolymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid. The concentration of the fluorosilicone reaction product in the solution applied to the textile product may be, for example, 0.5 wt% to 20 wt%, alternatively 1 wt% to 5 wt%. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

Alternatively, the fluoropolymer may be applied to the fiber product by a cleaning method, and may be applied to the fiber product in, for example, a laundry application or a dry cleaning method.

The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

The fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous emulsion) or an aerosol. The fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (in particular, a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the fluorine-containing composition.
In the fluorine-containing composition, the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

The fluorine-containing composition of the present invention can be applied to an object to be processed by a conventionally known method. Usually, the fluorine-containing composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured. Furthermore, insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the fluorine-containing composition of the present invention. The concentration of the fluoropolymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

Examples of objects to be treated with the fluorine-containing composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like. When the carpet is treated with the fluorine-containing composition of the present invention, the carpet may be formed after the fibers or yarns are treated with the fluorine-containing composition, or the formed carpet is treated with the fluorine-containing composition. Also good.
The fluorine-containing composition of the present invention can also be used as an internal release agent or an external release agent.

“Processing” means applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, “%” represents “% by weight” unless otherwise specified.
The test (analysis of fluoropolymer and measurement of water / oil repellency) was performed as follows.

"Molecular weight measurement 1":
The number average molecular weight (Mn) of the fluorine-containing polymer was measured using Shodex GPC-104 (column LF604 × 2 series) manufactured by SHOWA DENKO using tetrahydrofuran as a solvent. The chromatogram was calibrated using a standard polystyrene sample.

“Molecular weight measurement 2”:
The number average molecular weight (Mn) of the fluorinated polymer is a mixture of HCFC225 and 1,1,1,3,3,3-hexafluoro-2-propanol in a ratio of 90:10, and TOSOH TSK guard column HXL is used as a column. -L (6.0 mm ID × 4 cm), TOSOH TSKgel G4000HXL (7.8 mm ID × 30 cm), TOSOH TSKgel G3000HXL (7.8 mm ID × 30 cm), TOSOH TSKgel G2000HXL (7.8 mm ID) . × 30 cm) was measured by GPC analysis at 30 ° C. using a pipe connected in series. The chromatogram was calibrated using a standard PMMA (polymethyl methacrylate) sample.

"Thermal characteristics":
The glass transition temperature (Tg) or crystalline melting point (Tm) of the fluoropolymer is measured with a thermal analyzer DSC (SEIKO-RDC220) at a temperature increase rate of 10 ° C./min in the temperature range of −50 to 150 ° C. did.

"Water and oil repellency":
As a water / oil repellency evaluation of a fluoropolymer, the dynamic contact angle of water droplets (surface tension 72 mN / m) and n-hexadecane droplets (surface tension 27 mN / m, hereinafter abbreviated as HD) was measured as follows. did. As an index of the dynamic contact angle, the falling angle (deg) and the hysteresis (deg) representing the difference between the advancing contact angle and the receding contact angle were measured and evaluated. That is, the fluoropolymer was made into a 1% solution in an organic solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then dried to form a film. Next, using a contact angle meter (trade name “CA-VP”) manufactured by Kyowa Interface Science Co., Ltd., the dynamic contact angle of 20 μl of water droplet or 5 μl of HD droplet was measured. In accordance with JISR3257, the measurement is performed at a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70%. The smaller the falling angle and the smaller the hysteresis, the better the water / oil repellency.

"Shower water repellency":
Shower water repellency was measured according to JIS-L-1092 water repellency No. (See Table 1 below).

Example 1
A 300 ml autoclave was charged with 6.0 g (19 mmol) of vinyl stearate, 50 g of butyl acetate and 0.3 g of t-butyl peroxypivalate, and oxygen in the system was removed by nitrogen substitution. Next, 8.7 g (57 mmol) of hexafluoropropylene was charged, the temperature was gradually raised, and the polymerization reaction was carried out at 60 ° C. for 12 hours. The reaction solution cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, collected by filtration, washed, and then vacuum dried to obtain a fluoropolymer. Table 2 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from hexafluoropropylene was 42 mol%.

Example 2
A fluoropolymer was obtained by repeating the same procedure as in Example 1 except that hexafluoropropylene was changed to 5.7 g (57 mmol) of tetrafluoroethylene. Table 2 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from tetrafluoroethylene was 51 mol%.

Example 3
The same procedure as in Example 1 was repeated except that the vinyl stearate was changed to 1.7 g (19 mmol) of vinyl acetate, and the polymer was precipitated by putting the reaction solution after polymerization into a large amount of methanol. A fluoropolymer was obtained. Table 2 shows the analysis results of the fluoropolymer having a polymer unit content of 34 mol% derived from hexafluoropropylene.

Example 4
The same procedure as in Example 2 was repeated except that vinyl stearate was changed to 1.7 g (19 mmol) of vinyl acetate, and the polymer was precipitated by adding the reaction solution after polymerization into a large amount of methanol. A fluoropolymer was obtained. Table 2 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from tetrafluoroethylene was 52 mol%.

Example 5
A fluoropolymer was obtained by repeating the same procedure as in Example 3 except that hexafluoropropylene was changed to 6.9 g (57 mmol) of chlorotrifluoroethylene. Table 2 shows the analysis results of the fluoropolymer in which the content of polymerized units derived from chlorotrifluoroethylene was 53 mol%.

Comparative Example 1
To a 300 ml autoclave, 2- (perfluorooctyl) ethyl acrylate (CH ₂ ═CH—COO— (CH ₂ ) ₂ — (CF ₂ ) ₈ F) 9.8 g (19 mmol), HCFC225 50 g, t-butyl peroxypi 0.3 g of barate was added, and oxygen in the system was removed by nitrogen substitution. Next, the temperature was gradually raised and the polymerization reaction was carried out at 60 ° C. for 12 hours. The reaction solution cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, collected by filtration, washed, and then vacuum dried to obtain a fluoropolymer. Table 2 shows the analysis results of the obtained fluoropolymer.

Comparative Example 2
8.4 g (19 mmol) of 2- (perfluorooctyl) ethyl acrylate with 2- (perfluorohexyl) ethyl methacrylate (CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ — (CF ₂ ) ₆ F) The same procedure as in Comparative Example 1 was repeated except that the fluoropolymer was obtained. Table 2 shows the analysis results of the obtained fluoropolymer.

(Mn of Examples 1 to 5 was measured by the method of molecular weight measurement 1, and Mn of Comparative Examples 1 and 2 was measured by the method of molecular weight measurement 2. In the table, nd: not observed.)

Example 6
The fluoropolymer obtained in Example 1 was made into a 1% solution in a methyl isobutyl ketone solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then vacuum-dried at room temperature for 48 hours to form a film. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Example 7
A film was formed by repeating the same procedure as in Example 6 except that the fluoropolymer obtained in Example 2 was used. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Example 8
The fluoropolymer obtained in Example 3 was made into a 1% solution in a methyl isobutyl ketone solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then heat-treated at 75 ° C. for 3 minutes to form a film. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Example 9
A film was formed by repeating the same procedure as in Example 8 except that the fluoropolymer obtained in Example 4 was used. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Example 10
A film was formed by repeating the same procedure as in Example 8 except that the fluoropolymer obtained in Example 5 was used. Table 3 shows the results of measuring the falling angle and hysteresis of the water droplets of the obtained coating film.

Comparative Example 3
The fluoropolymer obtained in Comparative Example 1 was made into a 1% solution in HCFC225 solvent, applied to a glass substrate by spin coating (2000 rpm), and then heat treated at 75 ° C. for 3 minutes to form a film. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Comparative Example 4
A film was formed by repeating the same procedure as in Comparative Example 3 except that the fluoropolymer obtained in Comparative Example 2 was used. Table 3 shows the results of measuring the drop angle and hysteresis of water drops, and Table 4 shows the result of measuring the drop angle and hysteresis of HD drops.

Example 11
1 g of the fluoropolymer obtained in Example 1 and 99 g of methyl isobutyl ketone were mixed to obtain a treatment liquid. A Polyester cloth (taffeta, 25 cm × 25 cm) was immersed in the obtained treatment liquid and squeezed with a roll so that the wet pickup was 40%. The fabric was then dried in a local evacuator for 24 hours at room temperature and further heat treated at 120 ° C. for 3 minutes to complete the fabric treatment. Table 5 shows the results of a shower water repellency test on the obtained fabric.

Example 12
The fabric was treated by repeating the same procedure as in Example 11 except that the fluoropolymer obtained in Example 2 was used. Table 5 shows the results of a shower water repellency test on the obtained fabric.

Comparative Example 5
The fabric was treated by repeating the same procedure as in Example 11 except that 1 g of the fluoropolymer obtained in Comparative Example 1 and 99 g of HCFC225 were used as the treatment liquid. Table 5 shows the results of a shower water repellency test on the obtained fabric.

Comparative Example 6
The fabric was treated by repeating the same procedure as in Comparative Example 5 except that the fluoropolymer obtained in Comparative Example 2 was used. Table 5 shows the results of a shower water repellency test on the obtained fabric.

As can be seen from Tables 3 and 4, the fluoropolymer of the present invention has low measured values of the falling angle and hysteresis. The small falling angle and hysteresis indicate that the environmental responsiveness to water droplets and HD droplets is small, indicating that the fluoropolymer of the present invention is excellent in water and oil repellency. Further, from Table 5, it can be seen that the water- and oil-repellency of the fluoropolymer of the present invention is excellent even in the use of water and oil-repellent agents for fibers.

Example 13
A 300 ml autoclave was sealed with 10.0 g (32 mmol) of vinyl stearate, 50.0 g of butyl acetate and 0.3 g of t-butyl peroxypivalate, and oxygen in the system was removed by nitrogen substitution. Next, 21.0 g (210 mmol) of tetrafluoroethylene was charged, the temperature was gradually raised, and the polymerization reaction was carried out at 60 ° C. for 12 hours. The reaction solution cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, collected by filtration, washed, and then vacuum dried to obtain a fluoropolymer. Table 6 shows the analysis results of the fluoropolymer in which the content of polymer units derived from tetrafluoroethylene was 63 mol%.

Example 14
A fluoropolymer was obtained by repeating the same procedure as in Example 13 except that the amount of tetrafluoroethylene was changed to 1.0 g (10 mmol). Table 6 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from tetrafluoroethylene was 25 mol%.

Example 15
A fluoropolymer was obtained by repeating the same procedure as in Example 13 except that 21.0 g (210 mmol) of tetrafluoroethylene was changed to 1.3 g (9 mmol) of hexafluoropropylene. Table 6 shows the analysis results of the fluoropolymer in which the content of the polymerization units derived from hexafluoropropylene was 12 mol%.

Example 16
Except for changing 1 type of fluorine-containing olefin of 21.0 g (210 mmol) of tetrafluoroethylene to 2 types of fluorine-containing olefin of 8.0 g (80 mmol) of tetrafluoroethylene and 2.6 g (17 mmol) of hexafluoropropylene. The same procedure as 13 was repeated to obtain a fluoropolymer. Table 6 shows the analysis results of the fluoropolymer in which the content of polymer units derived from tetrafluoroethylene was 49 mol% and the content of polymer units derived from hexafluoropropylene was 12 mol%.

Example 17
The same procedure as Example 13 was repeated except that 21.0 g (210 mmol) of tetrafluoroethylene was changed to 3.0 g (47 mmol) of vinylidene fluoride and the amount of vinyl stearate was changed to 9.5 g (31 mmol). A fluoropolymer was obtained. Table 6 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from vinylidene fluoride was 16 mol%.

Example 18
The same procedure as in Example 13 was repeated except that 21.0 g (210 mmol) of tetrafluoroethylene was changed to 6.7 g (19 mmol) of perfluorohexylethylene and the amount of vinyl stearate was changed to 6.0 g (17 mmol). A fluoropolymer was obtained. Table 6 shows the analysis results of the fluoropolymer in which the content of the polymer units derived from perfluorohexylethylene was 15 mol%.

Example 19
Example 1 except that 21.0 g (210 mmol) of tetrafluoroethylene was changed to 10.0 g (88 mmol) of CH ₂ ═CFCF ₃ (hereinafter, 1234yf) and the amount of vinyl stearate was changed to 18.0 g (58 mmol). The same procedure as 13 was repeated to obtain a fluoropolymer. Table 6 shows the analysis results of the fluoropolymer in which the content of polymerization units derived from 1234yf was 51 mol%.

(Mn in Examples 13 to 19 was measured by the method of molecular weight measurement 1)

Example 20
The fluoropolymer obtained in Example 13 was made into a 1% solution in a methyl isobutyl ketone solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then vacuum-dried at room temperature for 48 hours to form a film. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 21
A film was formed by repeating the same procedure as in Example 20, except that the fluoropolymer obtained in Example 14 was used and that methyl isobutyl ketone was changed to toluene. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 22
A film was formed by repeating the same procedure as in Example 20 except that the fluoropolymer obtained in Example 15 was used and that methyl isobutyl ketone was changed to toluene. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 23
A film was formed by repeating the same procedure as in Example 20 except that the fluoropolymer obtained in Example 16 was used. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 24
A film was formed by repeating the same procedure as in Example 20 except that the fluoropolymer obtained in Example 17 was used and that methyl isobutyl ketone was changed to toluene. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 25
A film was formed by repeating the same procedure as in Example 20 except that the fluoropolymer obtained in Example 18 was used and that methyl isobutyl ketone was changed to toluene. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 26
A film was formed by repeating the same procedure as in Example 20, except that the fluoropolymer obtained in Example 19 was used. Table 7 shows the results of measuring the drop angle and hysteresis of the water droplets of the obtained coating film.

Example 27
A 1 L autoclave was charged with 38.3 g (123 mmol) of vinyl stearate, 79.8 g of pure water, 13.5 g of tripropylene glycol, 1.4 g of octadecyltrimethylammonium chloride, and 3.4 g of polyethylene glycol lauryl ether. And emulsified with ultrasonic waves for 15 minutes. After emulsification, 0.2 g of n-dodecyl mercaptan was added, sealed, and oxygen in the system was removed by nitrogen replacement. Further, 12.3 g (123 mmol) of tetrafluoroethylene was injected and filled. Further, 0.2 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted for 10 hours to obtain an aqueous dispersion of the fluorine-containing copolymer of the present invention. Finally, it was diluted with water so as to be a 20% aqueous dispersion of the fluorinated copolymer. The fluorine-containing copolymer had a molecular weight Mn of 25,900 (Mn was measured by the method of molecular weight measurement 1), and the content of polymer units derived from tetrafluoroethylene was 9 mol%.

Example 28
A 1 L autoclave was charged with 11.6 g (37 mmol) of vinyl stearate, 996.5 g of pure water, 3.5 g of tripropylene glycol, 0.4 g of octadecyltrimethylammonium chloride, and 0.9 g of polyethylene glycol lauryl ether, and the mixture was stirred at 60 ° C. And emulsified with ultrasonic waves for 15 minutes. After emulsification, the system was sealed and oxygen in the system was removed by nitrogen replacement. Further, 76.0 g (760 mmol) of tetrafluoroethylene was injected and filled. Further, 0.1 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted for 10 hours to obtain an aqueous dispersion of the fluorine-containing copolymer of the present invention. Finally, it was diluted with water so as to be a 20% aqueous dispersion of the fluorinated copolymer. The fluorine-containing copolymer had a molecular weight Mn of 44,800 (Mn was measured by the method of molecular weight measurement 1), and the content of polymer units derived from tetrafluoroethylene was 24 mol%.

Example 29
1.0 g of the aqueous dispersion of the fluorinated copolymer obtained in Example 27 was diluted with 99.0 g of water to obtain a treatment liquid. A Polyester cloth (taffeta, 25 cm × 25 cm) was immersed in the obtained treatment liquid and squeezed with a roll so that the wet pickup was 40%. The fabric was then treated by drying at 120 ° C. for 3 minutes and further heat treating at 170 ° C. for 1 minute. Table 8 shows the result of the shower water repellency test on the obtained fabric.

Example 30
The fabric was treated by repeating the same procedure as in Example 29 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Example 28 was used. Table 8 shows the result of the shower water repellency test on the obtained fabric.

Claims

A surface treating agent composition comprising: (i) a repeating unit derived from a fluorine-containing olefin; and (ii) a fluorine-containing polymer having a repeating unit derived from a hydrocarbon-based vinyl.
The fluorine-containing olefin has the general formula:
CR 1 R 2 = CR 3 R 4
[Wherein, R 1 , R 2 , R 3 and R 4 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. A carbon number represented by the general formula: C m H n F p , wherein m is an integer of 1 to 10, n is an integer of 1 to 2 m, and p is 2m + 1-n. A 1-10 polyfluoroalkyl group, a C6-C18 perfluoroaryl group or a C6-C18 polyfluoroaryl group,
At least one of R 1 , R 2 , R 3 and R 4 is a fluorine atom, a perfluoroalkyl group having 1 to 10 carbon atoms, a general formula: C m H n F p (wherein m is 1 to 10 An integer, n is an integer of 1 to 2 m, and p is 2m + 1-n), a polyfluoroalkyl group having 1 to 10 carbon atoms, a perfluoroaryl group having 6 to 18 carbon atoms, or 6 to 18 carbon atoms Of the polyfluoroaryl group. ]
The surface treatment agent composition according to claim 1, which is represented by:
Fluorine-containing olefin is tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, chlorotrifluoroethylene, CH 2 = CFCF 3 (1234yf), CH 2 = CHCF 3 (1243zf), CH 2 = CFCHF 2 (1243yf), CH 2 = CClCF 3 and a surface treatment composition according to claim 1 is at least one selected from the group consisting of perfluorohexyl ethylene.
The surface treating agent composition according to claim 1, wherein the fluorinated olefin is tetrafluoroethylene or hexafluoropropylene.
The surface treating agent composition according to any one of claims 1 to 4, wherein the hydrocarbon vinyl (ii) is a vinyl ester of a carboxylic acid obtained from a carboxylic acid having 1 to 30 carbon atoms.
Hydrocarbon vinyl (ii) is vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl caprylate, vinyl decanoate, vinyl laurate, vinyl myristate, The surface treating agent composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of vinyl palmitate, vinyl stearate, vinyl behenylate, vinyl cyclohexanecarboxylate and vinyl benzoate.
The surface treating agent composition according to any one of claims 1 to 6, wherein the hydrocarbon vinyl (ii) is vinyl stearate.
A fluoropolymer,
(iii) The surface treating agent composition according to any one of claims 1 to 7, which has a repeating unit derived from a non-fluorine non-crosslinkable monomer.
A fluoropolymer,
(iv) The surface treating agent composition according to any one of claims 1 to 8, which has a repeating unit derived from a non-fluorine crosslinkable monomer.
The surface treating agent composition according to any one of claims 1 to 9, further comprising a liquid medium.
In the fluorine-containing polymer, the ratio of the repeating unit (i) derived from the fluorine-containing olefin / the repeating unit (ii) derived from the hydrocarbon vinyl is 1 to 80 mol% / 20 to 99 mol%. The surface treating agent composition according to any one of 10.
The surface treating agent composition according to any one of claims 1 to 11, which is a water / oil repellent, an antifouling agent or a release agent.
A method for treating a substrate, comprising treating with the surface treating agent composition according to any one of claims 1 to 12.
A textile product treated with the surface treating agent composition according to any one of claims 1 to 12.