KR20130076757A - Fluorine containing composition and fluorine containing polymer - Google Patents

Abstract

PURPOSE: A fluorine-containing composition is provided to provide fiber products with excellent water and oil repellencies and to prevent polymers from being attached to a roll during a molding process. CONSTITUTION: A fluorine-containing composition contains a fluorine-containing polymer. The fluorine-containing polymer includes a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl; a repeating unit derived from a C12-30 linear or branched hydrocarbon group-containing acrylate monomer; and a repeating unit derived from a (meth)acrylate monomer of which the glass transition temperature (Tg) or the melting point (Tm) is 50 °C or more.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a fluorine-containing composition and a fluorine-

The present invention relates to a fluorine-containing composition and a fluorine-containing polymer. According to the present invention, it is possible to produce a fluorine-containing polymer which imparts excellent water repellency, oil repellency and antifouling property to a fiber product (for example, carpet), paper, nonwoven fabric, stone, electrostatic filter, dustproof mask, .

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. Using the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere, the fluorine-containing compound is used, for example, as a water- and oil- For example, U.S. Patent No. 5,247,008 discloses a process for the preparation of an aqueous dispersion of a copolymer of a perfluoroalkyl ester of acrylic acid or methacrylic acid with an alkyl ester of acrylic acid or methacrylic acid and an aminoalkyl ester of acrylic acid or methacrylic acid Finishing agents for textile, leather, paper and mineral substrates are described.

For the purpose of improving the durability of the water-repellent and oil repellent against conventional washing and dry cleaning, it is also possible to copolymerize a monomer having an adhesive group together with a fluoroalkyl group-containing polymerizable monomer, or to copolymerize a polymer containing a fluoroalkyl group and a Attempts have been made to blend polymers. In the field of paints (coatings), it has been succeeded to maintain the properties of fluorine and to impart new properties of processability by using a particle polymer having a multi-layer structure (for example, JP 06-56944 A).

In addition, a composition of a multi-layered particle polymer is proposed to have properties such as durability and low temperature curing (for example, Japanese Patent Application Laid-Open Nos. 02-001795, 07-278422, 172126, Japanese Patent Application Laid-Open No. 2007-291373).

In addition, in the water-repellent and oil repellent processing bath in which conventional general aqueous dispersions are diluted, the dispersion liquid is broken by the mechanical impact which is caused when the processed dough is introduced, and the aggregation and sedimentation of the emulsion particles are caused, Adhered to the paper, contamination of the paper, and contamination of the roll. (Japanese Patent Laid-Open No. 9-118877, for example, WO 2004/069924). However, according to the recent diversity of water-repellent oil processing, it is not always possible to provide sufficiently satisfactory stability Respectively. Further, as for the problem that a polymer is adhered to a roll, problems tend to occur as the stickiness of the polymer is higher. When the number of carbon atoms of the fluoroalkyl group of the fluoroalkyl group-containing polymer is 6 or less, the melting point of the polymer is lowered, so that the tackiness tends to be higher than that of the fluoroalkyl group having 8 or more carbon atoms.

U.S. Patent No. 5247008 Japanese Patent Laid-Open No. 06-56944 Japanese Patent Application Laid-Open No. 02-001795 Japanese Patent Laid-Open No. 07-278422 Japanese Patent Laid-Open No. 11-172126 Japanese Patent Application Laid-Open No. 2007-291373 Japanese Patent Laid-Open No. 9-118877 WO2004 / 069924

An object of the present invention is to provide a water- and oil-repellent composition which imparts excellent water- and oil-repellency to a base material such as a textile product, and is excellent in preventing adhesion of a polymer to a roll in its processing.

In order to solve the above problems, the present inventors have conducted intensive investigations with the object of providing a water- and oil-repellent composition which suppresses the production of a polymer portion having high stickiness, exhibits high water- and oil-repellency, and is also excellent in durability. As a result, it has been found that the above object can be achieved when the non-fluorine polymer portion of the fluorine-containing polymer has a specific composition, and thus the present invention has been accomplished.

According to the present invention,

(a) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group,

(b) a repeating unit derived from a second monomer which is an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms and

(c) a repeating unit derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or melting point (Tm) of not less than 50 DEG C of the homopolymer

Containing polymer is a fluorine-

In the fluorine-containing polymer, the amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight based on 100 parts by weight of the total amount of the second monomer (b) and the third monomer (c) And the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight.

The present invention also provides a fluorine-containing composition containing the fluorine-containing polymer.

The fluorine-containing composition of the present invention imparts excellent water and oil repellency to a base material such as a fiber product, and is excellent in preventing adhesion of a polymer to a roll in its processing.

In the present invention, the tackiness and the bumpability are low, and good processing can be performed.

In the present invention, (a) a fluorine-containing monomer, (b) a linear or branched hydrocarbon group-containing acrylate monomer, and (c) a third monomer other than the monomers (a) and (b) are used.

In the present invention, the fluorine-

(a) a repeating unit derived from a fluorine-containing monomer (e.g., acrylate, methacrylate,? -chlorosubstituted acrylate)

(b) a repeating unit derived from a linear or branched hydrocarbon group-containing acrylate monomer and

(c) a repeating unit derived from the third monomer

.

The fluorine-containing polymer of the present invention,

Containing only the repeating units derived from the monomer (a), the monomer (b) and the monomer (c), or

In addition to the repeating unit derived from the monomer (a), the monomer (b) and the monomer (c), a repeating unit derived from another monomer.

(a) a fluorine-containing monomer

The fluorine-containing monomer (a) has the formula:

CH ₂ = C (-X) -C (= O) -YZ-Rf

Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group,

And Rf is a fluoroalkyl group having 1 to 20 carbon atoms]

Is a fluorine-containing monomer.

The fluorine-containing monomer (a) may be substituted with a halogen atom or the like at the α-position (of acrylate (X: hydrogen atom) or methacrylate (X: methyl group) Therefore, when X is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² are each a hydrogen atom, A fluorine atom, a bromine atom or an iodine atom), a cyano group, a straight or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, and a substituted or unsubstituted phenyl group. Particularly, X may be a chlorine atom.

The fluorine-containing monomer (a) is preferably an acrylate ester in which the group Y is -O-.

The Z group is specifically a linear or branched aliphatic group (for example, an alkylene group) having 1 to 20 carbon atoms (e.g., 1 to 10 carbon atoms, particularly 1 to 4, especially 1 or 2) carbon atoms, For example, a group represented by the formula - (CH ₂ ) _x - (wherein x is 1 to 10), or

An aromatic group or a cyclic aliphatic group having 6 to 18 carbon atoms,

Formula ^{-R 2 (R 1) N-} SO 2 - , or, R ¹ a group (represented by the formula ^{-R 2 (R 1) N-} CO- is an alkyl group having 1 to 10, R ² is C 1 (R ¹ ) SO ₂ - group (provided that R ¹ is an alkyl group having 1 to 4 carbon atoms), or a linear or branched alkylene group having from 1 to 10 carbon atoms, for example, -CH ₂ CH ₂ N

Formula ^{_{-CH 2 CH (OR 3) CH}} 2 - [Ar- (O) q] p - (wherein, R ³ is an acyl group of a hydrogen atom, or 1 to 10 carbon atoms (e.g., formyl or acetyl, etc. ), Ar is an arylene group optionally having a substituent (for example, a phenylene group), p is 0 or 1, q is 0 or 1), or

The formula _{- (CH 2) n -Ar- (} O) q - ( wherein, Ar is an arylene group having a substituent as needed (e.g., phenylene group), n is from 0 to 10, q is 0 or 1 , ≪ / RTI >

- (CH ₂ ) _m --SO ₂ - (CH ₂ ) _n - group or - (CH ₂ ) _m -S- (CH ₂ ) _n- group wherein m is 1 to 10 and n is 0 to 10, It may be.

The aromatic group or cyclic aliphatic group may be substituted or unsubstituted. The S group or SO ₂ group may be bonded directly to the R f group.

It is preferable that the Rf group is a perfluoroalkyl group. The carbon number of the Rf group is preferably 1 to 12, for example, 1 to 6, particularly 4 to 6. Examples of Rf groups _{include, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) _{2, -C (CF 3) 3} , - (CF 2) 4 CF 3, - (CF 2) 2 CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF 2 CF ₂ CF ₃ , - (CF ₂ ) ₅ CF ₃ , - (CF ₂ ) ₃ CF (CF ₃ ) ₂ , - (CF ₂ ) ₄ CF (CF ₃ ) ₂ and -C ₈ F ₁₇ .

Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.

[Wherein Rf is a fluoroalkyl group having 1 to 20 carbon atoms]

(b) a second monomer ( Carbon number  12 to 30 Straight  or Bifurcated  Having a hydrocarbon group Acrylate  Monomer)

The second monomer (b) is a monomer having no fluoroalkyl group. The second monomer (b) has no cyclic hydrocarbon group. The second monomer (b) is a monomer generally not containing a fluorine atom. The linear or branched hydrocarbon group may have a linear hydrocarbon group in particular. The linear or branched hydrocarbon group preferably has 12 to 30 carbon atoms and is generally a saturated aliphatic hydrocarbon group.

The second monomer (b) may be an alkyl acrylate ester. The number of carbon atoms of the alkyl group may be 12 to 30, for example, 12 to 22, particularly 14 to 20. For example, the second monomer (b) has the formula:

CH ₂ = CHCOOA ¹

[Wherein,

A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30, particularly 12 to 22)

May be used.

Specific examples of the second monomer (b) include, for example, the following, but are not limited thereto.

(I.e., lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate)

(c) Third monomer: (glass of homopolymer Advantages ( Tg ) Or melting point ( Tm ) Is not less than 50 DEG C ( Mat ) Acrylate  Monomer)

The third monomer (c) is a (meth) acrylate monomer whose homopolymer has a glass transition point (Tg) or melting point (Tm) of not lower than 50 ° C, for example, not lower than 60 ° C. Glass transition point and melting point are the extrapolated glass transition end temperature (T e _g ) and the melting peak temperature (T _pm ) defined in JIS K7121-1987 "Method of measuring transition temperature of plastics", respectively. The upper limit of the glass transition point (Tg) or the melting point (Tm) may be 300 占 폚, for example, 200 占 폚.

The third monomer (c) is a monomer other than the monomers (a) and (b). The third monomer (c) has no fluoroalkyl group.

The third monomer (c) has the formula:

CH = CR ¹¹ -C (= O) OR ¹²

Wherein R ¹¹ is H, a C ₁ to C ₄ alkyl group or a halogen,

R ¹² is a C ₁ to C ₃₀ linear, branched or cyclic aliphatic group, a C ₆ to C ₂₀ aromatic group, a C ₇ to C ₂₅ aromatic aliphatic group,

Is an acrylate ester compound.

Examples of R ¹¹ are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom and an iodine atom. It is preferable that R ¹¹ is a methyl group.

Examples of R ¹² include an alkyl group (e.g., having 1 to 6 carbon atoms) (e.g., methyl group, ethyl group, propyl group, butyl group), a cycloalkyl group (e.g., A cyclohexyl group), a polycyclic aliphatic group (for example, having 7 to 20 carbon atoms) (for example, a norbornyl group, a boronyl group, an isobornyl group, an adamantyl group), a phenyl group, a naphthyl group, .

R ¹² preferably has a cyclic group, and is preferably a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an aromatic aliphatic group. In particular, when R ¹¹ is a hydrogen atom, R ¹² preferably has a cyclic group, and is generally a cycloalkyl group, a polycyclic aliphatic group, an aromatic group, or an aromatic aliphatic group.

As specific examples of the third monomer (c)

Acrylate, isobornyl acrylate, isobornyl acrylate, boronyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate , Benzyl acrylate, 2-t-butylphenyl acrylate, and naphthyl acrylate;

And examples thereof include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicyclopentyl methacrylate, (2-dimethylamino) ethyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, Methacrylate esters such as ridinyl methacrylate, aziridinyl ethyl methacrylate and dicyclopentenyl methacrylate;

And chloroacrylate esters such as methyl chloroacrylate, but are not limited thereto.

(d) Other monomers

Other monomers (d) other than the monomers (a), (b) and (c) may be used, for example, other non-fluorine-incompatible monomers.

Examples of other monomers include ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylate and vinyl alkyl ether. Other monomers are not limited to these examples.

Other monomers may be halogenated olefins.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms which is substituted with 1 to 10 chlorine, bromine or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, especially an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms. Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

Other monomers may be non-fluorine-crosslinkable monomers. The non-fluorine-crosslinkable monomer is a monomer not containing a fluorine atom. The non-fluorine-crosslinkable monomer may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine-crosslinkable monomer 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 the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, and a carboxyl group.

The non-fluorine-crosslinkable monomer may be mono (meth) acrylate, di (meth) acrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine-crosslinkable monomer may be di (meth) acrylate.

One example of the non-fluorine-crosslinkable monomer is a vinyl monomer having a hydroxyl group.

Examples of the nonfluorine-crosslinkable monomer include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like, but are not limited thereto.

In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

In the fluorine-containing polymer, the amount of the fluorine-containing monomer (a) may be 5 to 95% by weight, for example, 10 to 90% by weight, particularly 20 to 70% by weight, of the fluorine-containing polymer.

The total amount of the second monomer (b) and the third monomer (c) is 5 to 3000 parts by weight, for example, 10 to 2000 parts by weight, particularly 30 to 1000 parts by weight, based on 100 parts by weight of the fluorine- Grant is also good.

The amount of the other monomer (d) may be 500 parts by weight or less, for example, 1-200 parts by weight per 100 parts by weight of the fluorine-containing monomer (a).

The amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight, and the amount of the second monomer (b) is 100 parts by weight based on the total amount of the second monomer (b) and the third monomer , The amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight, the amount of the third monomer (c) is 50 to 99 parts by weight, 0.5 to 16 parts by weight or 50 to 95 parts by weight, in particular 1 to 15 parts by weight or 50 to 90 parts by weight.

When the fluorine-containing polymer contains a halogenated olefin (for example, vinyl halide), the amount of the halogenated olefin is preferably 30 to 30 parts by weight based on 100 parts by weight of the total amount of the second monomer (b), the third monomer (c) To 90 parts by weight, for example, 50 to 85 parts by weight, particularly preferably 60 to 80 parts by weight.

The number average molecular weight (Mn) of the fluorine-containing polymer may be generally from 1,000 to 1,000,000, for example, from 5,000 to 500,000, particularly from 3,000 to 200,000. The number average molecular weight (Mn) of the fluorine-containing polymer is generally measured by GPC (gel permeation chromatography).

In the present invention, the monomers (a) to (c) (and other monomer (d), if necessary) are copolymerized to obtain a fluorine-containing composition in which the fluorine-containing polymer is dispersed or dissolved in the medium.

The monomer may be polymerized in the presence of at least one compound selected from the group consisting of a block isocyanate compound and an organopolysiloxane compound. The amount of the block isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example, 1 to 50 parts by weight per 100 parts by weight of the monomer.

By polymerizing the monomers in the presence of a block isocyanate compound, a fluorine-containing polymer having a block isocyanate group is obtained. The block isocyanate compound is an isocyanate blocked by at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles and active methylene compounds. Other examples of the blocking agent include pyridines, thiophenols, diketones and esters. The block isocyanate compound may be modified by a compound having a hydrophilic group.

The monomer is polymerized in the presence of an organopolysiloxane compound (e.g., mercapto functional organopolysiloxane, vinyl functional organopolysiloxane) to obtain a fluorine-containing polymer having a siloxane group. In one embodiment, the mercapto functional organopolysiloxane has siloxy units having the following average formula:

(R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c

Wherein a is 0 to 4000, or 0 to 1000, or 0 to 400,

b is 1 to 1000, or 1 to 100, or 1 to 50,

c is 1 to 1000, or 1 to 100, or 1 to 50;

R is independently a monovalent organic group,

Or R is a hydrocarbon having 1 to 30 carbon atoms,

Or R is a monovalent alkyl group having 1 to 12 carbon atoms,

Or R is a methyl group;

R ^N is a monovalent amino functional organic group,

R ^S is a monovalent mercapto-functional organic group]

An amino functional organic group R ^N having an organic functional group is a group represented by the formula: -R ¹ NHR ² , the formula: -R ¹ NR ₂ ² or the formula: -R ¹ NHR ¹ NHR ^{2 wherein} each R ¹ is independently A divalent hydrocarbon group having 2 or more carbon atoms, and R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms). Each R < ^{1 >} is typically an alkylene group having 2 to 20 carbon atoms.

Some examples of suitable amino functional hydrocarbon groups include,

R ^S is a group represented by the formula: -R ¹ SR ^{2 wherein} each R ¹ is independently a divalent hydrocarbon group having at least 2 carbon atoms and R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, ¹ and R ² are as defined above. Each R < ^{1 >} is typically an alkylene group having 2 to 20 carbon atoms. Examples of the mercapto functional group are represented by the following formula:

-CH ₂ CH ₂ CH ₂ SH, -CH ₂ CHCH ₃ SH, -CH ₂ CH ₂ CH ₂ CH ₂ SH,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH,

-CH ₂ CH ₂ SCH ₃ . Typically, the mercapto functional group is -CH ₂ CH ₂ CH ₂ SH.

The fluorine-containing polymer in the present invention can be produced by any one of ordinary polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. Such polymerization methods include solution polymerization, suspension polymerization and emulsion polymerization.

In the solution polymerization, a method of dissolving the monomer in an organic solvent in the presence of a polymerization initiator, purging with nitrogen, and heating and stirring at 30 to 120 ° C for 1 to 10 hours is employed. As the polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicar And the like. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.

Examples of the organic solvent include those which are inert to the monomers and dissolve them, and examples thereof include 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, trichlorethylene, Ethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in an amount of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total amount of the monomers.

In the emulsion polymerization, a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifier, substituting with nitrogen, and then performing copolymerization by stirring at 50 to 80 ° C for 1 to 10 hours is employed. The polymerization initiator may be at least one selected from the group consisting of benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine- Examples of the organic solvent include water-soluble ones such as isobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, and organic solvents such as azobisisobutylonitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t -Butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like can be used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.

In order to obtain a copolymer aqueous dispersion having excellent stability in storage, it is preferable that the monomers are microparticulated in water and polymerized by using an emulsifying apparatus capable of imparting strong breaking energy such as a high pressure homogenizer or an ultrasonic homogenizer. As the emulsifier, various emulsifiers, such as anionic, cationic or nonionic emulsifiers, may be used, and they are used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomer is completely incompatible, it is preferable to add a compatibilizing agent sufficiently compatible with these monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. By the addition of the compatibilizing agent, it is possible to improve emulsification and copolymerization.

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 , For example, 10 to 40 parts by weight. Examples of the monomer having a low molecular weight include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate and the like. The amount of the monomer is preferably 1 to 50 By weight, for example, 10 to 40 parts by weight.

The fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous dispersion) or an aerosol. The fluorine-containing composition comprises a fluorine-containing polymer (an active component of the surface treatment agent) and a medium (particularly, 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 a subject to be treated by a known method. Usually, a method of dispersing and diluting the fluorine-containing composition in an organic solvent or water, and adhering the fluorine-containing composition to the surface of the object to be treated by a known method such as immersion coating, spray coating, foam coating, and the like is employed. If necessary, curing may be carried out by applying with a suitable crosslinking agent. It is also possible to add an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, etc. to the fluorine-containing composition of the present invention. The concentration of the fluorine-containing polymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of immersion coating), for example, 0.05 to 10% by weight.

The object to be treated with the fluorine-containing composition (for example, a water-repellent or oil-repellent agent) of the present invention includes a fiber product, a stone, a filter (for example, an electrostatic filter), a dustproof mask, Gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramics, plastics, plaster and plaster. Various examples of textile products are available. For example, synthetic fibers such as cotton, hemp, wool, silk and natural vegetable natural fibers, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic Inorganic fibers such as fibers, glass fibers, carbon fibers and asbestos fibers, and mixed fibers thereof.

The fiber product may be in the form of fiber, cloth or the like.

The fluorine-containing composition of the present invention can also be used as an internal mold releasing agent or an external mold releasing agent.

The fluorine-containing polymer may be applied to a fibrous substrate (e.g., a textile product) by any of the known methods for treating a textile product with a liquid. When the fiber product is in the cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed on the cloth. The treated fiber product is dried to exhibit oil repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.

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

The textile product to be treated is typically a fabric, which includes fabrics, knits and non-wovens, cloth-like fabrics and carpets in the form of garments, but may also include fibers or yarns or intermediate fabrics (such as slivers or roving ). The fiber product material may be selected from natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or lyocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers ), Or a mixture of fibers (e.g., a mixture of natural fibers and synthetic fibers). The production polymer of the present invention is particularly effective in making cellulose-based fibers (for example, cotton or rayon) to be oleophobic and oil repellent. In addition, the process of the present invention generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous substrate may be a leather. The preparation polymers may also be applied to the leather from aqueous solutions or aqueous emulsions during various stages of leather processing, for example during the wet processing period of the leather, or during the finishing period of the leather, in order to make the leather hydrophobic and oleophobic.

Alternatively, the fibrous substrate may be paper. The preparation polymer may be applied to preformed paper, or it may be applied during various stages of paper making, for example during paper drying.

By " treatment " is meant that the treatment agent is applied to the subject matter by immersion, spraying, application, or the like. By the treatment, the fluorine-containing polymer which is an effective component of the treatment agent penetrates into the inside of the object to be treated and / or is adhered to the surface of the object to be treated.

[Example]

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

In the following, parts or percentages or percentages refer to parts by weight or weight percentages or weight ratios unless otherwise specified.

The order of the test is as follows.

Shower water repellency test

The water repellency test of the shower was performed in accordance with JIS-L-1092. The shower water repellency test is indicated by the water repellency number (as shown in Table 1 below).

A glass funnel having a volume of at least 250 ml and a spray nozzle capable of spraying 250 ml of water for 20 seconds to 30 seconds are used. The test piece frame is a metal frame having a diameter of 15 cm. Prepare three sheets of test specimen approximately 20 cm x 20 cm in size, and secure the sheet to the specimen holder frame to prevent wrinkles on the sheet. The center of the spray is placed at the center of the sheet. Water (250 mL) at room temperature is placed in a glass funnel and sprayed onto the test piece sheet (over a period of 25 seconds to 30 seconds). Remove the retaining frame from the support, grasp one end of the retaining frame with the front surface down, and tap the other end with a hard material. The holding frame is further rotated by 180 DEG, and excess droplets of water are dropped by repeating the same procedure. Moisture test specimens are compared to wet comparison standards in order to score 0, 50, 70, 80, 90 and 100 in good order from poor water repellency. Results are obtained from the average of three measurements.

Inspection rate  exam

1,000 g of a diluted solution of hard water B (hardness 216: 1.9425 g of calcium chloride, 0.3975 g of magnesium chloride, 4.63 g of sodium sulfate / 10 L of water) was added to the polymer dispersion so that the solid content concentration became 5 wt% Put in the pad. A polyester cloth having a width of 20 cm and a length of 80 cm was circularly formed and allowed to be subjected to continuous processing, and continuous processing for one hour at a middlet pressure of 0.4 MPa was carried out.

The bump ratio is obtained from the following formula.

(The weight of the polyester cloth before the treatment + the weight of the solid diluent after the treatment) - (the weight after the treatment of the polyester cloth + the solid weight of the diluted solution after the treatment)

(Sieving rate) = 100 x (sieving rate of mangle) / (weight of solid diluent before treatment)

When the inspection rate is less than 4%, the inspection is inhibited.

Adhesion test

1 g of a solid of a fluorine-containing polymer was weighed into a metal plate, and heated at 60 DEG C for 1 hour. Then, when the finger was put on the fluorine-containing polymer and the finger was removed, the tackiness felt by the finger was evaluated as follows.

○: No stickiness is felt at all

△: A little sticky feeling

X: Adhesion was felt

××: I feel strong stickiness

Production Example 1

18.63 g of CF ₃ CF ₂ - (CF ₂ CF ₂ ) _n --CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (C6SFClA), 42.84 g of stearyl acrylate (StA) (EO: 20, EO = number of ethylene oxide units (number of ethylene oxide units), number of ethylene oxide units (EO), number of ethylene oxide units ) And 1.21 g of polyoxyethylene isotridecyl ether (EO: 3), and emulsified and dispersed by ultrasonic wave at 60 캜 for 15 minutes under stirring. After the inside of the reaction flask was purged with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added And reacted at 60 DEG C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer nearly matched the composition of the input monomers.

The bumpability test and the tackiness test were carried out. The test results are shown in Table 2.

Production Examples 2 to 51 and Comparative Production Examples 1 to 4

The monomers of the compositions (type and weight ratio of the charged monomers) shown in Table 2 were polymerized in the same manner as in Production Example 1 to prepare an aqueous dispersion of the polymer. The composition of the polymer nearly matched the composition of the input monomers.

The test results are shown in Table 2.

Example 1

The aqueous liquid (5 g and 7.5 g, respectively) prepared in Preparation Example 1 was diluted with pure water to prepare a test solution (1000 g). A polyester taffeta cloth (510 mm x 205 mm) was immersed in this test solution, passed through mangles, and treated with pin tenter at 160 캜 for 2 minutes. The shower water repellency test was performed with this test cloth. The test results are shown in Table 2.

Examples 2 to 51 and Comparative Preparations 1 to 5

The polymers produced in Production Examples 2 to 5 and Comparative Production Examples 1 to 5 were treated in the same manner as in Example 1 to conduct a shower repellency test. The test results are shown in Table 2.

The meanings of the abbreviations in the table are as follows.

C ₆ F ₁₃ CH ₂ CH ₂ OCOC (Cl) = CH ₂

_{C6SFMA C 6 F 13 CH 2 CH} 2 OCOC (CH 3) = CH 2

_{C8SFA C 8 F 17 CH 2 CH} 2 OCOCH = CH 2

StA stearyl acrylate

BeA behenyl acrylate

IBMA isoboronyl methacrylate (Tg > 50 DEG C)

StMA stearyl methacrylate (Tg < 50 DEG C)

CHMA cyclohexyl methacrylate (Tg > 50 DEG C)

VCM vinyl chloride

DAAM diacetone acrylamide

ADMA adamantyl methacrylate

ADA adamantyl acrylate

CPM dicyclopentyl methacrylate

&Lt; Industrial applicability >

The fluorine-containing composition of the present invention can be used for imparting excellent water repellency, oil repellency, and antifouling property to a fiber product (for example, carpet), paper, nonwoven fabric, stone, electrostatic filter, dustproof mask, fuel cell component.

Claims (12)

(a) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group,
(b) a repeating unit derived from a second monomer which is an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms and
(c) a repeating unit derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or melting point (Tm) of not less than 50 DEG C of the homopolymer
Containing fluorine-containing polymer, wherein the fluorine-
In the fluorine-containing polymer, the amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight based on 100 parts by weight of the total amount of the second monomer (b) and the third monomer (c) And the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight. The fluorine-containing monomer (a) according to claim 1, wherein the fluorine-containing monomer (a)
CH ₂ = C (-X) -C (= O) -YZ-Rf
Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-,
Z is a direct bond or a divalent organic group,
And Rf is a fluoroalkyl group having 1 to 20 carbon atoms]
Is a fluorine-containing monomer represented by the following formula (1). The fluorine-containing composition according to claim 2, wherein X in the fluorine-containing monomer (a) is a chlorine atom. The polymerizable composition according to any one of claims 1 to 3, wherein the second monomer (b) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Wherein,
A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30)
Wherein the fluorine-containing composition is an acrylate. The fluorine-containing composition according to claim 4, wherein the alkyl group of the second monomer (b) has 12 to 22 carbon atoms. 6. The composition according to any one of claims 1 to 5, wherein the third monomer (c) has the formula:
CH = CR ¹¹ -C (= O) OR ¹²
Wherein R ¹¹ is H, a C ₁ to C ₄ alkyl group or a halogen,
R ¹² is a C ₁ to C ₃₀ linear, branched or cyclic aliphatic group, a C ₆ to C ₂₀ aromatic group, a C ₇ to C ₂₅ aromatic aliphatic group,
Is an acrylate compound represented by the following formula (1). 7. The fluorine-containing composition according to any one of claims 1 to 6, further comprising an aqueous medium. 8. The fluorine-containing composition according to any one of claims 1 to 7, wherein the fluorine-containing composition is an aqueous dispersion. (a) a repeating unit derived from a fluorine-containing monomer having a fluoroalkyl group,
(b) a repeating unit derived from a second monomer which is an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms and
(c) a repeating unit derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or melting point (Tm) of not less than 50 DEG C of the homopolymer
Containing polymer is a fluorine-
In the fluorine-containing polymer, the amount of the second monomer (b) is 82 to 99.9 parts by weight or 2 to 60 parts by weight based on 100 parts by weight of the total amount of the second monomer (b) and the third monomer (c) And the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight. The water and oil repellent composition according to any one of claims 1 to 8, wherein the fluorine-containing composition is a fluorine-containing composition. 9. A method of treating a substrate, comprising treating the substrate with the fluorine-containing composition of any one of claims 1-8. 9. A fiber product treated by the fluorine-containing composition according to any one of claims 1 to 8.