KR102041857B1 - Fluorine containing composition and fluorine containing polymer - Google Patents

Abstract

This invention provides the water- and oil-repellent composition excellent in water- and oil-repellent property to base materials, such as a textile product, and excellent in preventing the adhesion of a polymer to a roll in the processing process.
(a) repeating units derived from fluorine-containing monomers having fluoroalkyl groups,
(b) a repeating unit derived from a second monomer which is an acrylate monomer having a straight or branched hydrocarbon group having 12 to 30 carbon atoms, and
(c) repeating units derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or a melting point (Tm) of at least 50 ° C of the homopolymer;
A fluorine-containing composition containing a fluorine-containing polymer having
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), The fluorine-containing composition whose amount of a 3rd monomer (c) is 0.1-18 weight part or 40-98 weight part.

Description

Fluorine-containing compositions and fluorine-containing polymers {FLUORINE CONTAINING COMPOSITION AND FLUORINE CONTAINING POLYMER}

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 gives excellent water repellency, oil repellency, and antifouling properties to a fiber product (for example, carpet), paper, nonwoven fabric, stone, electrostatic filter, dust mask, fuel cell component. .

Conventionally, various fluorine-containing compounds have been proposed. A fluorine-containing compound has the advantage that it is excellent in characteristics, such as heat resistance, oxidation resistance, and weather resistance. Taking advantage of the property that the free energy of the fluorine-containing compound is low, that is, difficult to adhere, the fluorine-containing compound is used, for example, as a water / oil repellent and an antifouling agent. For example, US Pat. No. 5247008 discloses an aqueous dispersion of a copolymer of perfluoroalkyl esters of acrylic acid or methacrylic acid, alkyl esters of acrylic acid or methacrylic acid, and aminoalkyl esters of acrylic acid or methacrylic acid. Finishing agents for textile products, leather, paper and mineral substrates which are water are described.

In addition, for the purpose of improving durability of water- and oil-repellent properties for conventional washing or dry cleaning, a monomer having an adhesive group is copolymerized with a fluoroalkyl group-containing polymerizable monomer, or a polymer having a fluoroalkyl group and high film strength Attempts have been made to blend polymers. In the field of coatings (coating agents), by using a particle polymer having a multi-layer structure, it has succeeded in maintaining the properties of fluorine and imparting new properties of workability (for example, Japanese Patent Laid-Open No. 06-56944).

Moreover, in order to have characteristics, such as durability and low temperature cure, the composition of a multilayer structure particle polymer is proposed (for example, Unexamined-Japanese-Patent No. 02-001795, Unexamined-Japanese-Patent No. 07-278422, Unexamined-Japanese-Patent No. 11-). 172126, Japanese Patent Laid-Open No. 2007-291373).

In addition, in a conventional water- and oil-repellent processing bath which is diluted and combined with a conventional general aqueous dispersion, the dispersion is broken by a mechanical impact received when the treated dough enters, so that the emulsion particles are agglomerated and precipitated, and the polymer is formed on the roll. Problems such as adhesion of rolls and contamination of rolls have often occurred. Although several methods have been proposed which are excellent in stability of impurities (for example, Japanese Patent Laid-Open No. 9-118877, WO2004 / 069924), depending on the variety of recent water / oil repellent processing, it is not always possible to provide sufficiently satisfactory stability. It was. Moreover, about the problem that a polymer adheres to a roll, a problem tends to occur, so that the adhesiveness of a polymer is high. Moreover, when the carbon number of the fluoroalkyl group of a fluoroalkyl group containing polymer is 6 or less, since melting | fusing point of a polymer falls, there exists a tendency for adhesiveness to become higher than carbon number 8 or more.

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

An object of the present invention is to provide a water- and oil-repellent composition excellent in imparting water- and oil-repellent property to substrates, such as textile products, and excellent in preventing polymer adhesion to rolls in the processing thereof.

MEANS TO SOLVE THE PROBLEM In order to solve the said problem, the present inventors earnestly examined for the purpose of providing the water- and oil-repellent composition which suppresses generation | occurrence | production of a highly adhesive polymer part, exhibits high water / oil repellency, and is excellent also in durability. As a result, it has been found that the above object can be achieved if the non-fluorine polymer portion of the fluorine-containing polymer has a specific composition, and the present invention has been completed.

The present invention,

(a) repeating units derived from fluorine-containing monomers having fluoroalkyl groups,

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

(c) repeating units derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or a melting point (Tm) of at least 50 ° C of the homopolymer;

It is a fluorine-containing polymer having

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), A fluorine-containing polymer is provided in which the amount of the third monomer (c) is 0.1-18 parts by weight or 40-98 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 substrates such as textile products, and is excellent in preventing polymer adhesion to a roll in its processing.

In this invention, adhesiveness and an inspection rate are low, and favorable processing can be performed.

In this invention, 3rd monomers other than (a) a fluorine-containing monomer, (b) linear or branched hydrocarbon group containing acrylate monomer, and (c) monomers (a) and (b) are used.

In the present invention, the fluorine-containing polymer,

(a) repeating units derived from fluorine-containing monomers (eg acrylates, methacrylates, α-chloro substituted acrylates),

(b) repeating units derived from linear or branched hydrocarbon group-containing acrylate monomers, and

(c) repeating units derived from the third monomer

Has

The fluorine-containing polymer of the present invention,

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

In addition to the repeating units derived from the monomers (a), (b) and (c), you may have repeating units derived from other monomers.

(a) fluorine-containing monomers

The fluorine-containing monomer (a) is of 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,

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

It is a fluorine-containing monomer represented by.

In the fluorine-containing monomer (a), the α position (of acrylate (X: hydrogen atom) or methacrylate (X: methyl group)) may be substituted with a halogen atom or the like. Accordingly, X is a C2-C21 linear or branched alkyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are hydrogen atom, fluorine atom, chlorine) Atom, bromine atom or iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. In particular, X may be a chlorine atom.

It is preferable that a fluorine-containing monomer (a) is an acrylate ester whose Y group is -O-.

Z group is specifically a linear or branched aliphatic group (for example, an alkylene group) of C1-C20 (for example, C1-C10, especially 1-4, especially 1 or 2), for example For example, a group represented by the formula-(CH ₂ ) _x- (wherein x is 1 to 10), or

Aromatic groups or cyclic aliphatic groups having 6 to 18 carbon atoms,

A group represented by the formula -R ² (R ¹ ) N-SO ₂ -or a formula -R ² (R ¹ ) N-CO-, wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon To a straight chain alkylene group or branched alkylene group of 10 to 10, for example, -CH ₂ CH ₂ N (R ¹ ) SO ₂ -group, provided that R ¹ is an alkyl group having 1 to 4 carbon atoms, or

Formula -CH ₂ CH (OR ³ ) CH _2- [Ar- (O) _q ] _p- (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl, etc.) ), Ar is a group represented by an arylene group (eg, a phenylene group) having a substituent as needed, p is 0 or 1, q is 0 or 1, or

Formula-(CH ₂ ) _n -Ar- (O) _q- (wherein Ar is an arylene group having a substituent as needed (for example, a phenylene group), n is 0 to 10, q is 0 or 1 Is represented by

-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -or-(CH ₂ ) _m -S- (CH ₂ ) _n -groups, where m is 1 to 10 and n is 0 to 10 You may.

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

It is preferable that Rf group is a perfluoroalkyl group. It is preferable that carbon number of Rf group is 1-12, for example, 1-6, especially 4-6. 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 , -C ₈ F _17, and the like.

As a specific example of a fluorine-containing monomer (a), although the following can be illustrated, it is not limited to these, for example.

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

(b) a second monomer ( Carbon number  12 to 30 Linear  or Basal  Acrylate monomer having a hydrocarbon group)

The second monomer (b) is a monomer having no fluoroalkyl group. The second monomer (b) does not have a cyclic hydrocarbon group. The second monomer (b) is generally a monomer that does not contain a fluorine atom. In particular, the linear or branched hydrocarbon group may be a linear hydrocarbon group. The linear or branched hydrocarbon group has 12 to 30 carbon atoms, and is preferably a saturated aliphatic hydrocarbon group.

The alkyl acrylate ester may be sufficient as a 2nd monomer (b). The number of carbon atoms in the alkyl group may be 12 to 30, for example, 12 to 22, particularly 14 to 20. For example, the second monomer (b) may be represented by the formula:

CH ₂ = CHCOOA ¹

[In the meal,

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

The acrylate represented by may be sufficient.

As a specific example of a 2nd monomer (b), although the following can be illustrated, it is not limited to these, for example.

(Ie, lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate)

(c) Third monomer: (free of single polymer Transition point ( Tg ) Or melting point ( Tm (Meth) acrylate monomer)

The third monomer (c) is a (meth) acrylate monomer whose homopolymer has a glass transition point (Tg) or a melting point (Tm) of 50 ° C or higher, for example, 60 ° C or higher. The glass transition point and melting point are extrapolated glass transition end temperature (T _eg ) and melting peak temperature (T _pm ), respectively, as defined in JIS K7121-1987 "Method of Measuring Transition Temperature of Plastics". 300 degreeC, for example, 200 degreeC may be sufficient as the upper limit of glass transition point (Tg) or melting | fusing point (Tm).

3rd monomer (c) is monomers other than monomer (a) and (b). The third monomer (c) does not have a fluoroalkyl group.

The third monomer (c) is represented by the formula:

CH = CR ¹¹ -C (= O) OR ¹²

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

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

It is preferable that it is an acrylate ester compound represented by.

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 (eg, having 1 to 6 carbon atoms) (eg, a methyl group, an ethyl group, a propyl group, a butyl group), and a cycloalkyl group (eg, having 5 to 10 carbon atoms) For example, a cyclohexyl group), a polycyclic aliphatic group (e.g., having 7 to 20 carbon atoms) (e.g., norbornyl group, bornyl group, isobornyl group, adamantyl group), phenyl group, naphthyl group, benzyl Qi.

It is preferable that R <^12> has a cyclic group, and it is preferable that they are 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 a specific example of a 3rd monomer (c),

Cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate Acrylate esters such as benzyl acrylate, 2-t-butylphenyl acrylate and naphthyl acrylate;

Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicy Clofentanyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, (2-dimethylamino) ethyl methacrylate, azi Methacrylate esters such as lidinyl methacrylate, aziridinylethyl methacrylate and dicyclopentenyl methacrylate;

Although chloroacrylate esters, such as methyl chloroacrylate, can be illustrated, It is not limited to these.

(d) other monomers

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

Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylates and vinylalkyl ethers are included. Other monomers are not limited to these examples.

The other monomer may be a halogenated olefin.

It is preferable that a halogenated olefin is a C2-C20 olefin substituted by 1-10 chlorine atoms, a bromine atom, or an iodine atom. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred embodiments of the halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides, such as vinylidene chloride, vinylidene bromide and vinylidene iodide.

The other monomer may be a non-fluorine crosslinkable monomer. A non-fluorine crosslinkable monomer is a monomer which does not contain 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 containing no 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 are a hydroxyl group, an epoxy group, a chloromethyl group, a block isocyanate group, an amino group, a carboxyl group and the like.

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.

As a non-fluorine crosslinkable monomer, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-, for example 2-hydroxypropyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1, Although 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. are illustrated, it is not limited to these.

As used herein, "(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 of the fluorine-containing polymer, for example, 10 to 90% by weight, in particular 20 to 70% by weight.

The sum of the amounts 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, in particular 30 to 1000 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a). Grant is also good.

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

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). For example 84 to 99.5 parts by weight or 5 to 55 parts by weight, in particular 85 to 99 parts by weight or 10 to 50 parts by weight, and the amount of the third monomer (c) is 0.1 to 18 parts by weight or 40 to 98 parts by weight, eg 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 30 to 100 parts by weight in total of the total amount of the second monomer (b), the third monomer (c) and the halogenated olefin. To 90 parts by weight, for example 50 to 85 parts by weight, in particular 60 to 80 parts by weight.

The number average molecular weight (Mn) of the fluorine-containing polymer is generally 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the fluorine-containing polymer is generally measured by GPC (gel permeation chromatography).

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

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

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

By polymerizing a monomer in presence of an organopolysiloxane compound (for example, mercapto functional organopolysiloxane, vinyl functional organopolysiloxane), the fluorine-containing polymer which has a siloxane group is obtained. In one embodiment, the mercapto functional organopolysiloxane has siloxy units having the following 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 which} is an organic functional group is represented by the formula: -R ¹ NHR ² , -R ¹ NR ₂ ^2, or -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 chemical formula: -R ¹ SR ² (wherein each R ¹ is independently a C 2 or more divalent hydrocarbon group, R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms, and each R is ¹ and R ² are as described above). Each R ¹ is typically an alkylene group having 2 to 20 carbon atoms. Examples of mercapto functional groups are represented by the following chemical formulas;

-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 of the usual polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization are mentioned.

In solution polymerization, the monomer is dissolved in the organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, a method of heating and stirring for 1 to 10 hours in the range of 30 to 120 ° C is employed. As a polymerization initiator, for example, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxy pivalate, diisopropyl peroxy dicaca Carbonate, etc. are 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, based on 100 parts by weight of the monomer.

As the organic solvent, those which are inert to monomers and dissolve them, for example, 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, perchloro Ethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like. The organic solvent is used in the range of 50 to 2000 parts by weight, for example 50 to 1000 parts by weight, based on 100 parts by weight of the total monomers.

In emulsion polymerization, a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, the method of copolymerizing by stirring for 1 to 10 hours in 50-80 degreeC is employ | adopted. The polymerization initiator is benzoyl peroxide, lauroyl peroxide, t-butylperbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride, azobis Water-soluble ones such as isobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate, or azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t Useful ones such as butyl peroxy pivalate and diisopropyl peroxy dicarbonate are used. A polymerization initiator is used in 0.01-10 weight part with respect to 100 weight part of monomers.

In order to obtain the copolymer aqueous dispersion excellent in the standing stability, it is preferable to finely polymerize the monomer in water using an emulsifying device capable of imparting strong crushing energy such as a high pressure homogenizer or an ultrasonic homogenizer. In addition, as an emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and it is used in 0.5-20 weight part with respect to 100 weight part of monomers. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible, it is preferable to add a compatibilizer, such as a water-soluble organic solvent or a low molecular weight monomer, which are sufficiently compatible with these monomers. By adding a compatibilizer, it is possible to improve the emulsification property and copolymerizability.

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 based on 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Moreover, as a low molecular weight monomer, methyl methacrylate, glycidyl methacrylate, 2,2, 2- trifluoroethyl methacrylate, etc. are mentioned, It is 1-50 with respect to 100 weight part of total amounts of a monomer. You may use in a weight part, for example, 10-40 weight part.

It is preferable that the fluorine-containing composition of this invention is a form of a solution, an emulsion (especially an aqueous dispersion liquid), or an aerosol. The fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treating 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 a workpiece by a conventionally known method. Usually, the said fluorine-containing composition is disperse | distributed to the organic solvent or water, and it diluted, adheres to the surface of a to-be-processed object by well-known methods, such as immersion coating, spray coating, foam coating, etc., and is employ | adopted. In addition, if necessary, it may be applied together with a suitable crosslinking agent to perform curing. Moreover, it is also possible to add together and use an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixer, an antiwrinkle agent, etc. to the fluorine-containing composition of this invention. The concentration of the fluorine-containing polymer in the treatment liquid 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.

As a to-be-processed object processed by the fluorine-containing composition (for example, a water / oil repellent agent) of this invention, a textile product, a stone, a filter (for example, an electrostatic filter), a dust mask, a fuel cell component (for example, Gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, drawings and plasters. Examples of the fiber products include various examples. For example, synthetic fibers such as animal and animal natural fibers such as cotton, hemp, wool, and silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, and semisynthetic such as rayon and acetate. Inorganic fibers, such as fiber, glass fiber, carbon fiber, asbestos fiber, or these mixed fiber, are mentioned.

The fiber product may be any of forms such as fibers and fabrics.

The fluorine-containing composition of this invention can be used also as an internal mold release agent or an external mold release agent.

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

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

Textile products to be treated are typically fabrics, which include fabrics, knits and nonwovens, cloths and carpets in the form of garments, but may be fibers or yarns or intermediate fiber products (eg, slivers or yarns, etc.). ) May be used. Fiber product materials may include natural fibers (e.g., cotton or wool), chemical fibers (e.g., viscose rayon or lyocell, etc.), or synthetic fibers (e.g., polyester, polyamide, or acrylic fibers, etc.). ), Or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers). The produced polymer of the present invention is particularly effective in making cellulosic fibers (for example, cotton or rayon, etc.) oleophobic and oil-repellent. In addition, the process of the invention generally makes the fiber product hydrophobic and water repellent.

Alternatively, the fibrous base may be leather. The produced polymer may be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of the leather processing, for example, during the wet processing of the leather, or during the finishing of the leather, in order to render the leather hydrophobic and oleophobic.

Alternatively, the fibrous substrate may be paper. The produced polymer may be applied to a preformed paper, or may be applied at various stages of paper making, for example, during the drying period of the paper.

"Treatment" means applying a processing agent to a to-be-processed object by immersion, spraying, application | coating, etc. By treatment, the fluorine-containing polymer, which is an active ingredient of the treatment agent, penetrates into the interior of the workpiece and / or adheres to the surface of the workpiece.

EXAMPLE

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

In the following, parts or% or ratios are parts by weight or weight percent or weight ratio unless otherwise specified.

The sequence of tests is as follows.

Shower water repellency test

The shower water repellency test was done according to JIS-L-1092. The shower water repellency test was indicated by the water repellency number (as shown in Table 1 described 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 to 30 seconds are used. The test piece frame is a metal frame having a diameter of 15 cm. Prepare three specimen sheets, approximately 20 cm x 20 cm in size, and secure the sheets to the specimen holder frame so that the sheets are free of wrinkles. Center the spray at the center of the sheet. Water at room temperature (250 mL) is placed in a glass funnel and sprayed (over a period of 25 seconds to 30 seconds) onto the specimen sheet. The retaining frame is removed from the support, grasps one end of the retaining frame and the front surface is lowered, and the opposite end is lightly patted with a hard material. Rotate the holding frame further 180 ° and repeat the same procedure to drop excess water droplets. Wet specimens are compared with a wet comparison standard to rank 0, 50, 70, 80, 90, and 100 in good order from poor water repellency. The results are obtained from the average of three measurements.

Inspection rate test

1000 g of a dilution liquid in 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 prepared so that the polymer dispersion was 5% by weight, and the temperature was adjusted to 40 ° C. In the pads. A mangled polyester cloth having a width of 20 cm and a length of 80 cm was formed in a circular shape so that the continuous treatment could be carried out, and the continuous treatment was carried out for one hour at a mangle pressure of 0.4 MPa.

Inspection rate is calculated | required from the following formula.

(Inspection rate of mangle) = (weight before the treatment of polyester cloth + weight of diluent solid before treatment)-(weight after the treatment of polyester cloth + weight of diluent solid after treatment)

(Inspection rate) = 100 * (manglow inspection rate) / (dilution solid weight before processing)

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

Adhesion test

After weighing 1 g of the solid of the fluorine-containing polymer on a metal plate and heating at 60 ° C. for 1 hour, the adhesiveness felt by the finger when the finger was put on the fluorine-containing polymer was released as follows.

○: no adhesion at all

△: little adhesion

×: adhesiveness is felt

××: Strong adhesion is felt

Preparation 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) (C ₆ SFClA) in a 300 mL autoclave, 42.84 g of stearyl acrylate (StA), iso Boronyl methacrylate (IBMA) 0.62 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, stearyl trimethyl ammonium chloride 2.57 g, polyoxyethylene lauryl ether (EO: 20, EO is the number of ethylene oxide units 2.65 g and 1.21 g of polyoxyethylene isotridecyl ether (EO: 3) were added thereto, and the mixture was emulsified and ultrasonically dispersed at 60 ° C. for 15 minutes under stirring. After nitrogen replacement in the reaction flask, 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 thereto. It was made to react at 60 degreeC for 5 hours, and the aqueous dispersion liquid of the polymer was obtained. The composition of the polymer was almost identical to the composition of the charged monomers.

An inspection rate test and an adhesive test were performed. The test results are shown in Table 2.

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

The monomer of the composition (type and weight ratio of input monomer) shown in Table 2 was superposed | polymerized in the procedure similar to the manufacture example 1, and the aqueous dispersion liquid of the polymer was manufactured. The composition of the polymer was almost identical to the composition of the charged 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 a mangle, and treated with a pin tenter at 160 ° C for 2 minutes. The shower water repellent test was done with this test cloth. The test results are shown in Table 2.

Examples 2 to 51 and Comparative Preparation Examples 1 to 5

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

In the table, the meaning of abbreviation is as follows.

C6SFClA 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 Stearylacrylate

BeA Behenylacrylate

IBMA Isoboroyl methacrylate (Tg> 50 ° C)

StMA stearyl methacrylate (Tg <50 ° C)

CHMA cyclohexyl methacrylate (Tg> 50 ° C)

VCM Vinyl Chloride

DAAM diacetone acrylamide

ADMA Adamantyl methacrylate

ADA adamantyl acrylate

CPM Dicyclopentanyl Methacrylate

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

Claims (13)

(a) repeating units derived from fluorine-containing monomers having fluoroalkyl groups,
(b) a repeating unit derived from a second monomer which is an acrylate monomer having a straight or branched hydrocarbon group having 12 to 30 carbon atoms,
(c) repeating units derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or a melting point (Tm) of at least 50 ° C of the homopolymer and
(d) repeating units derived from halogenated olefins
A fluorine-containing polymer having, and
Aqueous media
It is a fluorine-containing composition containing
In the fluorine-containing polymer, the amount of the second monomer (b) is 82 to 99.9 parts by weight based on 100 parts by weight of the total amount of the second monomer (b) and the third monomer (c). The amount is from 0.1 to 18 parts by weight, the amount of the second monomer (b) is from 2 to 60 parts by weight, the amount of the third monomer (c) is from 40 to 98 parts by weight, and the amount of the halogenated olefin (d) is It is 30-90 weight part with respect to a total of 100 weight part of the quantity of a 2 monomer (b), a 3rd monomer (c), and a halogenated olefin (d),
Fluorine-containing monomer (a) is represented by the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a chlorine atom,
Y is -O- or -NH-,
Z is a direct bond or a linear or branched aliphatic group having 1 to 20 carbon atoms,
Aromatic groups or cyclic aliphatic groups having 6 to 18 carbon atoms,
A group represented by the formula -R ² (R ¹ ) N-SO ₂ -or a formula -R ² (R ¹ ) N-CO-, wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon To 10 straight alkylene groups or branched alkylene groups),
Formula -CH ₂ CH (OR ³ ) CH _2- [Ar- (O) _q ] _p- (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group which may have a substituent) , p is 0 or 1, q is 0 or 1),
A group represented by the formula-(CH ₂ ) _n -Ar- (O) _q- (wherein Ar is an arylene group which may have a substituent, n is 0 to 10 and q is 0 or 1), or
-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -or-(CH ₂ ) _m -S- (CH ₂ ) _n -groups, where m is 1 to 10 and n is 0 to 10 ego,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms]
It is a fluorine-containing monomer represented by
The second monomer (b) is of the formula:
CH ₂ = CHCOOA ¹
[Wherein, A ¹ is a straight or branched hydrocarbon group having 12 to 30 carbon atoms]
Is an acrylate represented by
The third monomer (c) is of formula:
CH ₂ = CR ¹¹ -C (= O) OR ¹²
[Wherein, R ¹¹ is H, a C ₁ to C ₄ alkyl group or halogen,
R ¹² is a C ₁ to C ₃₀ cyclic aliphatic group having no hydroxyl group]
It is an acrylate compound other than a fluorine-containing monomer (a) and a 2nd monomer (b) represented by
Halogenated olefin (d) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms,
The fluorine-containing polymer does not include a block isocyanate group and a siloxane group,
The fluorine-containing composition in the fluorine-containing polymer, wherein the amount of the fluorine-containing monomer (a) is 10 to 70% by weight of the fluorine-containing polymer. The fluorine-containing composition according to claim 1, wherein the hydrocarbon group in the second monomer (b) has 12 to 22 carbon atoms. The fluorine-containing composition according to claim 1, wherein in the third monomer (c), R ¹² is a cycloalkyl group having 5 to 10 carbon atoms or a polycyclic aliphatic group having 7 to 20 carbon atoms. The amount of the second monomer (b) is 89 to 99.9 parts by weight, the amount of the third monomer (c) is 0.1 to 11 parts by weight, or the amount of the second monomer (b) is 2 to 43 A fluorine-containing composition having a weight part and the amount of the third monomer (c) is 57 to 98 parts by weight. The fluorine-containing composition of claim 1 which is an aqueous dispersion. (a) repeating units derived from fluorine-containing monomers having fluoroalkyl groups,
(b) a repeating unit derived from a second monomer which is an acrylate monomer having a straight or branched hydrocarbon group having 12 to 30 carbon atoms,
(c) repeating units derived from a third monomer which is a (meth) acrylate monomer having a glass transition point (Tg) or a melting point (Tm) of at least 50 ° C of the homopolymer and
(d) repeating units derived from halogenated olefins
It is a fluorine-containing polymer having
In the fluorine-containing polymer, the amount of the second monomer (b) is 82 to 99.9 parts by weight based on 100 parts by weight of the total amount of the second monomer (b) and the third monomer (c). The amount is from 0.1 to 18 parts by weight, the amount of the second monomer (b) is from 2 to 60 parts by weight, the amount of the third monomer (c) is from 40 to 98 parts by weight, and the amount of the halogenated olefin (d) is It is 30-90 weight part with respect to a total of 100 weight part of the quantity of a 2 monomer (b), a 3rd monomer (c), and a halogenated olefin (d),
Fluorine-containing monomer (a) is represented by the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a chlorine atom,
Y is -O- or -NH-,
Z is a direct bond or a linear or branched aliphatic group having 1 to 20 carbon atoms,
Aromatic groups or cyclic aliphatic groups having 6 to 18 carbon atoms,
A group represented by the formula -R ² (R ¹ ) N-SO ₂ -or a formula -R ² (R ¹ ) N-CO-, wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is 1 carbon To 10 straight alkylene groups or branched alkylene groups),
Formula -CH ₂ CH (OR ³ ) CH _2- [Ar- (O) _q ] _p- (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is an arylene group which may have a substituent) , p is 0 or 1, q is 0 or 1),
A group represented by the formula-(CH ₂ ) _n -Ar- (O) _q- (wherein Ar is an arylene group which may have a substituent, n is 0 to 10 and q is 0 or 1), or
-(CH ₂ ) _m -SO _2- (CH ₂ ) _n -or-(CH ₂ ) _m -S- (CH ₂ ) _n -groups, where m is 1 to 10 and n is 0 to 10 ego,
Rf is a fluoroalkyl group having 1 to 20 carbon atoms]
It is a fluorine-containing monomer represented by
The second monomer (b) is of the formula:
CH ₂ = CHCOOA ¹
[Wherein, A ¹ is a straight or branched hydrocarbon group having 12 to 30 carbon atoms]
Is an acrylate represented by
The third monomer (c) is of formula:
CH ₂ = CR ¹¹ -C (= O) OR ¹²
[Wherein, R ¹¹ is H, a C ₁ to C ₄ alkyl group or halogen,
R ¹² is a C ₁ to C ₃₀ cyclic aliphatic group having no hydroxyl group]
It is an acrylate compound other than a fluorine-containing monomer (a) and a 2nd monomer (b) represented by
Halogenated olefin (d) is an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms,
Does not contain blocked isocyanate groups and siloxane groups,
The fluorine-containing polymer whose quantity of a fluorine-containing monomer (a) is 10 to 70 weight% of a fluorine-containing polymer. The fluorine-containing polymer according to claim 6, wherein in the third monomer (c), R ¹² is a cycloalkyl group having 5 to 10 carbon atoms or a polycyclic aliphatic group having 7 to 20 carbon atoms. The method of claim 6, wherein the amount of the second monomer (b) is 89 to 99.9 parts by weight and the amount of the third monomer (c) is 0.1 to 11 parts by weight, or the amount of the second monomer (b) is 2 to 43 A fluorine-containing polymer having a weight part and the amount of the third monomer (c) is 57 to 98 parts by weight. The water / oil repellent composition which is a fluorine-containing composition in any one of Claims 1-5. A method of treating a substrate, comprising treating with the fluorine-containing composition according to any one of claims 1 to 5. The fiber product processed with the fluorine-containing composition in any one of Claims 1-5. The fluorine-containing composition according to claim 1, wherein the amount of the halogenated olefin (d) is 60 to 80 parts by weight based on 100 parts by weight of the total amount of the second monomer (b), the third monomer (c), and the halogenated olefin (d). . The fluorine-containing polymer according to claim 6, wherein the amount of the halogenated olefin (d) is 60 to 80 parts by weight based on 100 parts by weight of the total amount of the second monomer (b), the third monomer (c), and the halogenated olefin (d). .