JP2000129246A - Water repellent/oil repellent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which gives excellent water-repellency and oil repellency and water drop falling off properties to a substrate by incorporating a fluoro polymer with a fluoro hydroxy compound. SOLUTION: This composition comprises at least one fluoro polymer and a fluoro hydroxy compound represented by the formula: Rf1(CH2)nOH (wherein Rf1 is a polyfluoroalkyl having at least 7C, desirably, 7-16C on the average; and (n) is 2-4). It is desirable that the fluorohydroxy compound is a mixture containing at least two compounds having the identical n values and containing Rf1 groups having the different numbers of carbon atoms and having 7-16C on the average. It is desirable that the fluoro polymer is a polymer comprising both polymer units derived from a polyfluoroalkyl-group-containing (meth)acrylic ester and polymer units derived from at least one polymerizable monomer selected from among a 1-20C alkyl (meth)acrylate, a vinyl halide, and a vinylidene halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water / oil repellent composition or a treated fiber or a treated fiber woven fabric treated with the composition. More specifically, the water / oil repellent composition of the present invention is a composition that exhibits excellent water / oil repellency when treated to fibers or fiber fabrics, and can further improve the performance by curing.

[0002]

2. Description of the Related Art (Meth) having a polyfluoroalkyl group (hereinafter, a polyfluoroalkyl group is referred to as an ^Rf group).
BACKGROUND ART A technique for imparting water / oil repellency by treating a fiber with a water / oil repellent composition containing an acrylate polymer as an active ingredient has been conventionally known. Further, as the water / oil repellent composition obtained by blending a fluorine-containing alcohol compound with the water / oil repellent composition, R ^f2 (CH ₂ ) _n OH (where R ^f2 is a perfluoroalkyl group having 4 to 6 carbon atoms) Or 4 to 2 carbon atoms
5 perfluoropolyether group, n is 1-6. ) (JP-A-10-81873).

Further, a method has been proposed in which an alcohol compound containing no fluorine atom is contained in the water / oil repellent composition (JP-A-9-25478, JP-A-8-81883,
JP-A-8-31997, JP-A-9-111228).

[0004]

However, the conventional water / oil repellent composition has a problem in that the water / oil repellency and the durability thereof are poor. Further, even if a large amount of a fluorine-containing alcohol or an alcohol compound containing no fluorine atom is added for the purpose of improving this, the water / oil repellency and the durability of sulfur cannot be improved.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has excellent water and oil repellency and water and oil repellent composition excellent in durability. And a treated fiber or treated fiber product treated with the water / oil repellent composition. That is, the present invention provides at least one kind of the fluoropolymer (A) and R ^f1 (CH ₂ ) _n O
H (where R ^f1 is a polyfluoroalkyl group having an average carbon number of 7 or more, and n is an integer of 2 to 4). A water- and oil-repellent composition containing one or more fluorine-containing hydroxy compounds (B). Articles and fibers or textiles treated with the composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The R ^f group in the present specification refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms. The R ^f group is preferably a linear or branched group, and particularly preferably a linear group. In the case of a branched group, it is preferable that the branched portion is present at the terminal portion of the R ^f group and is a short chain having about 1 to 4 carbon atoms. The R ^f group is
A halogen atom other than a fluorine atom may be included. As another halogen atom, a chlorine atom is preferable.
An etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the R ^f group. The structure of the terminal portion of the R ^f group is -CF ₂ C
F ₃ , —CF (CF ₃ ) ₂ , —CF ₂ H, —CFH ₂ ,
—CF ₂ Cl and the like, and —CF ₂ CF ₃ is preferable. The number of fluorine atoms in the R ^f group is [(the number of fluorine atoms in the R ^f group) / (the number of hydrogen atoms contained in the corresponding alkyl group having the same carbon number as the R ^f group)] × 100 (%) When expressed by, it is preferably at least 60%, particularly preferably at least 80%.

The R ^f group is preferably a group in which all of the hydrogen atoms of the alkyl group have been replaced by fluorine atoms (ie, a perfluoroalkyl group) or a group having a perfluoroalkyl group at the terminal.

Specific examples of the R ^f group include the following groups. _{C 4 F 9 - [F (} CF 2) 4 -, (CF 3) 2
CFCF ₂ —, (CF ₃ ) ₃ C—, and CF ₃ CF ₂
CF (CF ₃ ) — etc.], C ₅ F ₁₁
- [e.g. _{F (CF 2) 5 -]} , C 6 F 13 - [ e.g. _{F (CF 2) 6 -]} , C 7 F 15 - [ e.g. F (CF
₂ ) _7- ], C ₈ F _17- [for example, F (CF ₂ ) ₈
−], C ₉ F ₁₉ − [for example, F (CF ₂ ) ₉ −], C ₁₀
F ₂₁ - [e.g. _{F (CF 2) 10 -]} , C 12 F 25 - [ e.g. _{F (CF 2) 12 -]} , C 14 F 29 - [ such as F
(CF ₂ ) _14- ], C ₁₆ F _33- [for example, F (CF ₂ )
₁₆ −], CHF ₂ (CF ₂ ) _j − (where j is 1 to 1)
5 _{integer), CF 2 Cl (CF 2} ) k - ( wherein, k is 1 to 18 _{integer), (CF 3) 2 CF} (CF 2) l -
(Where l is an integer of 1 to 17) and the like.

The term "R ^f group containing an etheric oxygen atom" as used herein means a group in which an etheric oxygen atom is inserted between carbon-carbon bonds of the R ^f group, and an R ^f group containing a thioetheric sulfur atom. ^{The f} group refers to a group in which a thioetheric sulfur atom is inserted between carbon-carbon bonds of the R ^f group.

Specific examples of the R ^f group containing an etheric oxygen atom include the following groups. F (CF ₂ ) ₅ O
_{CF (CF 3) -, F} [CF (CF 3) CF 2 O] y C
_{F (CF 3) CF 2 CF} 2 -, F [CF (CF 3) CF
_{2 O] z CF (CF 3} ) -, F [CF (CF 3) CF 2
_{O] u CF 2 CF 2 -} , F (CF 2 CF 2 CF 2 O) v
CF ₂ CF ₂ —, F (CF ₂ CF ₂ O) _w CF ₂ CF ₂
-(Y and z are integers of 1 to 10, u is an integer of 2 to 6, v is an integer of 1 to 11, w is an integer of 1 to 11) and the like.

Specific examples of the R ^f group containing a thioetheric sulfur atom include the following groups. F (CF ₂ ) _{5
SCF (CF 3) -, F} [CF (CF 3) CF 2 S] y
_{CF (CF 3) CF 2 CF} 2 -, F [CF (CF 3) C
_{F 2 S] z CF (CF} 3) -, F [CF (CF 3) CF
_{2 S] u CF 2 CF 2} -, F (CF 2 CF 2 CF 2 S)
_v CF ₂ CF _2- , F (CF ₂ CF ₂ S) _w CF ₂ CF
_2- (y, z are integers from 1 to 10, u is an integer from 2 to 6, v
Is an integer of 1 to 11, w is an integer of 1 to 11) and the like.

As the fluorinated polymer (A), a polymer having an R ^f group which may contain an etheric oxygen atom or a thioetheric sulfur atom is preferable, and particularly a polymer containing an etheric oxygen atom or a thioetheric sulfur atom is preferred. Polymers having no R ^f groups are preferred. Further, the fluorine-containing polymer is R ^f
A polymer containing a polymerized unit of a (meth) acrylate ester having a group is preferred. The polymer has R ^f group (meth) be a polymer obtained by only polymerizing acrylic acid ester, having ^the R ^f group (meth) polymerizable monomers other than acrylic acid ester and the ester (Hereinafter, referred to as other monomers), and the latter is preferable.

[0013] Here, the (meth) acrylic acid ester having ^the R ^f group, refers to a compound ^the R ^f group is present in the alcohol residue portion of the (meth) acrylic acid ester, the following formula 1
The compound represented by is preferred. However, in equation 1, R
^f represents an ^Rf group, Q represents a divalent organic group, and R represents a hydrogen atom or a methyl group. R ^f -Q-OCOCR = CH ₂ Formula 1 The R ^f group in Formula 1 is preferably an R ^f group containing no etheric oxygen atom or thioetheric sulfur atom, particularly preferably a perfluoroalkyl group, and particularly preferably-( CF ₂ )
_n F (where, n is 1 to 16 integer, preferably an integer of 4 to 16, especially 6 to 12 is preferably an integer of.) a group represented by preferred.

Q in the formula 1 is-(CH ₂ ) _{p + q-} ,
_{- (CH 2) p CONH (} CH 2) q -, - (CH 2)
_{p OCONH (CH 2) q -} , - (CH 2) p SO 2 N
^{_{R 2 (CH 2) q -}} , - (CH 2) p NHCONH (C
_{H 2) q -, - (} CH 2) p CH (OH) - (CH 2) q
-And the like are preferable. Here, R ² represents a hydrogen atom or an alkyl group. P and q each represent an integer of 0 or more, and p + q is an integer of 1 to 22.

Further, Q is-(CH ₂ ) _{p + q} -,-(C
_{H 2) p CONH (CH 2} ) q -, - (CH 2) p SO
₂ NR ² (CH ₂ ) _q- , q is an integer of 2 or more, and p + q is preferably 2 to 6, particularly preferably p +
q is when it is _{2~6 - (CH 2) p +} q -, i.e., preferably an ethylene group; hexamethylene group, especially, dimethylene group. It is preferable that a fluorine atom is bonded to the carbon atom of R ^f bonded to Q.

As the (meth) acrylate having an R ^f group, the following compounds can be mentioned. Here, R represents a hydrogen atom or a methyl group.

[0017]

Embedded image CF ₃ (CF ₂ ) ₄ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₅ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₉ CH ₂ OCOCR = CH ₂ , CF ₂ H (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₁ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₃ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₁₅ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₄ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₇ CONHCH ₂ CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ (CH ₂ ) ₃ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OCOCH ₃ ) OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₅ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , (CF ₃ ) ₂ CF (CF ₂ ) ₇ CH ₂ CH (OH) CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCR = CH ₂ , CF ₃ (CF ₂ ) ₈ CONHCH ₂ CH ₂ OCOCR = CH ₂ .

The fluoropolymer (A), when a polymer obtained by polymerizing a R ^f group (meth) acrylic acid esters, one a having ^the R ^f group (meth) acrylic acid ester or It may be a polymer obtained by polymerizing two or more kinds. When two or more (meth) acrylates having R ^f groups are polymerized, a mixture of (meth) acrylates having R ^f groups having different carbon numbers is preferable. The molar average carbon number of the ^Rf group of the (meth) acrylate having an ^Rf group having a different number of carbon atoms is preferably from 7 to 12, particularly preferably from 8 to 10. When the molar average carbon number of the R ^f group is 7 or more, the effect of the present invention is significantly improved.

The fluoropolymer (A) in the present invention comprises:
It is preferably a polymer obtained by polymerizing a (meth) acrylic acid ester having an R ^f group with another monomer. By changing the type and polymerization ratio of other monomers, water repellency, oil repellency, washing durability, dry cleaning durability, friction durability, antifouling performance, etc. Can change performance.

Examples of the other monomer include known or well-known polymerizable monomers, and a polymerizable monomer having one or two polymerizable unsaturated groups is preferable. As other monomers,
The following polymerizable monomer (a ¹ ) and the following polymerizable monomer (a
One or more selected from ² ) is preferred. Of these,
As the other monomer, it is preferable that the polymerizable monomer (a ¹ ) is essential, and in particular, the polymerizable monomer (a ² ) is essential together with the polymerizable monomer (a ¹ ). Is preferred.

Polymerizable monomer (a ¹ ): One or more polymerizable monomers selected from alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group, vinyl halides, and vinylidene halides. Monomer.

Polymerizable monomer (a ² ): olefin, vinyl carboxylate, styrene, substituted styrene (meth) acrylamide, N-substituted (meth) acrylamide, alkyl vinyl ether (substituted alkyl) vinyl ether, vinyl alkyl ketone, diene, Glycidyl (meth) acrylate, aziridinyl (meth) acrylate, substituted alkyl group (meth) acrylate, polyoxyalkylene mono (meth) acrylate, alkyl ether of polyoxyalkylene mono (meth) acrylate, polyoxyalkylene di (meth) acrylate, (Meth) acrylate having a polydimethylsiloxane group, triallyl cyanurate, allyl glycidyl ether, allyl carboxylate, N-vinylcarbazole, N-methylmaleimide, maleic anhydride, Maleic acid monoalkyl esters, maleic acid dialkyl esters, and blocked isocyanate group-containing (meth) one or more polymerizable monomers selected from acrylate.

In the polymerizable monomer (a ¹ ), in the alkyl (meth) acrylate having an alkyl group portion of 1 to 20 carbon atoms, the alkyl group is a straight-chain, branched,
Alternatively, the structure may be any of ring structures, and may be a structure partially having a ring structure. The alkyl (meth) acrylate may be of two or more types, and in the case of two or more types, may be composed of two or more types having different structures of the alkyl group portion. The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester having an alkyl group part having a linear or branched structure and having 1 to 18 carbon atoms, particularly methyl (meth) acrylate and stearyl (meth) yl. ) Acrylate, cetyl (meth) acrylate, or 2-ethylhexyl (meth)
Acrylates and the like are preferred.

The vinyl halide in the polymerizable monomer (a ¹ ) is preferably vinyl chloride or vinyl fluoride, particularly preferably vinyl chloride. Polymerizable monomer (a
^The vinylidene halide in ¹ ) is preferably vinylidene chloride or vinylidene fluoride, and particularly preferably vinylidene chloride.

As the polymerizable monomer (a ² ), ethylene, vinyl acetate, styrene, α-methylstyrene, p-
Methylstyrene, glycidyl (meth) acrylate (meth) acrylamide, N, N-dimethyl (meth) acrylamide, diacetone (meth) acrylamide, methylolated diacetone (meth) acrylamide, N-methylol (meth) acrylamide, vinyl alkyl ether, halogen Alkyl vinyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, aziridinylethyl (meth) acrylate, benzyl (meth) acrylate, aziridinyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyoxyalkylene mono (meth) ) Acrylate, polyoxyalkylene mono (meth) acrylate methyl ether, polyoxyalkylene mono (meth) acrylate (2-ethylhexyl) Ether, polyoxyalkylene (meth) acrylate, a polydimethylsiloxane (meth) acrylate, triallyl cyanurate, allyl glycidyl ether, allyl acetate, N- vinyl carbazole, maleimide, N- methyl maleimide,
(2-dimethylamino) ethyl (meth) acrylate,
Alternatively, a blocked isocyanate group-containing (meth) acrylate or the like is preferable.

The (meth) acrylate containing a blocked isocyanate group in the polymerizable monomer (a ² ) is an ester of (meth) acrylic acid having at least one blocked isocyanate group and having an isocyanate group. A compound having a structure in which the isocyanate group of the (meth) acrylate is blocked with a blocking agent is preferable.

The (meth) acrylic acid ester having an isocyanate group among the polymerizable monomers (a ² ) includes 2
A reaction product obtained by reacting isocyanateethyl (meth) acrylate or a (meth) acrylate having a functional group capable of binding to an isocyanate group with a polyisocyanate in such a proportion that one or more isocyanate groups remain. preferable.

Here, as the (meth) acrylate having a functional group capable of binding to an isocyanate group, a (meth) acrylate having a hydroxyl group is preferable.
Particularly, a mono- or diester of (meth) acrylic acid and a polyhydric alcohol is preferable. Examples of the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerin, an adduct of trimethylolpropane-alkylene oxide, and pentaerythritol.

Further, as the polyisocyanate, 4,
Aromatic isocyanates such as 4'-diphenylmethane diisocyanate, tolylene diisocyanate, aliphatic isocyanates such as hexamethylene diisocyanate, cycloaliphatic isocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, norbornene diisocyanate And modified products of these polyisocyanates, such as modified nurate, modified prepolymer and modified burette.

Examples of the polyisocyanate include aliphatic isocyanates, cycloaliphatic isocyanates (hereinafter collectively referred to as hydrocarbon-based isocyanates), and a nurate-modified hydrocarbon-based isocyanate and hydrocarbon. A modified prepolymer of an isocyanate or a modified buret of a hydrocarbon isocyanate is preferred.

As the blocking agent, alkyl ketoximes, phenols, alcohols, β-diketones and lactams are preferable, and methyl ethyl ketoxime, ε-caprolactam, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, Particularly preferred are t-butyl alcohol, maleic imide and the like. Further, as a blocking agent, a dissociation temperature of 12
A blocking agent comprising a compound at 0 to 180 ° C. is preferred, and alkyl ketoximes such as methyl ethyl ketoxime and ε-caprolactam are particularly preferred.

Specific examples of the blocked isocyanate group-containing (meth) acrylate among the polymerizable monomers (a ² ) include compounds in which the isocyanate group of 2-isocyanatoethyl (meth) acrylate is blocked with methyl ethyl ketoxime; A compound in which isocyanate groups of isocyanate ethyl (meth) acrylate are blocked with ε-caprolactam, isophorone diisocyanate
1: 1 with hydroxyethyl (meth) acrylate
(Molar ratio) a compound in which an isocyanate group of a reactant is blocked with methyl ethyl ketoxime, a compound in which an isocyanate group of a 1: 1 (molar ratio) of isophorone diisocyanate and 2-hydroxypropyl (meth) acrylate is blocked with methyl ethyl ketoxime, Compounds in which a 1: 1 (molar ratio) reaction product of norbornene diisocyanate and 2-hydroxyethyl (meth) acrylate is blocked with methyl ethyl ketoxime are exemplified.

When the fluorinated polymer (A) is a polymer obtained by polymerizing a (meth) acrylate having an R ^f group with another monomer, the R in the fluorinated polymer (A) The proportion of the polymerized unit of the (meth) acrylic acid ester having an ^f group is preferably from 5 to 95% by weight, particularly preferably from 60 to 95% by weight.

The water / oil repellent composition of the present invention contains a specific fluorinated hydroxy compound (B) together with the fluorinated polymer (A). Specific fluorinated hydroxy compound (B)
R ^f1 in is higher average carbon number 7 polyfluoroalkyl group. The average carbon number is an average carbon number obtained on a molar average. The fluorinated hydroxy compound (B) may be composed of one kind of fluorinated hydroxy compound, or may be composed of two or more kinds of different fluorinated hydroxy compounds.

When the fluorinated hydroxy compound (B) is composed of one kind of fluorinated hydroxy compound, R ^f1 preferably has 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms.

When the fluorine-containing hydroxy compound (B) is composed of two or more different compounds, it is preferable that two or more of the compounds having the same number of n are used. R ^f1 is the average number of 7 or more ^the R ^f group carbon, preferably ^the R ^f group having an average carbon number of 7 to 16, particularly preferably an average ^the R ^f group having 7 to 12 carbon atoms. Furthermore, a fluorine-containing hydroxy compound (B)
Fluorinated If is composed of two or more compounds is preferably composed of two or more fluorine-containing hydroxy compound the carbon number of R ^f1 moiety is 6 or more, particularly the number of carbon atoms of R ^f1 moiety is 6 to 16 It is preferably composed of two or more kinds of hydroxy compounds, and particularly preferably composed of two or more kinds of fluorine-containing hydroxy compounds (B) having 6 to 12 carbon atoms in the R ^f1 portion.

R ^f in the fluorine-containing hydroxy compound (B)
When the group has an average carbon number of 6 or less, the water repellency and the oil repellency tend to decrease, and the dispersion stability in the water repellent / oil repellent composition is undesirably low. When the average carbon number of the ^Rf group is more than 16, the molecular weight of the fluorinated hydroxy compound (B) becomes too large, and may be precipitated in the water / oil repellent composition.

The fluorine-containing hydroxy compound (B) is a known compound. Specific examples of the fluorinated hydroxy compound (B) in the present invention include compounds having a perfluoroalkyl group having 7 or more carbon atoms among the following compounds, or
A mixture of two or more of the following compounds in which the number of carbon atoms of the perfluoroalkyl group is different is exemplified. However, the perfluoroalkyl group in the following formula includes a group having structural isomerism.

[0039]

Embedded image C ₆ F ₁₃ (CH ₂ ) ₂ OH, C ₆ F ₁₃ (CH
₂ ) ₃ OH, C ₇ F ₁₅ (CH ₂ ) ₂ OH, C ₇ F ₁₅ (C
H ₂ ) ₃ OH, C ₈ F ₁₇ (CH ₂ ) ₃ OH, C ₈ F
₁₇ (CH ₂ ) ₃ OH, C ₉ F ₁₉ (CH ₂ ) ₃ OH, C ₁₀
F ₂₁ (CH ₂ ) ₂ OH, C ₁₀ F ₂₁ (CH ₂ ) ₃ OH, C
₁₂ F ₂₅ (CH ₂ ) ₂ OH, C ₁₂ F ₂₅ (CH ₂ ) ₃ OH,
C ₁₄ F ₂₉ (CH ₂ ) ₂ OH, C ₁₄ F ₂₉ (CH ₂ ) ₃ O
H, C ₁₆ F ₃₃ (CH ₂ ) ₂ OH, C ₁₆ F ₃₃ (CH ₂ ) ₃
OH.

The amount of the fluorine-containing hydroxy compound (B) contained in the water- and oil-repellent composition of the present invention is preferably 0.1 to 20% by weight, more preferably 0.1 to 20% by weight, based on the fluorine-containing polymer (A). 5-10% by weight is preferred. Further, the water / oil repellent composition of the present invention may contain components (hereinafter, referred to as other components) other than the fluoropolymer (A) and the fluorohydroxy compound (B). Other components include a medium. When an aqueous medium is used as the medium, the water / oil repellent composition of the present invention can be used as a water-dispersed water / oil repellent composition. When a solvent is used as the medium, the water / oil repellent composition of the present invention can be used as a solution type water / oil repellent composition.

Examples of the aqueous medium in the water-dispersed water / oil repellent composition include water alone or a mixture of water and a water-soluble organic solvent. As the water-soluble organic solvent, a glycol solvent or a glycol ether solvent is preferable.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like.

Examples of glycol ether solvents include dimethyl ether or monomethyl ether of ethylene glycol), dimethyl ether or monomethyl ether of propylene glycol, dimethyl ether or monomethyl ether of diethylene glycol, dimethyl ether or monomethyl ether of dipropylene glycol, and dimethyl ether or monomethyl ether of triethylene glycol. Examples thereof include dimethyl ether and monomethyl ether of ether and tripropylene glycol. The amount of the water-soluble organic solvent is 10 to 50% by weight based on water.
Is preferred.

Further, the water-dispersed water / oil repellent composition preferably contains a surfactant. As the surfactant, a cationic surfactant or a nonionic surfactant is preferable.

On the other hand, as the solvent for preparing the solution type water / oil repellent composition, a hydrocarbon solvent and / or a polar solvent are preferably used. As the hydrocarbon solvent, a solvent made of a known or well-known compound consisting only of carbon atoms and hydrogen atoms can be employed. Among these, a solvent composed of an aliphatic hydrocarbon compound, or a solvent mainly composed of an aliphatic hydrocarbon compound is preferable, and particularly, n-heptane,
n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffinic hydrocarbon solvent, liquid paraffin, decane, undecane, dodecane, mineral spirits, mineral terpenes, etc. preferable. Further, it is preferable to select the hydrocarbon solvent from those having a flash point higher than room temperature.

The polar solvent means a solvent having a polar group or a polar portion in the molecular structure, and is a polar group such as a hydroxyl group, a carboxyl group, an ester group, an acyl group, or an alkoxyl group, or a polar group such as an ether bond. A solvent having at least one is preferred. The number of polar groups or polar moieties is 1
One molecule or two or more molecules may be present in a molecule, and in the case of two or more molecules, different polar groups or polar moieties may be present in one molecule.

The polar solvent is selected from known polar solvents, and is preferably an alcohol solvent, a glycol solvent, an ester solvent, or a ketone solvent. Examples of the alcohol-based solvent include ethyl alcohol, butyl alcohol, and isopropyl alcohol.

Examples of glycol solvents include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether monoacetate, dipropylene glycol, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether. And the like.

Examples of the ester solvent include dibasic acid esters such as methyl acetate, ethyl acetate, butyl acetate, diethyl succinate, diethyl adipate, dibutyl phthalate and dioctyl phthalate. Examples of the ketone solvent include methyl isobutyl ketone, methyl ethyl ketone, acetone and the like.

As polar solvents, acetone, diethyl succinate, diethyl adipate, dibutyl phthalate, dioctyl phthalate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether monoacetate,
Propylene glycol monoethyl ether monoacetate is particularly preferred.

The solvent-type water / oil repellent composition preferably contains a surfactant. As the surfactant, a cationic surfactant or a nonionic surfactant is preferable.

The water- and oil-repellent composition of the present invention may contain additional components other than those described above according to the purpose. Other added components include other water repellents, oil repellents, crosslinking agents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents, and the like.

The method for preparing the water / oil repellent composition of the present invention is not particularly limited, and the following method is preferably employed. Method 1: A method of synthesizing a fluorinated polymer (A) in the presence of a fluorinated hydroxy compound (B). Method 2: A method of adding a fluorinated hydroxy compound (B) after the synthesis of the fluorinated polymer (A).

Of these, in the present invention, the method 1 is preferred from the viewpoint that the stability of the water / oil repellent composition after synthesis is high. When preparing the water-dispersed water / oil repellent composition by the method 1, a polymerizable monomer corresponding to the polymer (A), a fluorinated hydroxy compound (B), a surfactant, and an aqueous medium are essential. Preferably, the composition is prepared by a method such as an emulsion polymerization method or a suspension polymerization method, and directly polymerized by a method such as an emulsion polymerization method or a suspension polymerization method to obtain the water / oil repellent composition of the present invention.

Further, in the water / oil repellent composition of the present invention,
Further, it is preferable to include a blocked isocyanate compound other than the polymer (A). The blocked isocyanate compound is preferably a compound having no fluorine atom. It is believed that the blocked isocyanate compound functions as a crosslinking agent. The blocked isocyanate compound is preferably a compound in which all of the isocyanate groups in the isocyanate group-containing compound having no fluorine atom are blocked by a blocking agent.

Examples of the isocyanate group-containing compound include tolylene diisocyanate and its isomer, diphenylmethane diisocyanate and its isomer, naphthalene-1,5-diisocyanate and its isomer, xylylene diisocyanate and its isomer, hexamethylene diisocyanate and its isomer Isomers, 4,4-dicyclohexylmethane diisocyanate and isomers thereof,
Norbornane diisocyanate and its isomers, isophorone diisocyanate and the like can be mentioned. Further, these adducts, allophanate modified, buret modified, isocyanurate modified, carbodiimide modified,
Alternatively, it may be a urethane prepolymer or the like.

Examples of the blocking agent include oximes such as acetone oxime and methyl ethyl ketoxime, alcohols such as 2-ethylhexanol and methoxypropanol, phenols such as phenol and 2,4-dimethylphenol, ε-caprolactam and pyrrolidinone. Lactams, N-hydroxyimides such as N-hydroxysuccinimide and N-hydroxyphthalimide, imidazole, pentol, ethyl acetoacetate and the like are preferable.

In the water / oil repellent composition of the present invention, it is preferable to use it after diluting it to an arbitrary concentration according to the purpose and use. The amount of the fluoropolymer (A) after dilution is preferably 0.1 to 5% by weight in the water / oil repellent composition, and the amount of the fluorinated hydroxy compound is 0 in the water / oil repellent composition. .0
It is preferably set to 001 to 1% by weight. The amount of the blocked isocyanate compound is 0.1 to 5 in the water / oil repellent composition.
% By weight.

The water / oil repellent composition of the present invention is applied to an object to be treated to give the surface of the object water / oil repellency having excellent durability. An arbitrary method can be adopted as a method of applying to the object to be treated, depending on the type of the object to be treated, the preparation form of the composition, and the like. For example, a method is employed in which the material is adhered to the surface of the object to be processed by a coating method such as dip coating and dried. Further, the water / oil repellent composition of the present invention is preferably subjected to curing. The curing conditions are not particularly limited, and drying at a low temperature may be performed.

The object to be treated with the water / oil repellent composition of the present invention is not particularly limited, and fibers, fiber woven fabric, glass, paper, wood, leather, fur, asbestos, brick, cement, metal and the like can be used. Oxides, ceramic products, plastics and the like. Among these, the object to be treated is preferably a fiber or a fiber fabric. Examples of the fiber include animal and plant natural 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; Examples thereof include inorganic fibers such as carbon fiber and asbestos fiber. Examples of the fiber woven fabric include woven fabrics of the above fibers or mixed fibers.

The surface of an object to be treated, particularly the surface of a treated fiber or the surface of a treated fiber woven fabric, treated with the water / oil repellent composition of the present invention can be imparted with excellent water / oil repellency and excellent water-dropping property. On the surface of the object having excellent water droplet falling properties, the object is inclined, so that the water droplet easily rolls down due to the inclination of the object, and it is easy to remove the water droplet.

[0062]

EXAMPLES Next, the present invention will be specifically described with reference to Examples (Examples 1 to 3) and Comparative Examples (Example 4), but the present invention is not limited thereto. [Example 1] (Example) Perfluoroalkylethyl acrylate [F (CF
_{2) n CH 2 CH 2 OCOCH} = CH 2. n is 6-16
The average value of n was 9 in the mixture. (154 g), stearyl acrylate (90 g), cyclohexyl methacrylate (12.8 g), heptadecafluorodecanol [F (CF ₂ ) ₈ (CH ₂ ) ₂ OH, 20.5 g], stearyl mercaptan (0.77 g) , (Polyoxyethylene) oleyl ether (16.6 g), trimethylstearyl ammonium chloride (5.5 g), dipropylene glycol (97 g), ion-exchanged water (346
The composition containing g) was stirred at 50 ° C. for 30 minutes.

Further, while maintaining the composition at 40 to 50 ° C., using a high pressure emulsifier manufactured by
emulsified at g / cm ² . The particle size of the emulsion after emulsification was 0.24 μm. Next, this was transferred to a 1-liter glass autoclave, to which azobis (dimethyleneisobutyramide) hydrochloride (0.5 g) was added, and then the autoclave was replaced with nitrogen. The temperature was raised to 60 ° C. with stirring, and polymerization was carried out for 6 hours to obtain a milky white emulsion containing a polymer having an average molecular weight of 92,000. As a result of analyzing the milky white emulsion by gas chromatography, no unreacted polymerizable monomer of 10 ppm or more was detected. The solid concentration of the emulsion was 37.0% by weight, and the particle size was 0.12 μm. The emulsion was adjusted with water so that the solid content concentration became 20% by weight, and this was used as a stock solution.

Example 2 (Example) Heptadecafluoroundecanol [F (CF ₂ ) ₈ (CH ₂ ) ₃ O instead of heptadecafluorodecanol
H, 20.5 g], and polymerization was carried out in the same manner as in Example 1 to obtain an emulsion.

[Example 3] (Example) Instead of heptadecafluorodecanol, henicosafluorododecanol [F (CF ₂ ) ₁₀ (CH ₂ ) ₂ OH,
0.5 g] was used to carry out polymerization in the same manner as in Example 1 to obtain an emulsion.

Example 4 (Comparative Example) Nonafluorohexanol [F (CF ₂ ) ₄ (CH ₂ ) ₂ OH, instead of heptadecafluorodecanol, 20.
5 g], and an emulsion was obtained in the same manner as in Example 1.

[Processing Method for Cloth] The emulsion obtained above was contained in an amount of 5% by weight, and mayanate MF (block isocyanate manufactured by Meisei Chemical Industry Co., Ltd.) in an amount of 2% by weight.
After adjusting each of the treatment liquids diluted with water, a cotton broad cloth was immersed therein, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 70% by weight. Then 11
It was dried at 0 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds. The durability test of the test cloth was performed according to JIS-L021.
7 Washing was repeated 40 times in accordance with the water washing method shown in Appendix 103, followed by hot-air drying at 70 ° C. for 3 minutes. Water repellency, oil repellency,
Table 3 summarizes the evaluation results of the falling angle.

[Evaluation of Water Repellency] The water repellency numbers shown in Table 1 were obtained according to the spray test of JIS-L1092.

[0069]

[Table 1]

[Evaluation of Oil Repellency] AATCC-TM118
The results are shown in Table 2.

[0071]

[Table 2]

[Evaluation of water drop falling performance]
A 0 μl drop of water was made. After allowing the cloth to stand horizontally (0 °) for 1 minute, the cloth was inclined at 5 ° per minute, and the angle at which the water droplet began to roll was defined as the falling angle. The smaller the value of the falling angle is, the more excellent the water droplet falling property is.

[0073]

[Table 3]

[0074]

The water / oil repellent composition of the present invention is a composition which imparts excellent water / oil repellency to a material to be treated. Further, the performance imparted to the water / oil repellent composition is excellent in durability. The object treated with the water / oil repellent composition of the present invention is also provided with excellent water droplet falling properties, and thus has an advantage that water droplets can be easily removed.

Claims (9)

[Claims] (1) at least one kind of a fluoropolymer (A) and R ^f1 (CH ₂ ) _n OH (where R ^f1 has an average carbon number of 7)
The above polyfluoroalkyl group, n represents 2 to 4 integers. A water- and oil-repellent composition comprising at least one fluorine-containing hydroxy compound (B) represented by the formula (1). 2. The water / oil repellent composition according to claim 1, wherein R ^f1 is a polyfluoroalkyl group having an average of 7 to 16 carbon atoms. 3. A fluorine-containing hydroxy compound (B) is the number of n is from same and and two or more compounds having different numbers of carbon atoms of R ^f1, the average number of carbon atoms of R ^f1 is 7 to 16 wherein Item 3. The water / oil repellent composition according to Item 1 or 2. 4. The water / oil repellent composition according to claim 1, wherein the fluorinated polymer (A) is a polymer containing polymerized units of a (meth) acrylate having a polyfluoroalkyl group. object. 5. The fluoropolymer (A) is a polymer comprising a polymer unit of the following polymerizable monomer (a ¹ ) together with a polymer unit of a (meth) acrylate having a polyfluoroalkyl group. The water / oil repellent composition according to claim 1, 2, 3, or 4. Polymerizable monomer (a ¹ ): at least one polymerizable monomer selected from alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group, vinyl halide, and vinylidene halide . 6. The water / water repellency according to claim 1, wherein the fluorine-containing hydroxy compound (B) is contained in an amount of 0.1 to 20% by weight based on the fluorine-containing polymer (A). Oil composition. 7. The water / oil repellent composition according to claim 1, further comprising a blocked isocyanate compound. 8. The water / oil repellent composition according to claim 1, which is for treating fibers. 9. A treated fiber or woven fabric treated with the water / oil repellent composition according to claim 8.