JPH10325079A - Antifouling processing method - Google Patents

Abstract

(57) Abstract: Provided is an antifouling method with improved durability while having an initial soil release property, and a cellulosic fiber product subjected to antifouling processing. An antifouling method comprising treating a fluorinated cellulosic fiber product with an antifouling agent, and a cellulosic fiber product treated by the method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling processing method and a cellulosic fiber product subjected to antifouling processing, and more particularly, to a cellulosic fiber product having excellent antifouling property and durable soil release. The present invention relates to an antifouling method for imparting property.

[0002]

2. Description of the Related Art A (meth) acrylic ester containing a fluoroalkyl group is used as an antifouling agent which imparts water repellency and oil repellency to textile fabrics and the like, and makes it easy to remove stains attached to the fibers by washing or the like. Copolymers with a hydrophilic group-containing compound are known (see JP-A-53-134786, JP-A-59-204980, and JP-A-62-7782).

Further, among polymers of a (meth) acrylic ester containing a fluoroalkyl group, a (meth) acrylic ester containing a fluoroalkyl group is used in order to improve the water- and oil-repellent durability against washing. A copolymer composed of a (meth) acrylic acid ester having a hydroxyl group and, optionally, an alkyl (meth) acrylate has been developed (see, for example, Japanese Patent Publication No. 50-3798 and U.S. Pat. No. 3,356,628).

However, a copolymer of a (meth) acrylate having a hydroxyl group or a hydrophilic group such as polyethylene glycol and a (meth) acrylate having a fluoroalkyl group has an initial property of removing soil and repelling. Although the water repellency and the oil repellency are somewhat good, the stain release property and the durability of the water repellency are slight, and are not satisfactory. In order to solve such issues, we have previously (1)
(Meth) acrylic acid ester containing a fluoroalkyl group, (2) polyalkylene glycol (meth) acrylate, (3) (meth) acrylic acid ester having a hydroxyl group, and (4) alkyl (meth) acrylate or butadiene. A copolymer containing a derived structural unit was found, and a tentative solution was found (JP-A-3-10341).
No. 1). Unfortunately, there is still room for improvement in terms of durability, and it was not always satisfactory.

Conventionally, when imparting antifouling properties to cellulosic fibers, only treating the antifouling agent with the antifouling agent causes the antifouling agent to be removed from the cellulosic fibers when the cellulosic fibers expand and contract during washing or the like. It is difficult to obtain a durable dirt-removing property due to falling off.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an antifouling method and an antifouling cellulosic fiber product having improved durability while having an initial soil release property.

[0007]

The present invention provides an antifouling method comprising treating a fluorinated cellulosic fiber product with an antifouling agent.

In the present invention, since the fluorinated cellulosic fiber product has low water absorption and low hygroscopicity, there is almost no expansion and contraction due to water absorption and drying, and an antifouling agent is added to the fluorinated cellulosic fiber product. Even after treatment and washing, the antifouling agent does not fall off from the fluorinated cellulosic fiber, so that it is possible to obtain a durable stain release property.

Hereinafter, a method for fluorinating cellulosic fibers will be described. It is preferred that the cellulose fiber product is reacted with a fluorine-containing olefin compound, a fluorine-containing acrylate compound, or a fluorine-containing methacrylate compound in the presence of a catalyst to fluorinate the cellulosic fiber product. The reaction between the cellulosic fiber product and the fluorine-containing olefin compound, fluorine-containing acrylate compound, or fluorine-containing methacrylate compound is preferably an ionic reaction. Generally, an OH group of a cellulosic fiber product reacts with a fluorine-containing olefin compound, a fluorine-containing acrylate compound, or a fluorine-containing methacrylate compound. By the reaction, the cellulosic fiber product becomes a fluorocarbon group (Rf
Group, Rf 'group).

[0010] Textile products include fibers, yarns and fabrics formed from the fibers. The object to be processed may be any of fiber, yarn, and cloth. Cellulose-based fiber products include natural cellulose such as cotton and hemp, and regenerated cellulose such as viscose rayon and copper ammonia rayon. Others have 1 to 20 carbon atoms such as cellulose acetate and cellulose butyrate. Organic acid esters up to and including methylcellulose, ethylcellulose, alkyl ethers which may have a substituent having 1 to 6 carbon atoms, such as hydroxypropylcellulose, and cellulose derivatives such as nitrocellulose which are inexpensive and easily available. In addition, the present invention is also effective for those obtained by blending cellulosic fibers with other fibers.

The catalyst is preferably a basic catalyst, and particularly preferably a non-nucleophilic catalyst. Electrophilic catalysts are preferred. Of these, alkali metal / alkaline earth metal fluorides such as KF, NaF and CsF are mentioned from the viewpoint of not decomposing and coloring the cellulosic fiber products.
It is preferable to use The catalyst is preferably a dried one having a high activity. The amount of the catalyst added is-
It is preferably 0.5 to 20 equivalents, particularly preferably 1 to 5 equivalents, per equivalent of the OH group.

As the fluorine-containing olefin compound, R
fCF = CF ₂ , RfCF = CCIF, RfCF = CH ₂ , R
fCH = CH ₂ , Rf ₂ C = CF ₂ , Rf ₂ C = CH ₂ , and the fluorine-containing acrylate compound is RfOCOCH = C
H _2, the fluorine-containing methacrylate compound, RfO
COC (CH ₃ ) = CH _{2 wherein} Rf is F, Cl, a C _1-30 polyfluoroalkyl group, a C _1-30 polyfluoroalkenyl group, a C _1-30 polyfluoroalkoxy group, or _{2 to 300} polyfluoropolyether groups. ].

Rf may be, for example, a perfluoroalkyl group, a perfluoroalkenyl group, a perfluoroalkoxy group, or a perfluoropolyether group. Specific examples of Rf include the following. _{F- Cl- CF 3 - (CF 3} ) 2 CF (CF 2 CF 2) x- CF 3 CF 2 (CF 2 CF 2) x- CF 3 O- (CF 3) 2 CF (CF 2 CF 2) xO _{- CF 3 CF 2 (CF 2} CF 2) xO- H (CF 2 CF 2) yCH 2 O- [ wherein, x = 0 integer, y = 1 to 10 integer] (CF _{3) 2} CF (CF ₂ CF ₂ ) mCH ₂ CH ₂ OCH ₂ CH (O
_{H) CH 2 -, CF 3} CF 2 (CF 2 CF 2) mCH 2 CH 2 OC
_{H 2 CH (OH) CH 2} -, H (CF 2 CF 2) mCH 2 CH 2 O
_{CH 2 CH (OH) CH 2} -, (CF 3) 2 CF (CF 2 CF 2) m
_{CH 2 CH (OH) CH 2} -, CF 3 CF 2 (CF 2 CF 2) mC
_{H 2 CH (OH) CH 2} -, (CF 3) 2 CF (CF 2 CF 2) mC
_{H 2 CH 2 -, CF 3} CF 2 (CF 2 CF 2) mCH 2 CH 2 -,
H (CF ₂ CF ₂ ) 1 CH _2- [wherein, m is an integer of 0 to 10, l is an integer of 1 to 10]

(CF ₃ ) ₂ CF (CF ₂ CF ₂ ) mCH ₂ CH ₂ O
_{CH 2 CH (OH) CH 2} O-, CF 3 CF 2 (CF 2 CF 2) m
_{CH 2 CH 2 OCH 2 CH (} OH) CH 2 O-, H (CF 2 CF
_{2) mCH 2 CH 2 OCH 2} CH (OH) CH 2 O -, (CF 3) 2
_{CF (CF 2 CF 2) mCH} 2 CH (OH) CH 2 O-, CF 3
_{CF 2 (CF 2 CF 2)} mCH 2 CH (OH) CH 2 O -, (CF
_{3) 2 CF (CF 2 CF} 2) mCH 2 CH 2 O-, CF 3 CF 2 (C
_{F 2 CF 2) mCH 2 CH} 2 O-, H (CF 2 CF 2) lCH 2 O
-[Wherein, m = an integer of 0 to 10, l = an integer of 1 to 10]

HCF ₂ CF _2- , HCClFCF _2- , HC
F ₂ CClF−, CF ₃ CFHCF ₂ −, CF ₃ CF = CF
_{-, CF 2 = CFCF 2 -} , CH 3 CF 2 -, CF 3 CH
_2- , (CF ₃ ) ₂ CHCF _2- , HOC (CF ₃ ) _2- , Cl (C
F ₂ CClF) iCFHCClF- [wherein, i = 1 to 10 integer]

(CF ₃ ) ₂ CFCFHC (F) (CF ₃ )-, (C
F ₃ ) ₂ CFC (F) (CFHCF ₃ )-, (CF ₃ ) ₂ C (CFH
_{CF 2 CF 3) -, (} CF 3) 2 CHC (F) (CF 2 CF 3) -,
(CF ₃ ) ₂ CFC (F) [C (CF ₃ ) (H) CF ₂ CF ₂ CF ₃ ]
_{- (CF 3) 2 CFCFHC (} CF 3) (CF 2 CF 2 CF 3) -,
[(CF ₃ ) ₂ CF] ₂ C (CFHCF ₃ )-, [(CF ₃ ) ₂ C
F] ₂ CHC (F) (CF ₃ )-, (CF ₃ ) ₂ CFCF = C (C
F ₃ )-, (CF ₃ ) ₂ CFC (= CFCF ₃ )-, (CF ₃ ) ₂ C
(CF = CFCF ₃ )-, (CF ₃ ) ₂ C = CFC (F) (CF ₃ )
−,

(CF ₃ ) ₂ CFC (F) (CF = CF ₂ )-, C
_{F 2 = C (CF 3)} C (F) (CF 2 CF 3) -, (CF 3) 2 C = C
(CF ₂ CF ₃ )-, (CF ₃ ) ₂ CFC [= C (CF ₃ ) CF ₂ C
_{F 2 CF 3] -, (} CF 3) 2 C = CFC (CF 3) (CF 2 CF 2
CF ₃ )-, (CF ₃ ) ₂ CFC (F) [C (CF ₃ ) = CFCF _{2
CF 3] -, [(CF} 3) 2 CF] 2 C (CF = CF 2) -,
[(CF ₃ ) ₂ CF] ₂ C = C (CF ₃ )-, (CF ₃ ) ₂ C = C
_{[CF (CF 3) 2]} C (F) (CF 3) -

HCF ₂ CF ₂ O-, HCClFCF ₂ O-,
HCF ₂ CClFO-, CF ₃ CFHCF ₂ O-, CH ₃ C
_{F 2 O-, CF 3 CH 2} O- R (CF 2 CF 2 CF 2 O) a (CFHCF 2 CF 2 O) b (CH
_{2 CF 2 CF 2 O) c-} (CCl 2 CF 2 CF 2 O) d (CClFCF
_{2 CF 2 O) e-R} 2 -, R 1 (CF (CF 3) CF 2 O) f (CF
_{2 CF 2 O) g (CF} 2 O) h-R 2 - [ wherein, a, b, c, d , e, f, g, h is an integer of 0 to 100 does not become 0 at the same time; R, R ¹ Is hydrogen, halogen, or an alkoxy group having 1 to 3 carbon atoms.
Alternatively, all may be fluorinated. R ² is a divalent organic group having 1 to 5 carbon atoms, for example, a divalent alkyl group, a divalent alkenyl group, a divalent alkyl ether group, a divalent alkyl alcohol group and the like, and is partially or completely fluorinated. May be. ]

Alternatively, as fluorine-containing olefin compounds, Rf '[CF = CF ₂ ] _n , Rf' [CF = CClF] _n , R
_{f '[CF = CH 2]} n, Rf' [CH = CH 2] n, as the fluorine-containing acrylate _{compound, Rf '[OCOCH = CH 2} ] n,
As a fluorine-containing methacrylate compound, Rf '[O
COC (CH ₃ ) = CH ₂ ] _{n wherein} n is an integer of 2 to 4, R
f 'is a _C1-30 polyfluoro organic group or a _C2-300 polyfluoropolyether group. ].
Rf 'may be, for example, a perfluoro group. Also,
Rf 'may be a perfluoro organic group and a _C2-300 perfluoropolyether group.

The following are specific examples of Rf '. _{- (CF 2 CF 2) j-} - (CFClCF 2) j- - (CFHCF 2) j- - (CH 2 CF 2) j- [ wherein, j is 1 to 15 integer] -R ³ (CF ₂ CF ₂ CF ₂ O) a (CFHCF ₂ CF ₂ O) b
_{(CH 2 CF 2 CF 2 -O} ) c (CCl 2 CF 2 CF 2 O) d (CCl
_{FCF 2 CF 2 O) e-} R 2 -, -R 4 (CF (CF 3) CF 2 O) f (CF 2 CF 2 O) g (CF 2
O) h-R ² -wherein a, b, c, d, e, f, g, and h are not simultaneously 0 and are an integer of 0 to 100; R ² , R ³ , and R ^{4 each} have 1 carbon atom
To 5 divalent organic groups, for example, a divalent alkyl group, a divalent alkenyl group, a divalent alkyl ether group, a divalent alkyl alcohol group, and the like, and may be partially or entirely fluorinated. ]

[0021]

Embedded image [R ⁵ , R ⁶ , and R ⁷ are divalent organic groups having 1 to 5 carbon atoms, for example, a divalent alkyl group, a divalent alkenyl group, a divalent alkyl ether group, a divalent alkyl alcohol group, and the like. Or all may be fluorinated. ]

The amount of the fluorine-containing olefin compound, fluorine-containing acrylate compound or fluorine-containing methacrylate may be 0.1 to 50 equivalents, for example, 5 to 20 equivalents, per equivalent of glucose residue of the cellulosic fiber product. .

The fluorination reaction may be carried out in a state in which the cellulosic fiber product is not dissolved in a solvent (for example, using an aprotic polar organic solvent) or in a state in which it is dissolved (for example, using a homogeneous solvent system). . The fluorination reaction may be performed in an aprotic polar organic solvent. The aprotic polar organic solvent includes acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylenephosphamide, monoglyme, diglyme, triglyme, tetraglyme, and the like, with acetonitrile and dimethylformamide being particularly preferred.

The amount of the organic solvent may be 1 to 500 parts by weight, for example, 5 to 200 parts by weight per 1 part by weight of the cellulose fiber product.

The fluorination reaction may be carried out in a homogeneous solvent system in which the cellulosic fiber product is dissolved. Examples of the homogeneous solvent system include paraformaldehyde-dimethyl sulfoxide (preferable weight ratio of paraformaldehyde and dimethyl sulfoxide 1: 5 to 1:40), N-methylmorpholine oxide, chloral-dimethylformamide (chloral and dimethylformamide). Lithium chloride-dimethylacetamide type (preferable weight ratio of lithium chloride and dimethylacetamide 1: 3 to 1:30), sulfur dioxide-dimethylamine type (sulfur dioxide and dimethylamine) (Weight ratio 1:20 to 1:60), aprotic polar solvent-sulfuryl chloride-amine compound (the amount of sulfuryl chloride and amine compound is preferably 0.1 to 100 parts by weight of the aprotic polar solvent. 1 to 20 parts by weight and 0.1 to
20 parts by weight), aprotic polar solvent-thionyl chloride-
Amine compounds (preferable amounts of thionyl chloride and amine compounds are 0.1 to 20 parts by weight and 0.1 to 20 parts by weight, respectively, with respect to 100 parts by weight of the aprotic polar solvent.
Parts by weight) or an aprotic polar solvent-metal halide system (a preferable amount of the metal halide is 0.1 to 30 parts by weight based on 100 parts by weight of the aprotic polar solvent). preferable.

Examples of the aprotic polar solvent include acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylenephosphamide, monoglyme, diglyme, triglyme, tetraglyme, etc., with dimethylacetamide and dimethylsulfoxide being particularly preferred. Examples of the amine compound include triethylamine, diethylamine, propylamine, and butylamine, and triethylamine is particularly preferable.
Examples of metal halides are lithium chloride, lithium bromide, lithium iodide and the like, with lithium chloride being particularly preferred.

The amount of the homogeneous solvent is based on the cellulosic fiber product 1
20 to 200 parts by weight per part by weight, for example, 40 to 6 parts by weight
It may be 0 parts by weight. The amounts of sulfuryl chloride and thionyl chloride are 0.1 parts per part by weight of the cellulosic textile.
It may be 1 to 100 parts by weight, for example 1 to 10 parts by weight. The amount of the amine compound may be 0.1 to 100 parts by weight, for example, 1 to 10 parts by weight, per 1 part by weight of the cellulosic fiber product. The amount of the metal halide may be 0.1 to 600 parts by weight, for example, 1 to 20 parts by weight, per 1 part by weight of the cellulosic fiber product.

In order to dissolve the cellulosic fiber product in a homogeneous solvent system, the cellulosic fiber product may be added to a homogeneous solvent system (for example, an aprotic polar solvent, thionyl chloride, an amine compound, etc.). Preferably, the cellulosic fiber product and the aprotic polar solvent are refluxed, and after cooling, the remaining components of the homogeneous solvent system (for example, metal halides and the like) are added to the solution.

The reaction pressure for fluorination is 0.
-100 kg / cm ² G, and the reaction temperature is preferably 0 ° C.-150 ° C. The reaction time is usually 1 to 120 hours.

The antifouling agent will be described below. The antifouling agent may comprise a fluoropolymer. The antifouling agent may comprise the following copolymer (A) and / or copolymer (B). The antifouling agent is (A-1)
Acrylic ester or methacrylic ester having a fluoroalkyl group, (A-2) polyalkylene glycol acrylate, or polyalkylene glycol methacrylate, (A-3) 3-chloro-2-hydroxypropyl acrylate, or 3-chloro (A-4) glycerol monoacrylate or a copolymer (A) containing a structural unit derived from glycerol monomethacrylate.

Hereinafter, the monomers giving each structural unit will be described. The monomer (A-1) generally has the formula: Rf ″ R ⁸ OCOR ⁹ C ＝ CH ₂ , wherein Rf ″ is a linear or branched par having 3 to 20 carbon atoms. A fluoroalkyl group, R ⁹ is a hydrogen atom or a methyl group, R ⁸ is a linear or branched alkylene group having 1 to 10 carbon atoms, —SO ₂ N (R ¹⁰ ) R ¹¹
A group (R ¹⁰ represents an alkyl group having 1 to 10 carbon atoms, R ¹¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms) or —CH ₂ CH (OR ¹² )
A CH ₂ — group (R ¹² represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms)].

Specific examples of the monomer (A-1) are shown below. _{CF 3 (CF 2) 7 (} CH 2) 10 OCOCH = CH 2 CF 3 (CF 2) 6 CH 2 OCOC (CH 3) = CH 2 (CF 3) 2 CF (CF 2) 8 (CH 2) 2 OCOCH _{= CH 2 CF 3 (CF 2} ) 7 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 (CH 2) 2 OCOCH = CH 2 CF 3 (CF 2) 7 SO 2 N ( _{CH 3) (CH 2) 2} OCOH = CH 2 CF 3 (CF 2) 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOC (C
_{H 3) = CH 2 (CF} 3) 2 CF (CF 2) 8 CH 2 CH (OCOCH 3) CH 2 O
COC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH (OH) CH ₂ OCOCH
= CH ₂

The monomer (A-2) has the formula: CH ₂ ＣＲCR ¹³ COO- (R ¹⁴ O) p-R ^{15 wherein} R ¹³ and R ¹⁵ are a hydrogen atom or a methyl group, and R ¹⁴ is An alkylene group having 2 to 6 carbon atoms, p is represented by an integer of 3 to 50. ] Is preferable.

As R ¹⁴ , -CH ₂ CH _2- is usually preferred, but -CH (CH ₃ ) CH _2- , -CH (C ₂ H ₅ ) CH
_2- and so on. That is, in the present invention, R ¹⁴
Is particularly preferably a polyethylene glycol acrylate or methacrylate in which is —CH ₂ CH ₂ —. Also, p is selected from an integer of 3 to 50, and particularly good results are obtained when p is selected from an integer of 9 to 25. Of course, it may be in the form of a mixture of two or more kinds of R ¹⁴ and different p.

Specific examples of the monomer (A-2) are shown below. _{CH 2 = C (CH 3)} COO (CH 2 CH 2 O) 3-9 H CH 2 = C (CH 3) COO (CH 2 CH 2 O) 9 H CH 2 = C (CH 3) COO (CH 2 CH ₂ O) ₆ H CH ₂ ＣＨCHCOO (CH ₂ CH (CH ₃ ) O) ₁₁ CH ₃ CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O) ₉ H CH ₂ 3C (CH ₃ ) COO (CH ₂ CH ₂ O) ₅ (CH ₂ CH (C
_{H 3) O) 3 H CH} 2 = C (CH 3) COO (CH 2 CH 2 O) 9 CH 3 CH 2 = C (CH 3) COO (CH 2 CH 2 O) 23 CH 3 CH 2 = C ( CH ₃ ) COO (CH ₂ CH ₂ O) ₄₀ H

The 3-chloro-2-hydroxypropyl (meth) acrylate of the monomer (A-3) has the formula: CH ₂ ＣC (R ¹⁶ ) COOCH ₂ CH (OH) CH ₂ Cl [wherein R ¹⁶ is a hydrogen atom or a methyl group].

The glycerol mono (meth) acrylate of the monomer (A-4) is represented by the formula: CH ₂ ＣC (R ¹⁷ ) COOCH ₂ CH (OH) CH ₂ OH wherein R ¹⁷ is a hydrogen atom or methyl Is a group].

In the copolymer in the antifouling agent, the amount of the (meth) acrylic ester having a fluoroalkyl group (monomer (A-1)) is preferably at least 25% by weight, based on the copolymer. Is 30 to 70% by weight. 2
If it is less than 5% by weight, the water / oil repellency is not sufficient.

The amount of the polyalkylene glycol (meth) acrylate (monomer (A-2)) is at least 15% by weight, preferably 20 to 60% by weight, based on the copolymer.
If it is less than 15% by weight, the dispersibility in water is not good, so that the durability is not sufficient.

The amount of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (A-3)) is at least 0.5% by weight, preferably 0.5 to 3% by weight, based on the copolymer.
0% by weight. The amount of glycerol mono (meth) acrylate (monomer (A-4)) in the copolymer is at least 0.5% by weight, preferably 0.5 to 30% by weight.

The sum of 3-chloro-2-hydroxypropyl (meth) acrylate (monomer (A-3)) and glycerol mono (meth) acrylate (monomer (A-4)) is calculated as At least 5% by weight, preferably 8 to 3%
It is preferably 0% by weight. If the weight is less than 5%, the soil release property and durability are not sufficient. The monomer (A-
3) and 3-chloro- relative to the sum of the monomers (A-4)
The ratio of 2-hydroxypropyl (meth) acrylate is 1
It is preferably 0-90% by weight, preferably 20-80%. If the content is less than 10% by weight or more than 90% by weight, the durability is not sufficient.

The average molecular weight of the copolymer (A) is 1000
５００500,000, preferably 5,000 to 200,000. If it is less than 1000, the durability is not sufficient and it is 5000
If it is more than 00, the viscosity of the treatment liquid is too high, and the workability is reduced. The average molecular weight is a value determined by gel permeation chromatography (GPC) in terms of polystyrene. The copolymer (A) may be a random copolymer or a block copolymer.

The antifouling agent comprises (B-1) 5 to 95% by weight of repeating units derived from a fluoroalkyl group-containing monomer, and (B-2) a general formula: CH ₂ ＣＲCRCOO (CH
₂ CH ₂ O) _pH [wherein, R is a hydrogen atom or a methyl group, and p is a number of 1 to 50. And a copolymer (B) having a repeating unit of 95 to 5% by weight derived from a non-fluorinated monomer represented by the formula (B):

Fluoroalkyl group-containing monomer (B-1)
Is preferably a (meth) acrylate ester having a fluoroalkyl group. Preferred specific examples of the fluoroalkyl group-containing monomer (B-1) are as follows. _{CF 3 (CF 2) 4 CH} 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 (CH 2) 2 OCOC (CH 3) = CH 2 CF 3 (CF 2) 7 (CH 2) 2 OCOCH _{= CH 2 (CF 3) 2} CF (CF 2) 4 (CH 2) 2 OCOCH = CH 2 CF 3 (CF 2) 7 SO 2 N (C 3 H 7) (CH 2) 2 OCOC (C
_{H 3) = CH 2 CF 3} (CF 2) 7 (CH 2) 4 OCOCH = CH 2 CF 3 (CF 2) 7 SO 2 N (CH 3) (CH 2) 2 OCOC (CH 3)
_{= CH 2 CF 3 (CF 2} ) 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = C
H ₂ CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH
_{2 (CF 3) 2 CF (} CF 2) 6 (CH 2) 3 OCOCH = CH 2 (CF 3) 2 CF (CF 2) 6 CH 2 CH (OCOCH 3) CH 2 O
COC (CH ₃ ) = CH ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH (OH) CH ₂ OCOCH
= CH ₂ CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOCH = CH ₂ CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ CF ₃ (CF ₂ ) ₉ CONH (CH ₂ ) ₂ OCOC (CH ₃ ) = CH
₂ (CF ₂ Cl) (CF ₃ ) CF (CF ₂ ) ₆ CONH (CH ₂ ) ₂ OC
OCH = CH ₂ H (CF ₂ ) ₁₀ CH ₂ OCOCH = CH ₂ CF ₂ Cl (CF ₂ ) ₁₀ CH ₂ OCOC (CH ₃ ) = CH ₂

In the non-fluorinated monomer (B-2), p
Is 1 to 50, preferably 1 to 35, more preferably 1 to
25. The non-fluorinated monomer (B-2) may be used in combination of one or more. As the non-fluorinated monomer (B-2),
For example, CH ₂ ＣC (CH ₃ ) COOCH ₂ CH ₂ OH and CH
₂ = CHCOO (CH ₂ CH ₂ O) _6-8 H (preferable weight ratio 5:95 to 95: 5) or CH ₂ CHCO
OCH ₂ CH ₂ OH and CH ₂ ＣC (CH ₃ ) COO (CH ₂ CH
₂ O) _18-23 H (preferred weight ratio 5:95 to 95: 5) a combination of such is optimal.

In the copolymer (B), the fluoroalkyl group-containing monomer (B-1) / non-fluorinated monomer (B-
The weight ratio of 2) is 5/95 to 95/5, preferably 30/95.
70-80 / 20, more preferably 40 / 60-70 /
30. Fluoroalkyl group-containing monomer (B-1)
If the amount exceeds 95% by weight, the soil removability is insufficient. On the other hand, if it is less than 5% by weight, the oil repellency is insufficient. The average molecular weight of the copolymer (B) is usually from 1,000 to 10,000.
00, preferably 2000 to 100,000. This average molecular weight is measured by gel permeation chromatography (GPC) (in terms of polystyrene). The copolymer (B) may be a random copolymer or a block copolymer.

When durability is required, the monomer (B
-1), In addition to (B-2), 3-chloro-2-hydroxypropyl (meth) acrylate, n-methylol (meth)
Acrylamide, diacetone (meth) acrylamide, glycidyl (meth) acrylate, glycerol mono (meth)
Acrylate, polyoxydiene (meth) acrylate,
Polymerization may be carried out by adding a crosslinkable monomer such as trimethoxysilyl (meth) acrylate or (meth) acrylic acid. The amount of the crosslinkable monomer is usually from 0 to 1 based on the copolymer (B).
0% by weight, preferably 0 to 5% by weight, more preferably 0.1 to 5% by weight.

The copolymer (A) or (B) may be, in addition to the above-mentioned monomers, ethylene, vinyl chloride, vinylidene halide, alkyl (C ₁ -C ₁₈ ) ester of (meth) acrylic acid, styrene Acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, maleic anhydride, butadiene, and other polymerizable compounds that do not contain fluoroalkyl groups. By polymerizing, in addition to water and oil repellency, durability, and flexibility, a copolymer that is advantageous in terms of cost can be obtained, or solubility, water pressure resistance, and various other properties can be appropriately improved. . The amount of these copolymerizable compounds not containing a fluoroalkyl group is from 0 to 40% by weight, preferably from 0 to 20% by weight, based on the copolymer.

The antifouling agent may contain a solvent (C) in addition to the copolymer (A) or (B). In the solvent (C) used in the present invention, the solubility parameter is 5.5 to 12.0, preferably 6.0 to 11.5, more preferably 7.0 to 10.0, and the dielectric constant (20). ℃)
Is less than 20, preferably 19.0 to 2.0, more preferably 19.0 to 4.0.

Specific examples of the solvent (C) include trichloroethane,
Chlorine such as chloroform: ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone: toluene,
Aromatics such as benzene: esters such as ethyl acetate and butyl acetate: 1,1-dichloro-1-fluoroethane (1
41b) 1,1-dichloro-2,2,3,3,3-pentafluoropropane (225ca), 1,3-dichloro-1,
1,2,2,3-pentafluoropropane (225cb),
2,3-dihydroperfluoropentane (4310me
e) Alternative freons such as 1,4-dihydroperfluorobutane and 1,2-dihydroperfluorocyclobutane (C-336ee): petroleums such as hexane, heptane and mineral terpene. For alcohols, isopropyl alcohol having a relatively small solubility parameter (solubility parameter: 11.5) can be used. These can be used not only alone but also by mixing several liquids. In the antifouling agent, the amount of the solvent (C) is 20,000 parts by weight or less, for example, 100 to 2 parts by weight per 100 parts by weight of the copolymer.
0000 parts by weight, preferably 200 to 1000 parts by weight.

The solvent (C) can be used alone, but a solvent having a solubility parameter other than 5.5 to 12.0 or having a dielectric constant of 20 or more is used in an amount of about 20 parts by weight or less based on 100 parts by weight of the copolymer. And an antifouling agent.

Such a solvent is, for example, methanol,
Ethanol, ethylene glycols, diethylene glycols, propylene glycols, dipropylene glycols and the like.

In the present specification, the value of the solubility parameter (SP) is determined by a method of measuring latent heat of vaporization and a method described in Small literature (Small, Journal of Applied Chemistr).
y, 3, 71-80, Feb (1953)).

The value of the dielectric constant is determined by A. Weissborger;
ganic Solvent, 3rd Ed. And JARiddick, et al; Org
anic Solvent, 2nd, Ed. Or New Experimental Chemistry Course, published October 2, 1976 (The Chemical Society of Japan), vol. 5, p2
65 is a value obtained by a general method described in No. 65.

In order to further improve water repellency and oil repellency, it is possible to use a water repellent and oil repellent in combination. For example,
Commercially available TG-652 (manufactured by Daikin Industries, Ltd.) can be mixed in the copolymer solution at an arbitrary ratio. Preferably, the ratio of copolymer / water / oil repellent active ingredient is 10/0 to 1/5.

The antifouling agent may contain an isocyanate compound (D). The isocyanate compound (D) includes a blocked isocyanate. By adding the isocyanate compound (D) to the composition, the antifouling property and the durability of soil release are improved. Specific examples of isocyanates include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, resinester triisocyanate,
Polyisocyanates such as hexamethylene triisocyanate: adducts of polyisocyanates with monohydric alcohol polyhydric alcohols and polyols: block isocyanates obtained by blocking polyisocyanates with oximes, phenols, alcohols and the like. The amount of the isocyanate compound (D) is 0 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the copolymer.
More preferably, it is 20 to 80 parts by weight.

The antifouling agent contains, in addition to the copolymer (A) or (B), a solvent (C) or an isocyanate compound (D), or both a solvent (C) and an isocyanate compound (D). Can be. In the antifouling agent, the amount of the copolymer (A) or (B) depends on the amount of the antifouling agent 1
The amount is 50 to 0.01 part by weight, preferably 30 to 0.5 part by weight, per 100 parts by weight.

In order to obtain a copolymer in an antifouling agent, various polymerization methods and conditions can be arbitrarily selected, and various polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization and radiation polymerization can be used. Can be adopted. For example, a method in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized with stirring may be employed.

As the polymerization initiator of the reaction system, various compounds of peroxide, azo type or persulfate type can be used. When a surfactant contains polyethylene glycol acrylate or methacrylate as a constituent unit, it functions and does not need to be added separately, but various anionic, cationic or nonionic emulsifiers are optional. May be added. The polymerizable compound as a raw material can be dissolved in an appropriate organic solvent and subjected to solution polymerization by the action of a polymerization initiation source (eg, peroxide, azo compound or ionizing radiation soluble in the solvent used).

The copolymer thus obtained can be prepared in an arbitrary form such as a solvent solution, an emulsion or an aerosol according to a conventional method, and can be used as an antifouling agent. The copolymer can be applied to an article to be treated as an antifouling agent by any method according to the type of the article to be treated and the preparation form (solvent solution type, aerosol type, etc.). For example, in the case of an aqueous emulsion or a solvent solution type, a method in which a copolymer is adhered to the surface of an object to be treated and dried by a known method of coating such as dip coating is employed. sell. If necessary, curing may be performed together with a suitable crosslinking agent. The aerosol-type antifouling agent may be simply sprayed and sprayed on the object to be processed, and after drying immediately, can exhibit sufficient water and oil repellency and soil release properties. Further, the copolymer may be used as an antifouling agent by mixing another polymer blender. It is of course possible to obtain an antifouling agent by appropriately using other water repellents, oil repellents, insect repellents, flame retardants, antistatic agents, dye stabilizers, anti-wrinkle agents and the like as additives.

[0061]

Next, the present invention will be described in more detail by way of examples. However, "%" means "% by weight" unless otherwise specified.

Measurement method of degree of fluorination The degree of fluorination was determined by elemental analysis of fluorine (F (wt%)) by the bomb combustion method and the ion electrode method.

Test of dirt release performance (SR property) A test cloth was spread on blotting paper spread horizontally, and 5 dirty motor oils (SAE20W-40, which was put into the engine of a small passenger car and discharged after traveling 4,000 km) were discharged.
Add a polyethylene sheet on top of the drop
After 60 seconds, remove the weight and the polyethylene sheet, wipe off the excess oil, leave at room temperature for 1 hour, add a ballast cloth to the test cloth to make 1 kg, detergent (Super Zab (trade name), Kao Using 25 g of an electric washing machine with a bath volume of 35 L and a liquid temperature of 40 ° C.
Treat for minutes, rinse and air dry. The state of the remaining stain of the dried test cloth is compared with a judgment standard photographic plate, and the stain release performance is expressed by a corresponding judgment grade (see Table 1). The standard photographic plate used was AATCC-test method 130-1970.

[0064]

TABLE 1 determined grade criterion 1.0 as inconspicuous as 4.0 stain that 3.0 remains slightly stain that is left stain 2.0 equivalent what remains significantly stain 5.0 No stain left

Example 1 (1) Preparation of fluorinated cotton cloth In an autoclave, a raw cotton broad cloth: 5.84 g (3.67 × 10 ⁻² mol of glucose residues), dried KF (Crocat-F, Morita Chemical Co., Ltd.): 10.93g
(4 equivalents per equivalent of glucose residue) and 750 ml of dimethylformamide were added, and 141 g of tetrafluoroethylene (8.5 equivalents per equivalent of glucose residue) was gradually introduced at room temperature under a nitrogen atmosphere. After completing the introduction of tetrafluoroethylene, heat to 80 ° C.
Reacted for hours. After the reaction, the sample was purified water, HCFC-1
Each was washed 5 times with 41b, and air-dried all day and night. The fluorine content of the fabric was 1.46% by weight.

(2) Preparation of antifouling composition CF ₃ CF ₂ (CF ₂ CF ₂ ) qCH ₂ CH ₂ OCOC (CH ₃ ) =
Compound represented by CH ₂ (mixture of q = 3, 4, 5 in a weight ratio of 5: 3: 1): 20 g, CH ₂ ＣC (CH ₃ )
COO (CH ₂ CH ₂ O) ₉ CH ₃ : 10 g, CH ₂ ＣC (CH
₃ ) COO (CH ₂ CH (CH ₃ ) O) ₁₂ H: 5 g, CH ₂ ＣC
(CH ₃ ) COOCH ₂ CH (OH) CH ₂ Cl: 4 g, CH ₂
ＣC (CH ₃ ) COOCH ₂ CH (OH) CH ₂ OH: 1 g,
60 g of isopropanol was placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen. Then, 0.1 g of azobisisobutyronitrile was added, and a copolymerization reaction was carried out with stirring at 70 ° C. for 10 hours. . Gas chromatography showed that the conversion of the copolymerization reaction was 97% or more. From this conversion, it was found that the ratio of each structural unit in the obtained copolymer was almost equal to the ratio of the charged monomers. When the polymerization reaction was completed, 40 g of isopropyl alcohol and 60 g of deionized water were further charged and diluted. The resulting copolymer solution contained 19.5% copolymer solids. The average molecular weight of the copolymer is
According to gel permeation chromatography (GPC), it was 12000 (in terms of styrene).

Next, this copolymer dispersion was diluted with water so as to have a copolymer content of 0.6% by weight. The cotton broad cloth fluorinated in the treatment (1) was immersed in this, squeezed with a roll, and the wet pickup was adjusted to 80%. Next, it was dried at 110 ° C. for 2 minutes, and further heat-treated at 180 ° C. for 30 seconds to complete the water / oil / oil repellent / antifouling treatment.

Table 2 shows the results of measuring the soil release performance of the cloth treated as described above at the initial stage and after 10 washes.

Comparative Example 1 The procedure of Example 1 was repeated except that the diluting solution was applied to an untreated (no fluorination reaction) cotton broad cloth in place of the fluorinated cotton broad cloth of Example 1. ) The same procedure as above was repeated. Table 2 shows the results.

[0070]

[Table 2]

Example 2 (1) Preparation of fluorinated cotton cloth Raw cotton broad cloth: 5.84 g (glucose residue 3.67 × 10 ^-2 mol) in an autoclave, dried KF (Crocat-F, Morita Chemical Co., Ltd.): 10.93 g
(4 equivalents per equivalent of glucose residue) and 750 ml of dimethylformamide were added, and 141 g of tetrafluoroethylene (8.5 equivalents per equivalent of glucose residue) was gradually introduced at room temperature under a nitrogen atmosphere. After completing the introduction of tetrafluoroethylene, heat to 80 ° C.
Reacted for hours. After the reaction, the sample was purified water, HCFC-1
Each was washed 5 times with 41b, and air-dried for one day and night. The fluorine content of the fabric was 1.46% by weight.

(2) Preparation of antifouling composition CF ₃ CF ₂ (CF ₂ CF ₂ ) qCH ₂ CH ₂ OCOC (CH ₃ )
ＣＨCH ₂ (weight ratio of the compounds of q = 3, 4, 5: 5: 3: 1)
Mixture) 20 g, CH ₂ ＣＨCHCOO (CH ₂ CH ₂ O)
rH (r = 6, 7 and 8 by weight ratio of compounds 20:60:
20 mixture) 6 g, CH ₂ ＣC (CH ₃ ) CH ₂ CH ₂ OH
6 g and 59 g of isopropanol were placed in a four-necked flask. After sufficiently replacing the oxygen in the system with nitrogen, 0.17 g of 2,2'-azobis (2-methylbutyronitrile) was added, and 7
The polymerization reaction was carried out with stirring at 0 ° C. for 10 hours to obtain a dispersion of the copolymer. Gas chromatography showed that the conversion of the copolymerization reaction was 97% or more. From this conversion, it was found that the ratio of each structural unit in the obtained copolymer was almost equal to the ratio of the charged monomers.

Further, 82 g of methyl ethyl ketone was charged and diluted. The resulting copolymer solution contained 18.5% by weight of copolymer solids. The average molecular weight of the copolymer was determined by gel permeation chromatography (GP
According to C), it was 15000 (styrene equivalent).

This copolymer solution was used when the copolymer content was 0.7.
It was diluted with methyl ethyl ketone to 5% to obtain a diluted solution. The cotton broad cloth fluorinated in the treatment (1) was immersed in the diluent, squeezed with a roll, and the wet pickup was adjusted to 40%. Next, dry for 4 hours, and further 160
The water / oil repellent / antifouling treatment was completed by performing a heat treatment at 1 ° C. for 1 minute.

Table 2 shows the results of measuring the soil release performance of the cloth treated as described above at the initial stage and after ten selections. Comparative Example 2 The same procedure as in (2) and subsequent steps of Example 2 was repeated, except that the diluent was applied to untreated cotton broad cloth instead of the fluorinated cotton broad cloth of Example 2. Table 3 shows the results.

[0076]

[Table 3]

[0077]

According to the present invention, a good antifouling property and a very good soil release property can be imparted to a cellulosic fiber product to which sufficient soil release property has not been imparted so far. The effect can be maintained for a long time.

Claims (13)

[Claims] An antifouling method comprising treating a fluorinated cellulosic fiber product with an antifouling agent. 2. The cellulosic fiber product which is fluorinated by reaction with a fluorine-containing olefin compound, a fluorine-containing acrylate compound, or a fluorine-containing methacrylate compound in the presence of a catalyst. Item 7. The method according to Item 1. 3. The method according to claim 2, wherein the cellulosic fiber product is a cellulosic fiber product selected from the group consisting of natural cellulose and regenerated cellulose. 4. The method according to claim 2, wherein the catalyst is a basic catalyst. 5. The method according to claim 2, wherein the catalyst is a fluoride salt of an alkali metal or an alkaline earth metal. 6. The method according to claim 2, wherein the catalyst is potassium fluoride (KF). 7. The method according to claim 1, wherein the fluorine-containing olefin compound is RfC
F = CF ₂ , RfCF = CCIF, RfCF = CH ₂ , RfC
H = CH ₂ , Rf ₂ C = CF ₂ , Rf ₂ C = CH ₂ , the fluorine-containing acrylate compound is RfOCOCH = CH ₂ , and the fluorine-containing methacrylate compound is RfOCOC (CH ₃ ) =
CH _{2 wherein} Rf is F, Cl, or a C _1-30 polyfluoroalkyl group, a C _1-30 polyfluoroalkenyl group,
It is a _C1-30 polyfluoroalkoxy group or a _C2-300 polyfluoropolyether group. ).
The described method. 8. The method according to claim 8, wherein the fluorine-containing olefin compound is Rf ′
(CF = CF ₂ ) _n , Rf ′ (CF = CClF) _n , Rf ′ (CF =
_{CH 2) n, Rf '(} CH = CH 2) n, fluorine-containing acrylate _{compound, Rf' (OCOCH = CH 2} ) n, also the fluorine-containing methacrylate _{compound, Rf '[OCOC (CH 3} ) = C
H _{2] n} (wherein, n an integer from 2 to 4, Rf 'is a C _{1 to 30} polyfluoroorganic group, or C _{2 to 300} is a polyfluoropolyether group) of claim 2 wherein Method. 9. The antifouling agent comprises: (A-1) an acrylate or methacrylate having a fluoroalkyl group; (A-2) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate; 3) 3-chloro-2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate, and (A-4) glycerol monoacrylate or a molecular weight containing a structural unit derived from glycerol monomethacrylate of 1,000 to 500,000 (A)
The method of claim 1, comprising: 10. The antifouling agent comprises repeating units 5 to 9 derived from (B-1) a fluoroalkyl group-containing monomer.
5% by weight, and (B-2) general formula: CH ₂ ＣＲCRCOO
(CH ₂ CH ₂ O) _pH [wherein, R is a hydrogen atom or a methyl group, and p is a number of 1 to 50. The method according to claim 1, comprising a copolymer (B) having 95 to 5% by weight of a repeating unit derived from a non-fluorinated monomer represented by the following formula: 11. An antifouling agent comprising, in addition to the copolymer (A) or (B), (C) a solubility parameter of 5.5 to 5.5.
The method according to claim 9 or 10, comprising a solvent having a dielectric constant (20 ° C) of less than 20. 12. The method according to claim 9, wherein the antifouling agent also contains (D) an isocyanate compound. 13. A cellulosic fiber product treated by the method according to claim 1.