JP2000290640A - Water and oil repellent - Google Patents

Abstract

(57) [Problem] To provide a water / oil repellent which is extremely excellent in soil removability. SOLUTION: (a) The melting point of the homopolymer is 60 to 80.
A water / oil repellent comprising a copolymer of a fluoroalkyl group-containing monomer at (C) and a hydrophilic group-containing monomer (b) as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water / oil repellent containing a copolymer and a textile product treated with the same.

[0002]

2. Description of the Related Art As an antifouling agent [also referred to as an SR (Soil Release) agent] for imparting water repellency and oil repellency to a textile fabric and the like and easily removing dirt attached to the fiber by washing, a fluoroalkyl group ( A (meth) acrylate (hereinafter abbreviated as R _f group) (hereinafter referred to as R _f group)
_f group-containing monomer also called) and the copolymer of the hydrophilic group-containing monomer are known (JP 53-134786, JP same 59-204980, JP-the 62-7782 JP reference). However, the stain release property (SR property) and the durability of water repellency were not so good.

[0003] Recently, an antifouling agent having improved stain release property and durability of water repellency has been developed (Japanese Unexamined Patent Application Publication No. Hei 3 (1994)).
JP-A-103411, JP-A-4-68006, JP-A-6-106
116340). However, it was necessary to use a considerable amount of polymer in order to obtain sufficient soil release properties.
Therefore, development of a water / oil repellent exhibiting high stain removal performance and durability even at a low concentration has been desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water and oil repellent which can be used as an antifouling agent having a further improved soil release property than conventional antifouling agents.

[0005]

According to the present invention, there is provided a copolymer comprising (a) a fluoroalkyl group-containing monomer having a melting point of 60 to 80 ° C. in a homopolymer state and (b) a hydrophilic group-containing monomer. Provided is a water / oil repellent containing a polymer as a main component (active ingredient).

[0006] Sherman et al._fGroup-containing monomers and
Water and water repellency mainly composed of a copolymer with a hydrophilic group-containing monomer
Fluorinated water-repellent oil containing no hydrophilic group-containing monomer
The reasons for the higher soil release compared to oil repellents are as follows.
[P. Sherman, S. Smith, B. Johannesse
n, Textile Research Journal, 39, 449 (1969)]. R _f
Group-containing compounds have very low surface free energy
Because of this, the treated cloth has high water and oil repellency in air
Shows sex. On the other hand, R_fGroup-containing compounds are almost repellent in water
In order to not show oiliness, once oil stains adhere to the cloth,
It is very difficult to remove oil stains by washing.

However, a copolymer comprising an _Rf group-containing monomer and a hydrophilic group-containing monomer exhibits oil repellency even in water, so that oil stains are easily removed by washing. This is because the _Rf groups are oriented on the surface in the air to make it difficult for dirt to adhere, and in water (during washing), the hydrophilic groups are oriented on the surface and the surface is hydrophilized, thus removing oil stains. This is because it is easy to be done. Sherman et al. Call the property that the molecular structure of the surface changes depending on the environment in the air and in the water as flip-flop properties.

The present inventors have studied in detail the mechanism of developing water and oil repellency and soil release properties. As a result, the surface characteristics in air and water prove surface-chemically that the flip-flop property actually occurs, and the flip-flop property is confirmed.
It has been found that the one in which the property is easy to produce is superior in the stain removal property. In other words, in order to realize a water- and oil-repellent agent having a higher soil-removing property than the conventional antifouling agent, it is necessary to use R
_{What is} necessary is just to lower the crystallinity of the _f group and to increase the mobility of the polymer. On the other hand, _if the crystallinity of the _Rf group is too low, the oil repellency will be lost in the air, and the oil stain will penetrate the polymer film and enter the interior of the fiber, and it will be difficult to remove it by washing. That is, it is necessary that the crystallinity of the _Rf group is such that the flip-flop property and the oil repellency in the air are compatible.

The present invention is a further improvement of the soil release performance of a conventional antifouling agent. The melting point of the homopolymer originates from the crystallinity of the R _f group, which can be measured by differential scanning calorimetry (DSC). The presence of the R _f group crystal is also confirmed by observing a peak derived from its self-aggregation by wide-angle X-ray diffraction. Usually, the crystallinity is represented by the crystallinity shown in the following formula. [Crystallinity (%)] = I _Rf / (I _Rf + I _am ) × 100 where I _Rf is the peak intensity of the _Rf group appearing at 2θ = 18 °, and I _am is the peak intensity of the amorphous region. .

The monomers used in the present invention will be described below. The monomer (a) is represented by a general formula: R _f -R ¹ -X-R ² C = CH ₂ [wherein, R _f is a linear fluoroalkyl group having 3 to 20 carbon atoms, and R ¹ is a carbon atom. A linear or branched alkylene group of Formulas 1 to 10, R ² is a hydrogen atom or a methyl group, X is
-O-C (= O) - or ^{_{-SO 2 -N (A 1) -A}} 2 -
(In the formula, A ¹ is an alkyl group having 1 to 4 carbon atoms, A ² is a direct bond or —A ³ —O—C (＝ O) — (A ³ is
To 4 alkylene groups). ). ] Is preferable. The melting point of the homopolymer of the monomer (a) is 60 to 80C, for example, 65 to 75C. The crystallinity of the monomer (a) in a homopolymer state is preferably 50 to 85%, for example, 60 to 80%. The monomer (a) may be a mixture of two or more.

As the antifouling agent which has been put to practical use, a mixture of _Rf group-containing monomers having different R _f group chain lengths has been used. For example, a mixture of fluoroalkyl (meth) acrylates having 8, 10, or 12 carbon atoms in the _Rf group (weight ratio of 5: 3: 1) has been used. This is because the fluoroalkyl intermediate is industrially produced by telomerization of tetrafluoroethylene and CF ₃ CF ₂ I, and at this time, it is obtained as a mixture of perfluoroalkyl iodide telomers having different carbon numbers.

[0012] The present inventors have found that in such _the R _f group chain of distribution length monomers, _the R _f group chain length long monomer (carbon number of specifically _the R _f group is It has been found that the smaller the ratio of 10 or 12) is, the higher the mobility of the polymer is, and hence the more excellent the soil release property is. For example, rather than using a fluoroalkyl acrylate obtained by telomerization (the _Rf group having 8, 10, and 12 carbon atoms in a weight ratio of 5: 3: 1), R It has been found that the use of a fluoroalkyl acrylate in which the _f group has 8 carbon atoms has higher flip-flop properties of the polymer, and therefore, is more excellent in soil release properties.

R_fSpecific examples of the group-containing monomer (a) are shown below.
I will. CF_Three(CF_Two)₇(CH_Two)_TwoOCOCH = CH_Two CF_Three(CF_Two)_Five(CH_Two)_TwoOCOCH = CH_TwoAnd CF_Three(CF_Two)₇(CH_Two)_TwoOCOCH = C
H_Two2: 8 mixture by weight of CF_Three(CF_Two)₇(CH_Two)_TwoOCOCH = CH_TwoAnd CF_Three(CF_Two)₉(CH_Two)_TwoOCOCH = C
H_Two8: 2 mixture by weight of CF_Three(CF_Two)₇(CH_Two)_TwoOCOCH = CH_TwoAnd CF_Three(CF_Two)₁₁(CH_Two)_TwoOCOCH =
CH_Two9: 1 by weight mixture CF_Three(CF_Two)₇SO_TwoN (CH_Three) (CH_Two)_TwoOCOCH = CH_Two CF_Three(CF_Two)₇SO_TwoN (C_TwoH_Five) (CH_Two)_TwoOCOCH = CH_Two CF_Three(CF_Two)₇(CH_Two)_TwoSO_TwoN (CH_TwoCH_Three) CH = CH_Two CF_Three(CF_Two)₇(CH_Two)_TwoSO_TwoN (CH_TwoCH_Three) CH = CH_TwoAnd CF_Three(CF_Two)₉(CH_Two)
_TwoSO_TwoN (CH_TwoCH_Three) CH = CH_Two8: 2 mixture by weight of CF_Three(CF_Two)₇(CH_Two)_TwoSO_TwoN (CH_TwoCH_Three) CH = CH_TwoAnd CF_Three(CF_Two)₁₁(C
H_Two)_TwoSO_TwoN (CH_TwoCH_Three) CH = CH _Two9: 1 by weight mixture CF_Three(CF_Two)₇(CH_Two)_TwoSO_TwoN (CH_Three) CH = CH_Two

As the _Rf group-containing monomer (a), those having 8 carbon atoms in the _Rf group are preferably used alone. R
The weight ratio of the monomer having 8 carbon atoms in the _f group to the monomer having 8 carbon atoms in the R _f group other than 8 (for example, 3 to 7 or 9 to 20) is 100: 0.5 to 50. May be used as the _Rf group-containing monomer.

The hydrophilic group-containing monomer (b) may have a carbon-carbon double bond and a hydrophilic group. Examples of hydrophilic groups are ether groups such as alkylene ethers, hydroxyl groups, carboxyl groups, carbonyl groups, sulfo groups, sulfonamide groups and phospho groups.

The hydrophilic group-containing monomer (b) has the formula: CH ₂ ＣＲCR ³ COO— (R ⁴ O) _n —R ^{5 wherein} R ³ and R ⁵ are a hydrogen atom or a methyl group; ^Four
Represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 50, for example, 3 to 40. ] Is preferable.

As R ⁴ , -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, polyethylene glycol acrylate or methacrylate in which R ⁴ is —CH ₂ CH ₂ — can be particularly preferably used. Further, it may be in the form of a mixture of two or more kinds having different types of R ⁴ and different values of n.

Specific examples of the hydrophilic group-containing monomer (b) are shown below. _{CH 2 = C (CH 3)} COOCH 2 CH 2 OH CH 2 = C (CH 3) COO (CH 2 CH 2 O) 9 H CH 2 = CHCOO (CH 2 CH (CH 3) O) 11 CH 3 CH 2 = CHCOO (CH ₂ CH ₂ O) ₉ H CH ₂ = C (CH ₃ ) COO (CH ₂ CH ₂ O) ₅ (CH ₂ CH (CH ₃ ) O) ₃ H CH ₂ = C (CH ₃ ) COO ( (CH ₂ CH ₂ O) ₄₀ H

The proportion of the _Rf group-containing monomer (a) is at least 25% by weight, preferably 30 to 8%, based on the copolymer.
It may be 0% by weight, especially 40-70% by weight. If it is less than 25% by weight, the water / oil repellency may not be sufficient.

The proportion of the hydrophilic group-containing monomer (b) is at least 10% by weight, preferably 20 to 20% by weight, based on the copolymer.
It may be 70% by weight, especially 30-60% by weight. 10
If the amount is less than the weight percentage, the soil removability may not be sufficient.

The molecular weight of the copolymer of the present invention is 1,000
~ 500,000, preferably 5,000 ~ 200,00
It may be 0. If it is less than 1,000, the durability may not be sufficient, and if it is more than 500,000, the viscosity of the treatment liquid may be too high and the workability may be reduced. The molecular weight is a value determined by gel permeation chromatography in terms of polystyrene. The copolymer of the present invention may be a random copolymer or a block or graft copolymer.

The copolymer of the present invention comprises, in addition to the _Rf group-containing monomer (a) and the hydrophilic group-containing monomer (b), ethylene, vinyl chloride, vinylidene halide, styrene and acrylic acid. The alkyl ester, methacrylic acid and its alkyl ester, benzyl methacrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene,
It may contain a monomer that does not contain an _Rf group, such as chloroprene, maleic anhydride, butadiene, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and glycidyl (meth) acrylate. . By copolymerizing a monomer containing no _Rf group, a copolymer which is advantageous in terms of water repellency, oil repellency, durability, flexibility, solubility, and water pressure resistance can be obtained. Also, by adjusting the molecular weight with a chain transfer agent,
Various other properties can be improved as appropriate. The proportion of these polymerizable compounds not containing an R _f group may be 0 to 40% by weight, preferably 0 to 20% by weight, based on the copolymer.

In order to obtain the copolymer of the present invention, various polymerization systems such as bulk polymerization, solution polymerization, emulsion polymerization and radiation polymerization can be selected. For example, a method in which a polymerizable compound as a raw material is dissolved in an appropriate organic solvent and solution polymerization is performed by the action of a polymerization initiation source (eg, a peroxide, an azo compound, or ionizing radiation that is soluble in the organic solvent used). Can be done. Specifically, various compounds of peroxide, azo type or persulfate type can be used as the polymerization initiator of the reaction system. Further, 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.

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 a water / oil repellent. The water- and oil-repellent agent of the present invention may contain, in addition to the copolymer, a medium such as water and an organic solvent, a surfactant (for example, an anionic surfactant, a cationic surfactant and / or a nonionic surfactant).
May be included.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate and butyl acetate;
Ethanol, isopropanol, butanol, 1,3-
Alcohols such as butanediol, 1,5-pentanediol, perchlorethylene, trichlene, 1,1-
Dichloro-2,2,3,3,3-pentafluoropropane,
1,3-dichloro-1,2,2,3,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane (HCF
Halogenated hydrocarbons such as C-141b), octane,
Petroleum, hydrocarbons such as toluene and xylene, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether,
Polypropylene glycol, triethylene glycol dimethyl ether, propylene glycol, and ethylene glycol.

Examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonyl phenyl ether sulfate, polyoxyethylene lauryl ether triethanolamine sulfate, cocoyl sarcosine. Sodium, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coco alkyl ether sulfate, sodium dietherhexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxylic acid Acid salt (trade name Unidyne DS-
101, 102 (manufactured by Daikin Industries, Ltd.)).

Examples of cationic surfactants are dialkyl
(C ₁₂ -C ₂₂ ) dimethylammonium chloride, alkyl (coconut) dimethylbenzylammonium chloride, octadecylamine acetate, tetradecylamine acetate,
Tallow alkylpropylenediamine acetate, octadecyltrimethylammonium chloride, alkyl (tallow) trimethylammonium chloride, dodecyltrimethylammonium chloride, alkyl (coconut) trimethylammonium chloride, hexadecyltrimethylammonium chloride, biphenyltrimethylammonium chloride, alkyl (tallow) imidazoline 4 Grade salts, tetradecylmethylbenzylammonium chloride, octadecyldimethylbenzylammonium chloride, dioleyldimethylammonium chloride, polyoxyethylene dodecylmonomethylammonium chloride,
Polyoxyethylene alkyl (C ₁₂ -C ₂₂₎ benzylammonium chloride, polyoxyethylene lauryl monomethyl ammonium chloride, 1-hydroxyethyl-2-alkyl (tallow) imidazoline quaternary salt, a silicone cationic surfactant having a siloxane group as a hydrophobic group Surfactant, a fluorine-based cationic surfactant having a fluoroalkyl group as a hydrophobic group (trade name: Unidyne DS-202)
(Manufactured by Daikin Industries, Ltd.)).

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxypropylene cetyl ether,
Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolau Rate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate,
Sorbitan sesquioleate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxysorbitan monooleate, polyoxyethylene polyoxypropylene block polymer, poly Glycerin fatty acid ester, polyether-modified silicone oil (trade names: SH3746, SH3748, SH3749, SH
3771 (Toray Dow Corning Silicone Co., Ltd.)
Manufactured)), perfluoroalkyl ethylene oxide adduct
(Trade name: Unidyne DS-401, DS-403 (manufactured by Daikin Industries, Ltd.), fluoroalkyl ethylene oxide adduct (trade name: Unidyne DS-406 (Daikin Industries, Ltd.)
And perfluoroalkyl oligomers (trade name: Unidyne DS-451 (Daikin Industries, Ltd.)).

The proportion of the copolymer in the water / oil repellent is as follows:
It may be up to 60% by weight, preferably 1 to 30% by weight.

The water / oil repellent of the present invention can be applied to an article to be treated as an antifouling agent by any method according to the kind of the article to be treated and the preparation form (solvent solution type, aerosol type, etc.). obtain. For example, in the case of a solvent solution type or an aqueous emulsion, a method of attaching to a surface of an object to be processed and drying by a known method of coating such as dip coating may be adopted. If necessary, curing may be performed by applying 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, it can exhibit sufficient water and oil repellency and soil release properties.

Further, the copolymer of the present invention may be mixed with another polymer blender to form an antifouling agent. Of course, it is also 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.

The material to be subjected to the antifouling treatment is usually a fiber product. Various examples can be given as fiber products. For example, 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; and carbon fibers. And inorganic fibers such as asbestos fibers, or a mixed fiber thereof.

The fiber product may be in any form of fiber, yarn, cloth and the like. The copolymer of the present invention is 0.1% when treated.
It can be used after being diluted to ３０30% by weight, preferably 1-10% by weight. If the concentration is too low, the performance will be insufficient, and if the concentration is too high, the texture of the treated fiber will be poor.

[0034]

Next, the present invention will be described in more detail with reference to Examples, Comparative Examples and Test Examples. However, it goes without saying that these descriptions do not limit the present invention. The test of the soil release property (SR property) was performed as follows.
That is, a test cloth was spread on blotting paper laid horizontally, 0.05 ml of a dispersion of carbon black 0.1% dispersed in triolein was dropped as a stain, and a polyethylene sheet was placed on the dispersion, followed by 500 g of 500 g. A weight was placed, and after 60 seconds, the weight and the polyethylene sheet were removed, and left at room temperature for 24 hours to attach a stain to the test cloth. Next, a ballast cloth was added to the test cloth to make 500 g, and a detergent (trade name: Lion Super Compact Top) 1
Using 2.5g, electric washing machine, bath volume 25 liters,
Washing was performed for 5 minutes at a bath temperature of 40 ° C., followed by rinsing and drying at room temperature. The lightness of the portion of the dried test cloth where the stain remained was measured with a color difference meter (CR-200 manufactured by MINOLTA), and the stain removal performance was evaluated from the following stain rate (%).

The stain release performance is evaluated by using the lightness of the remaining colored solid particles (in this case, carbon black) as an index, and is evaluated by the “contamination rate” represented by the following equation. [Stain ratio (%)] = (R ₀ −R) / R ₀ × 100 Here, R ₀ is the lightness of the unstained cloth, and R is the lightness of the contaminated cloth. This is based on the premise that the solid particle soil is washed together with the oily soil (here, triolein) at the time of washing, and by measuring the lightness of the solid particle soil that can be visually discriminated, the composite composed of the solid particles and oil is measured. This is a method for evaluating the stain removal rate. The present inventors have confirmed that there is a correlation between the relationship between the carbon black and the triolein removal rate. Therefore, although the evaluation of the soil detachability based on the above-mentioned contamination rate is simple, it is a practical method capable of simultaneously measuring solid particle soil and oily soil. Here, it is shown that the smaller the contamination rate is, the higher the stain removal performance is.

Reference Production Example 1 CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH = CH ₂
Monomer (n = 3) (abbreviated as “17FA”) 1
0 g, 1,1,2,3,4,4-hexafluorotetrachlorobutane (40 g) was placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen. Then, t-butyl peroxypivalate (Japan 0.5 g of oil-and-fat perbutyl PV)
The reaction was carried out with stirring at 0 ° C. for 6 hours. The obtained polymer was reprecipitated with ethanol and purified to obtain 9 g of a fine white powder polymer.

Reference Production Examples 2 to 4 Similar to Reference Production Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) _n
A monomer which is a mixture of CH ₂ CH ₂ OCOCH = CH ₂ and n = 3, 4, 5 in a weight ratio of 5: 3: 1 (“T-
Each of homopolymers of a monomer having an FA of 2), a monomer having an n of 2 (abbreviated as "13FA"), and a monomer having an n of 4 (abbreviated as "21FA") was polymerized.

Production Example 1 24 g of 17FA shown in Reference Production Example 1, CH ₂ ＣC (C
H ₃ ) COOCH ₂ CH ₂ OH (abbreviated as “HEMA”)
6 g and 360 g of isopropanol were placed in a four-necked flask, and oxygen in the system was sufficiently replaced with nitrogen. Then, 2,2-azobis (2-methylbutyronitrile) [V-5 manufactured by Wako Pure Chemical Industries, Ltd.]
9] 0.1 g was added, and the copolymerization reaction was started at 60 ° C.
After 30 minutes, the temperature of the system was raised to 70 ° C., and after 30 minutes, 1 hour later, 0.01 g of the initiator was added. The reaction was allowed to proceed for 6 hours from the first addition of the initiator. The obtained polymer was reprecipitated with n-hexane and purified to obtain 36 g of a fine white powder polymer.

Comparative Production Examples 1-3 Copolymers of T-FA and HEMA (Comparative Production Example 1), copolymers of 13FA and HEMA (Comparative Production Example 2), and 21FA The HEMA copolymer (Comparative Production Example 3) was polymerized.

Example 1 The polymers obtained in Reference Production Examples 1 to 4 were subjected to DSC
Table 1 shows the results of the melting point measured and the crystallinity determined by X-ray diffraction. DSC measurement was made by Shimadzu DSC-50.
Was performed at a sample amount of 10 mg and a heating rate of 20 ° C./min. X-ray diffraction is Rigaku Rotor Flex RA
Cu-Kα (15.42 nm) for X-ray source by D-rA type
And the output was measured at 40 kV and 50 mA. Then, the crystallinity was calculated from the following equation. [Crystallinity (%)] = I _Rf / (I _Rf + I _am ) × 1
Here, I _Rf is the peak intensity of the _Rf group appearing at 2θ = 18 °, and I _am is the peak intensity of the amorphous region.

[0041]

[Table 1]

The melting point and crystallinity of the _Rf group-containing monomer homopolymer decreased as the _Rf group chain length became shorter. Therefore, it is considered that the shorter the carbon number of the R _f group, the higher the molecular mobility of the polymer. Further, the melting point was not observed for the 13FA homopolymer having 6 carbon atoms in the R _f group. This is because the _Rf base chain length is short and the molecular mobility is considerably large, so that crystallization does not occur.

Example 2 The polymer obtained in Production Example 1 and Comparative Production Examples 1 to 3 was heated on a hot plate, and the temperature at which the appearance became round when observed with a microscope (softening point). Table 2 shows the results obtained by examining the crystallinity by X-ray diffraction in the same manner as in Example 1.

[0044]

[Table 2]

It is considered that a copolymer having a shorter R _f group chain length has a lower softening point and crystallinity and a higher molecular mobility. This is thought to be because, as shown in Example 1, the shorter the _Rf chain length, the higher the molecular mobility of the homopolymer.

Example 3 The polymers obtained in Production Example 1 and Comparative Production Examples 1 to 3 were diluted with a mixed solvent of toluene and isopropanol so as to have a polymer content of 1% by weight. The immersion treatment was performed at 0.5 mm / sec. After air drying, heat treatment was performed at 80 ° C. for 3 minutes. Then, the contact angle of water in air and the contact angle of air bubbles in water (after immersion for 5 minutes) were measured with a contact angle meter manufactured by Kyowa Interface Science. The contact angle of bubbles in water was measured using the original cell. Table 3 shows the results.

[0047]

[Table 3]

Each of the copolymers had a contact angle of water in the air of about 110 ° and exhibited high water repellency. However, the contact angle of bubbles in water was about 50 °, which was considerably smaller than that of 17FA / stearyl acrylate copolymer (about 100 °), which is a copolymer of hydrophobic monomers. This indicates that the substance is hydrophobic in the air but hydrophilic in the water, and that the structure of the surface changes when the substance is moved from the air to the water (flip-flop property). When compared by polymer structure, the contact angle of bubbles in water was smaller in the 13FA copolymer and the 17FA copolymer having a shorter _Rf group chain length. This is presumably because the shorter the _Rf group chain length, the higher the molecular mobility, so that flip-flop properties tend to occur.

Example 4 The same film treated with the polymer in Example 3 was used to measure the dry and hydrated ESCA. ESCA750 manufactured by Shimadzu Corporation was used. The emission angle was 20 °. The dry state was measured with the film after heat treatment as it was. The hydration state was measured immediately after the film was immersed in water for 5 minutes to remove excess water. Then, the ratio of the peak area derived from fluorine to the peak area derived from carbon (F / C) and the ratio of the peak area derived from oxygen to the peak area derived from carbon (O / C) were examined. Table 4 shows the results.

[0050]

[Table 4]

In each of the copolymers, the F / C was small and the O / C was slightly large from the dry state to the hydrated state. This indicates a decrease in R _f groups and an increase in hydrophilic groups on the polymer surface, indicating that the surface structure was changed by immersion in water. Also, when comparing by polymer structure,
F / C reduction rate from dry state to hydrated state, and O /
The rate of increase in C was as follows: 13FA copolymer having a short R _f
The 7FA copolymer was larger. This is presumably because, as shown in Example 3, the shorter the _Rf group chain length is, the higher the molecular mobility is, so that flip-flop property is likely to occur.

Example 5 The polymers obtained in Production Example 1 and Comparative Production Examples 1 to 3 were diluted with a mixed solvent of toluene and isopropanol so that the polymer content was 0.5% by weight. A cotton broad cloth was immersed in this, squeezed with a roll, and the wet pickup was adjusted to 50%. After air drying, heat treatment was performed at 80 ° C. for 3 minutes. The cloth thus treated was subjected to a soil removal performance test. Table 5 shows the results.

[0053]

[Table 5]

T-FA copolymers (mixtures of 8, 10 and 12 carbon atoms) having a distribution in the R _f group chain length which are practically used as raw materials for antifouling agents, and long R _f group lengths (C 1
0) R _{f is} a main component of T-FA rather than 21FA copolymer.
The 17FA copolymer having a shorter base chain length and a constant (8 carbon atoms) had a lower contamination rate and a higher soil release property. this is,
The 17FA copolymer has higher molecular motility and flip-
It is considered that flop is likely to occur. On the other hand, the 13FA copolymer, which is considered to have the highest molecular mobility, had poorer soil release properties than the 17FA copolymer.

Example 6 Table 6 shows the results obtained by dropping eight types of oils (hydrocarbons) having different surface tensions onto the cloth treated in Example 5 and examining the oil repellency. The surface tension of the dropped oil (25 ° C) is 1
Point-31.2,2 points-29.6,3 points-27.3,4 points-
26.7, 5 points-25.0, 6 points-23.5, 7 points -2
1.8, 8 points-20.0 mN / m, and the maximum oil score that did not soak into the cloth was taken as oil repellency. Therefore, the higher the oil repellency score, the lower the surface free energy of the treated cloth.

[0056]

[Table 6]

17FA copolymer, T-FA copolymer, 2
The 1FA copolymer showed high oil repellency, but 13FA
The copolymer had poor oil repellency and soaked all oils.
Therefore, it is considered that the molecular mobility is the highest 1
The reason why the 3FA copolymer has poorer soil releasability than the 17FA copolymer is that the _Rf group is too short, resulting in poor crystallinity and loss of oil repellency. It is thought that it became difficult to be done.

Example 7 The cloth treated in Example 5 was washed five times in the same manner as in the soil release test, and then the soil release performance test was performed. Table 7 shows the results.

[0059]

[Table 7]

As in Example 5, the contamination rate of the 17FA copolymer was smaller than that of the T-FA copolymer or 21FA copolymer. This indicates that the 17FA copolymer exhibits high stain release properties even after repeated washing, and is excellent in durability.

[0061]

The water- and oil-repellent using the copolymer of the present invention is extremely excellent in soil release properties as compared with conventional water- and oil-repellents.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 15/277 D06M 15/277 // D06M 101: 04 (72) Inventor Kubo Motonobu West of Settsu-shi, Osaka Ichitsuya 1-1 Daikin Industries, Ltd. Yodogawa Works

Claims (6)

[Claims] (1) a melting point of 60% in a homopolymer state;
A water- and oil-repellent agent comprising, as a main component, a copolymer comprising a fluoroalkyl group-containing monomer having a temperature of from 80 to 80 ° C and (b) a hydrophilic group-containing monomer. 2. A fluoroalkyl group-containing monomer (a)
Is a general formula: R _f —R ¹ —X—R ² C ＝ CH _{2 wherein} R _f is a straight-chain fluoroalkyl group having 3 to 20 carbon atoms, and R ¹ is a straight-chain fluoroalkyl group having 1 to 10 carbon atoms. A chain or branched alkylene group, R ² is a hydrogen atom or a methyl group, X is
-O-C (= O) - or ^{_{-SO 2 -N (A 1) -A}} 2 -
(In the formula, A ¹ is an alkyl group having 1 to 4 carbon atoms, A ² is a direct bond or —A ³ —O—C (＝ O) — (A ³ is
To 4 alkylene groups). ). The water / oil repellent according to claim 1, which is a compound represented by the formula: 3. A compound having a hydrophilic group-containing monomer (b) represented by the following general formula: CH ₂ ＣＲCR ³ COO— (R ⁴ O) _n —R ^{5 wherein} R ³ and R ⁵ are hydrogen atoms or methyl Group, R ⁴
Represents an alkylene group having 2 to 6 carbon atoms, and n represents an integer of 1 to 50. The water / oil repellent according to claim 1, which is a compound represented by the formula: 4. The water / oil repellent according to claim 1, wherein the fluoroalkyl group of the fluoroalkyl group-containing monomer (a) has 8 carbon atoms. 5. The water / oil repellent according to claim 1, wherein the degree of crystallinity of the homopolymer of the fluoroalkyl group-containing monomer (a) is 50 to 85%. 6. A textile product treated with the water / oil repellent according to claim 1.