WO2004067499A1

WO2004067499A1 - Fluorinated urethane compound and use thereof

Info

Publication number: WO2004067499A1
Application number: PCT/JP2004/000639
Authority: WO
Inventors: Ikuo Yamamoto; Kayo Kusumi; Takuya Toshioka; Fumihiko Yamaguchi
Original assignee: Daikin Industries, Ltd.
Priority date: 2003-01-31
Filing date: 2004-01-26
Publication date: 2004-08-12
Also published as: JP2006188431A

Abstract

A fluorinated urethane compound represented by the general formula I[-NHC(=O)O-((Rf-A1-)X1O)a-R1]m[-NHC(=O)O-((ClCH2-)X2O)b-R2]n (1) (wherein I is a group formed by removing isocyanate groups from a polyisocyanate compound; Rf is C3-21 perfluoroalkyl; X1 and X2 each is a trivalent, C2-5, linear or branched, aliphatic group; A1 is a direct bond or a C1-21 divalent organic group; and R1 and R2 each is hydrogen or C1-10 alkyl). The compound imparts high water and oil repellency.

Description

Description Fluorinated urethane compounds and their applications

The present invention relates to a novel fluorine-containing urethane compound, a composition containing the same, and a treating agent. The fluorine-containing urethane compound of the present invention is suitable for treating (especially, surface treating) various substrates, for example, textiles. Background art

Conventionally, various fluorine-containing compounds have been proposed. Fluorine-containing compounds have the advantage of having excellent properties such as heat resistance, oxidation resistance, and weather resistance. Utilizing the property that the free energy of the fluorine-containing compound is low, that is, the property that it is hard to adhere, the fluorine-containing compound is used as, for example, a water and oil repellent and an antifouling agent.

Fluorine-containing compounds that can be used as water and oil repellents are, for example,

No. 21, JP-B2-60702, JP-B2-60702, and JP-B-63-45665. Examples of the fluorine-containing compound include, for example, USP 5414111, USP 5565564, EP-A-383365, JP-T 7-505190 (WO 93/17165), WO 97/25308, USP 3547894, JP-T 2001-525010 ( WO 98/51 727), JP-T 2001-525871 (WO 98/51723), JP-T 2001-258

It is also disclosed in JP 525872 (WO 98/51726), JP 2001-525874 (WO 98/51724) and JP 2002-504938 (WO 98/51725).

These fluorine-containing compounds did not give sufficient water / oil repellency. Disclosure of the invention

An object of the present invention is to provide a novel fluorine-containing compound that gives high water / oil repellency. The novel fluorine-containing compound of the present invention has a general formula:

I [-HC (= 0) 0— ((Rf-A ^1- ) X ¹ 0) _a — R ¹ ] _m [-NHC (= 0) 0— ((C1CH ₂ —) X ²⁰ ) _b —] _n (1) [wherein I is a group obtained by removing an isocyanate group from a polyisocyanate compound, R f is a C 3-21 perfluoroalkyl group,

X ¹ and X ² are a trivalent linear or branched aliphatic group having 2 to 5 carbon atoms,

A ¹ is a direct bond or a divalent organic group having 1 to 21 carbon atoms,

R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

a and b are numbers from 1 to 20;

Ι is a number from 1 to 15;

n is a number from 0 to 14,

The sum of m and n is 2; L5 is the number. ]

And a fluorine-containing urethane compound represented by the formula: BEST MODE FOR CARRYING OUT THE INVENTION

In the formula (1), I is a group obtained by removing the isocyanate group from the polyisocyanate compound. A polyisocyanate compound is a compound having at least two isocyanate groups. The polyisocyanate compound may be an aliphatic polyisocyanate, an aromatic polyisocyanate, or a derivative of these polyisocyanates.

Examples of aliphatic polyisocyanates, particularly aliphatic diisocyanates, include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. One is hydrogen hexylmethane diisocyanate. Examples of aromatic polyisocyanates, especially aromatic diisocyanates, are tolylene diisocyanate, diphenylmethane diisocyanate (MDI), trizine diisocyanate, and naphthalene diisocia. Nart. Polyisocyanate compounds include diisocyanate, polymeric MD I (diphenylmethane diisocyanate), and modified isocyanate (particularly, trimer of diisocyanate or adduct of polyhydric alcohol and diisocyanate). It is preferable that Examples of modified isocyanates include urethane-modified diisocyanates, arophanates, modified individual diisocyanates, biuret-modified individual diisocyanates, isocyanurate-modified diisocyanates, carposimid-modified diisocyanates, uretonimine-modified isocyanates. It is.

R f is a C 2-21 perfluoroalkyl group. The number of carbon atoms in R f may be, for example, from 3 to; L 2, especially 4 to 8, especially 4 to 6.

A ¹ is a direct bond or a divalent organic group having from L to 21 carbon atoms. An example of ^one A group is of the formula:

One (CH Yamaichi

-CONR ¹¹ -R ¹² -one CH ₂ C (OH) HCH ₂ --CH ₂ C (〇C〇R ¹³ ) HCH ₂ one or

-OA r -CH ₂ ~

[Wherein, R ¹¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ¹² is an alkylene group having 1 to 10 carbon atoms,

R ¹³ is hydrogen or a methyl group,

Ar is an arylene group which may have a substituent (for example, having 6 to 20 carbon atoms). P is an integer of 1 to: L0. ]

It is. A ¹ may especially be an alkylene group having 1 to 5 carbon atoms.

X ¹ and X ² are a trivalent linear or branched aliphatic group having 2 to 5 carbon atoms.Examples of X ¹ and X ² are:

> CHCHo-(-CHo CH <),> CHCH, CH _2- (one CH ₂ CH ₂ CH),

— CH ₂ CHCH _2-

_{_{_{> CHCH 2 CH 2 CH 2 -}}} (_CH 2 CH 2 CH 2 CH <),

> CHCH ₂ CH ₂ CH ₂ CH ₂ -(_ CH ₂ CH ₂ CH ₂ CH ₂ CH).

R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl groups R ¹ and R ² are methyl, ethyl, propyl.

Specific examples of the fluorine-containing urethane compound (1) of the present invention are as follows.

CONH (CH) ₆ NHCO— 0- (ΟΗ ₂ ΟΗΟ) _η --ΟΗ ₃

CH _3- (OCHCH ₂ ) ₁₁ -0-CONH- (CH ₂ ) ₆ -N c _g F ₁₇

C¾ \

C ₈ F ₁₇ CONH (CH) ₆ NHCO— 0- (CH ₂ CHO) _{n to} CH ₃

C¾

C ₈ F ₁₇

Wherein n is a number from 1 to 20. ]

The fluorine-containing urethane compound (1) of the present invention is, for example, a polyisocyanate compound,

Formula: ■

H0-((Rf— A ¹ —) ^ 0) ₃ — R ¹ (i)

A fluorine-containing alcohol represented by the formula:

H0-((C1CH _2- ) X ²⁰ ) _b -R ² (ii)

And a chlorine-containing alcohol represented by the following formula.

[Wherein, R f, A \ XX ² , R \ R a and b are as defined above. ]

In this reaction, the total number of moles of the fluorinated alcohol (i) and the chlorinated alcohol (ii) relative to 1 mole of the isocyanate group of the polyisocyanate compound is from 0.5 to 2.0, particularly preferably from 0.5 to 2.0. It is preferably from 8 to 1.5 mol. The chlorine-containing alcohol (ii) is a component that may or may not be used. This reaction is preferably performed in the presence of a solvent at a temperature of 0 to 150 ° C., for 1 to 1 hour; Solvents are organic solvents that are inert to isocyanates. Examples of the solvent include hydrocarbons, ketones, and halogenated hydrocarbons (for example, chlorine-containing hydrocarbons). The amount of the solvent may be 20 to 500 parts by weight, for example 100 to 300 parts by weight, based on 100 parts by weight of the reactants.

At the time of the reaction, it is preferable to use a catalyst. Examples of catalysts include amines (eg, monoamine, diamine, triamine, alcoholamine, etheramine), organic metals (eg, metal salts of organic acids (eg, di-n-butyltin dilaurate)). It is. The amount of catalyst may be from 0.001 to 0.5 parts by weight, for example from 0.01 to 0.3 parts by weight, based on 100 parts by weight of the reactants. The fluorinated alcohol (i) has, for example, the formula:

[Wherein, R f, A ¹ and X ¹ are as defined above. ]

Can be obtained by polymerizing a fluorine-containing cyclic ether compound represented by the following formula:

The fluorinated cyclic ether compound is, for example, an oxysilane compound or an oxetane compound.

The chlorinated alcohol (ii) is, for example, of the formula:

Wherein X ² is as defined above. ]

And obtained by polymerizing a chlorine-containing cyclic ether compound represented by the formula: An example of a chlorine-containing cyclic ether compound is epichlorohydrin.

The fluorine-containing urethane compound of the present invention may be contained in a composition. The composition may be in the form of a solution or an emulsion. The solution-type composition comprises a fluorine-containing urethane compound and a solvent. Examples of solvents (particularly organic solvents) in the solution type composition are hydrocarbons, ketones, and halogenated hydrocarbons (eg, chlorine-containing hydrocarbons). The emulsion-type composition contains a fluorine-containing urethane compound, an emulsifier, and water. The emulsion-type composition may further contain an organic solvent, particularly an organic solvent that dissolves the fluorine-containing urethane compound. The emulsifier may be either nonionic or ionic (eg, cationic, anionic, amphoteric). In the composition, the amount of the fluorine-containing urethane compound is 0.1 to 70% by weight ⁰ /. For example, it may be 5 to 30% by weight. In the emulsion type composition, fluorine-containing For 100 parts by weight of the urethane compound, the amount of the emulsifier is 0.1 to 30 parts by weight, for example, 2 to: 0 parts by weight of L, the amount of water is 30 to 99.9 parts by weight, For example, 70 to 95 parts by weight, and the amount of the organic solvent may be 10 to 200 parts by weight, for example, 50 to: L00 parts by weight. The fluorinated urethane compound of the present invention can be used as a surface treatment agent for treating the surface of various articles, and modifies the surface of the article to provide, for example, water / oil repellency.

The fluorinated urethane compound of the present invention has excellent water and oil repellency, is rich in molecular stability, and has high durability. Therefore, when the treatment is performed using the fluorine-containing urethane compound, the treated material can maintain excellent properties for a long period of time.

In performing the treatment, an arbitrary method is adopted according to the form of the surface treatment agent. For example, an aqueous emulsion or a solvent solution type surface treatment agent is used. In such a case, a treatment liquid is attached to at least the surface of the object to be treated by a method such as dip coating, and then dried. In the case of the emulsion type, it is desirable to carry out curing after drying for the purpose of continuity of the treating agent, adhesion of the particles to the treating agent, and penetration. As a result, great water and oil repellency can be expected. The solvent type has an advantage that a sufficiently large water and oil repellency can be expected without performing curing or cleaning since a film is formed on the object to be processed by drying. If necessary, further curing may be performed. The drying temperature may be selected arbitrarily, but in the case of an emulsion type, it may be room temperature, and drying with hot air at 50 to 120 ° C is efficient. In the case of a solvent type, drying at a temperature of about 50 to 50 ° C is appropriate.

Examples of the object to be treated with the surface treatment agent of the present invention include various objects. Examples of objects to be treated are textiles, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces and plasters.

In the present invention, the article to be treated is preferably a textile, such as a carpet. 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, polybutyl alcohol, polyacrylonitrile, polychlorinated vinyl, and polypropylene; semi-synthetic fibers such as rayon and acetate; glass fibers; and carbon. Fiber,

Inorganic II such as ト fiber; 锥, or a mixed fiber thereof. Textile products may be in the form of fiber, yarn, cloth, etc. When treating the carpet according to the method of the present invention, the carpet may be formed after treating the fiber or yarn, or the carpet formed may be treated. The surface treating agent can contain the fluorine-containing urethane compound in a state diluted to 0.02 to 30% by weight, preferably 0.02 to 10% by weight. Preferred embodiments of the invention

Hereinafter, the present invention will be described specifically.

Synthesis example 1

Synthesis of fluorinated alcohol (1)

1.19 g (37.36 mmol) of methanol and 0.50 g (3.5 ramol) of boron trifluoride / getyl etheno compound are placed in a 200 ml four-necked flask equipped with a stirrer, thermometer, nitrogen inlet tube, cooling tube and dropping funnel. The temperature was set to 70 ° C and the mixture was stirred.

Then, with a dropping funnel under a stream of nitrogen

Les 8 · ^ 17. , (Hereinafter referred to as "fluorine-containing epoxy compound")

95.2 g (200 mmol) was added dropwise over 45 minutes. After completion of the addition, the reaction was further performed at 70 ° C. for 3 hours. The content of the fluorinated epoxy compound remaining by gas chromatography was 0.52% in the composition. After completion of the reaction, the reaction mixture was transferred to a separatory funnel, and 100 g of HCFC225, 100 g of pure water, and a 10% aqueous solution of sodium hydrogen carbonate were added to neutralize the mixture. The organic solvent layer was recovered. Further, 70 g of pure water was added, and the same operation as above was performed again, and an organic solvent layer was recovered. Next, 15 g of anhydrous magnesium sulfate was added thereto, followed by drying overnight, followed by filtration and removal of the solvent. As a concentrated residue, a white wax-like reaction product (fluorinated alcohol (1)) was obtained:

HO [CH ₂ CH (CH ₂ C ₈ F i 7) θ] _η CH ₃

Got. (Yield 79 g, yield 82 ° /.) The structure of the obtained product was confirmed by ¹ H MR and ¹⁹ F R. The average polymerization degree (n number) was 4.85. Production Example 1

Preparation of Fluorine-Containing Urethane (1)

Hexane modified with isocyanurate,

(Sumijur N-3300 manufactured by Sumika Bayer Perethane Co., Ltd., content of isocyanate is 21.8%) 1.66 g (8.62 ol), methyl isobutyl ketone (MIBK) 40 g, diptyltin dilaurate as catalyst 0 .06 g was placed in a 200 ml square flask equipped with a stirrer, thermometer, nitrogen inlet tube, cooling tube and dropping funnel, and stirred at an internal temperature of 90 ° C.

Then, 20 g (8.54 mol) of the fluorinated alcohol (1) (n = 4.85) prepared in Synthesis Example 1 dissolved in 35 g of methyl isobutyl ketone (MIBK) was placed in the dropping funnel and placed under a nitrogen stream. It was dropped over 30 minutes.

After completion of the dropwise addition, the reaction was further performed at 95 ° C for 2 hours. By IR, it was confirmed that the peak derived from the raw material isocyanate had disappeared. After the completion of the reaction, the solvent is removed by a rotary evaporator, and a white crystalline reaction product (fluorine-containing urethane (1)) is obtained as a concentrated residue:

[The average of n is 4.85. ] Got. (Yield 20.2 g, 93%) The structure of the obtained product was confirmed by ¹ H NMR and ¹⁹ F. Production Example 2

Preparation of Fluorine-Containing Urethane (2)

Bullet-modified hexamethylene dissociation

OC (CH ₂ ) ₆ N [CONH (CH ₂ ) ₆ NC0] ₂ (Sumijur N-3200 manufactured by Sumika Bayer Urethane Co., Ltd., isocyanate content is 23%) 1.55 g (8.49 mmol), methyl 40 g of isobutyl ketone (MIBK) and 0.06 g of dibutyl tin dilaurate as a catalyst are placed in a 200 ml square flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a cooling tube and a dropping funnel, and the internal temperature is brought to 90 ° C. And stirred.

After that, 19.97 g (8.53 mol) of the fluorinated alcohol (1) prepared in Synthesis Example 1 dissolved in 35 g of methyl isobutyl ketone (MIBK) was placed in the dropping funnel, and dropped in a nitrogen stream over 30 minutes. did.

After the completion of the dropwise addition, the reaction was further performed at 90 ° C for 2 hours. It was confirmed by IR that the peak derived from the raw material isocyanate had disappeared. After the completion of the reaction, the solvent is removed by a rotary evaporator, and a white crystalline reaction product (fluorine-containing urethane (2)) is obtained as a concentrated residue:

[The average of n is 4.85. ]

Got. (Yield 19. 63g, ⁹ 1% yield) The structure of the resulting product confirmed by ¹ H NMR and ^{1 9} F丽R, the. Water repellency test

Repellent treatment finished ^^. , And store in a thermo-hygrostat at a temperature of 21 ° C and a humidity of 65% for at least 4 hours. Use a test solution (isopropyl alcohol (IPA), water, and a mixture thereof, shown in Table 1) stored at a temperature of 21 ° C. The test is performed in a constant temperature and humidity room with a temperature of 21 ° C and a humidity of 65%. Five drops (50 μ1) of the test solution are gently dropped on the carpet with a micropipetter, and after standing for 10 seconds, if four or five drops remain on the carpet, It is assumed that the test solution has passed. The water repellency was scored based on the maximum isopropyl alcohol (ΙΡΑ) content (volume./.) Of the passed test solution. Fail, 0, 1, 2, 3 from poor water repellency to a good level , 4, 5, 6, 7, 8, 9, and 10 are evaluated on a 12-point scale. Table 1 Water repellency test liquid

(Volume ratio ⁰ / o)

Score isopropyl alcohol water

10 100 0

9 90 10

8 80 20

7 70 30

6 60 40

5 50 50

4 40 60

3 30 70

2 20 80

1 10 90

0 0 100

Fail Less than isopropyl alcohol 0 / water 100

Oil repellency test

Store the treated carpet in a thermo-hygrostat at a temperature of 21 ° C and a humidity of 65% for at least 4 hours. Use the test solution (shown in Table 2) stored at 21 ° C. The test is performed in a constant temperature and humidity room with a temperature of 21 ° C and a humidity of 65%. 5 drops the test solution on the carpet with a micropipetter 1) Gently drop the solution and leave it for 30 seconds.If 4 or 5 drops remain on the carpet, pass the test solution. And Oil repellency is the pass From the poor oil repellency to a good level.

Evaluate on a 9-point scale of 2, 3, 4, 5, 6, 7, and 8. Table 2 Oil repellency test liquid

Antifouling test

The test was performed according to the MTCC Test Method 123-1989.

The antifouling property was evaluated using a gray scale for discoloration and fading, and compared with the cartilage sample before the antifouling test, from a level of significant discoloration to a level of no discoloration. Evaluation is made on a 9-point scale of 2, 2-3, 3, 3-4, 4, 4-5 and 5. Example 1

5 g of the fluorinated urethane compound (1) synthesized in Production Example 1 and 5 g of methyl isobutyl ketone (MIBK) were mixed, and heated at 75 ° C to 80 ° C for 10 minutes. Pure water in a separate container 14. 4 _g, Po Rio carboxymethyl ethylene alkyl ether (Noyuon emulsifier) 0. 5 g and alpha - Orefi Nsuruhon Sodium (Anion emulsifier) were mixed 0. l _g, 75 ° C~80 ° Heated at C for 10 minutes. The two liquids were mixed and emulsified with an ultrasonic emulsifier.

97.5 g of water was added to 2.5 g of this solution to make a total amount of 100 g, which was used as a treatment solution. Apply this treatment solution to a carpet (20craX 20 cm, nylon 6, nylon pile, density 32 ozZyd ² ) WPU (wet pick up) .If 20 g of liquid is put on 100 g of carpet, WPU is 20%. Sprayed so that the amount was 20%. Next, heat curing was performed at 120 ° C for 10 minutes. Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 3 shows the results Shown in Example 2

According to Example 1, the fluorinated urethane compound (2) synthesized in Production Example 2 was emulsified. 97.5 g of water was added to 2.5 g of this milk solution to make a total amount of 100 g, which was used as a treatment liquid. This treatment liquid was treated with a water repellent according to Example 1 by force.

Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 3 shows the results. Comparative Example 1

95 g of water was added to 5 g of a fluorine-containing urethane compound solution manufactured by DuPont to make a total amount of 100 g, which was used as a treatment solution. This treatment solution was treated with a repellent on a carbet according to Example 1.

Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 3 shows the results. Table 3

Example 3

5 g of the fluorinated urethane compound (1) synthesized in Production Example 1,

(MIBK) was mixed and heated at 75 ° C. to 80 ° C. for 10 minutes. Pure water in a separate container 14. 4g, poly O key Chez Ji alkylether '(nonionic emulsifier) 0. 5 g and alpha - Orefin sodium sulfonate (§ - one emulsifier) were mixed 0. l _g, 75. C-80. C for 10 minutes. The two liquids were mixed and emulsified with an ultrasonic emulsifier.

1 g of this emulsified solution and a stimplock agent (a mixture of phenol / formaldehyde condensate and polymethacrylic acid at a weight ratio of 50:50) (hereinafter referred to as “SB agent”) 5 g were added to water to make a total amount of 1000 _g. It was diluted to become. This of _P H to obtain 1.5 become so 10% scan Rufamin acid aqueous solution was added to the processing solution. Rinse this treatment solution with water and about 25% WPU

(WPU: wet pick up, when 25g of liquid is put on 100g of carpet, WPU is Then, a squeezed carpet (20 cm × 20 cm, nylon 6, cut pie / dish, density 32 oz Vd ² ) was immersed in the carpet for 30 seconds and squeezed so that the WPU (wet pick up) amount was 300%. The fluorine concentration on the treated power pipe was 300 ppm. Next, with the pile surface of the carpet facing upward, a normal-pressure steamer treatment (temperature: 100 to 107 ° C) was performed for 90 seconds. Next, after rinsing with 10 L of water, centrifugal dehydration was performed to reduce the amount of WPU to about 25%. Finally, heat curing was performed at 110 ° C for 10 minutes.

Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 4 shows the results. Example 4

The fluorinated urethane compound (2) synthesized in Production Example 2 according to Example 3 was emulsified.

Water was added to 1 g of this emulsion and 5 g of the SB agent to dilute the total amount to 1000 g. A 10% aqueous solution of sulfamic acid was added to adjust the pH to 1.5 to obtain a treatment solution. A carpet was treated with a repellent according to Example 3.

Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 4 shows the results. Comparative Example 2

Water was added to ² g of a fluorine-containing urethane compound solution manufactured by DuPont and 5 g of a stinblocking agent A, and diluted to 1000 g with water. A treatment solution was obtained by adding a 10% aqueous solution of sulfamic acid so that the pH of the solution became 1.5.

A carpet was treated with a repellent according to Example 3.

Next, a water repellency test, an oil repellency test, and an antifouling test were performed. Table 4 shows the results. Table 4

Water repellency Lake repellent Antifouling

Example 3 Production Example 3 2 2 4-5

Example 4 Production Example 4 2 2 4-5

Comparative Example 2 Fluorine containing DuPont ゥ 1.5 2 4

Rethane compounds

Claims

The scope of the claims

1. —General formula:

I [- NHC (= 0) 0- ((Rf- A 1 - 1 0) a -] " [- thigh C (= 0) 0- (( C1C¾-) X 2 0) b -R 2] n ( l) [wherein, I is a group obtained by removing an isocyanate group from a polyisocyanate compound, and R f is a C 3-21 perfluoroalkyl group;

A ¹ is a direct bond or a divalent organic group having 1 to 21 carbon atoms,

R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, a and b are a number of 1 to 20,

m is a number from 1 to 15,

n is a number from 0 to L4;

The sum of m and n is a number from 2 to 15. ]

A fluorine-containing urethane compound represented by the formula:

2. When the polyisocyanate compound constituting the I group is an aliphatic polyisocyanate

3. The fluorine-containing polyurethane compound according to claim 1, which is a derivative of an aromatic polyisocyanate or a derivative of these polyisocyanates.

3. The fluorine-containing urethane compound according to claim 1, wherein the polyisocyanate compound constituting the I group is a diisocyanate, a polymeric diphenylmethane diisocyanate, or a modified isocyanate.

4. A ¹ group is the formula:

One (CH ₂ ) _P -One CONR ¹¹ — R ¹² —

-CH ₂ C (OH) HCH ₂ -one CH ₂ C (OCOR ¹³ ) HCH ₂ one or

-0-A r-CH _2- Wherein R ¹¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R ¹² is an alkylene group having 1 to 10 carbon atoms,

R ¹³ is hydrogen or a methyl group,

Ar is an arylene group which may have a substituent (for example, having 6 to 20 carbon atoms), and p is an integer of 1 to: L0. ]

2. The compound according to claim 1, which is

5. A composition comprising the fluorine-containing polyurethane compound according to claim 1, an emulsifier, and water.

6. A treating agent comprising the composition according to claim 5.

7. A method for treating textile products with the treatment agent according to claim 6.