JPH0355516B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent stain-proofing agent, and more specifically, to a water- and oil-repellent stain-proofing agent comprising a specific urethane compound base material containing a polyfluoroalkyl group and a specific blender copolymer. Conventionally, various polyfluoroalkyl group-containing urethane compounds have been proposed as substances useful for antifouling treatment of interior products such as carpets. For example, see US Pat. No. 3,398,182, US Pat. No. 3,484,281, JP-A-53-112855, JP-A-54-74,000, and the like. and,
In JP-A-47-7600, etc., it has been proposed to antifouling carpets by using a polyfluoroalkyl group-containing main agent in combination with a water-insoluble addition polymer blender having a specific main transition temperature and solubility parameter. There is. However, hydrocarbon blenders have a problem in that they impair water and oil repellency. The present inventor has identified a polyfluoroalkyl group (hereinafter referred to as
As a result of various studies and studies on antifouling treatment using urethane compounds containing R _f group (sometimes abbreviated as R _f group), we found that certain R f group-containing urethane compounds include R _f- containing vinyl monomer/branched butyl methacrylate/methyl methacrylate. It has been found that by using the copolymer in combination, it is possible to simultaneously impart high water and oil repellency and stain resistance against dry stains in the treatment of carpets and the like. In particular, good results can be obtained with an antifouling agent in which a specific R _f group-containing urethane compound is dispersed in an aqueous medium in the coexistence of a specific hydrophilic group-containing urethane compound. Thus, the present invention provides the general formula R _f ¹ −X ¹ −A ¹ −
A new water-repellent, oil-repellent and stain-proofing agent characterized by consisting of a urethane compound represented by CONH-Y ¹ -NHCO-A ² -Z and an R _f -containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer. It is provided to A particularly preferred embodiment of the antifouling agent of the present invention is in the form of an aqueous dispersion dispersed in a medium mainly consisting of water. In the case of such an aqueous dispersion, it is desirable to perform the dispersion in the coexistence of a specific hydrophilic group-containing urethane compound. That is, the general formula, R _f ²
The urethane compound is dispersed in a medium mainly composed of water in the coexistence of a urethane compound containing a hydrophilic group represented by -X ² -A ³ -CONH-Y ² -NHCO-W. Therefore, R _f ¹ and R _f ² of the urethane compound and
are each a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and those in which the terminal end is a perfluoroalkyl group are usually used,
Those containing a hydrogen atom or a chlorine atom at the end,
Alternatively, an oxyperfluoroalkylene-containing group can also be used. A preferred embodiment of R _f ¹ and R _f ² is a perfluoroalkyl group, which has 6 to 12 carbon atoms.
Particularly preferred are X ¹ and X ² are each −R ¹
−, −CON(R ² )−Q ¹ −, and −SO ₂ N(R ² )−Q ¹
- (However, -R ¹ - represents an alkylene group, R ² represents a hydrogen atom or lower alkyl group, and Q ¹ represents a divalent organic group)
It is one of the alkylene groups, especially those with 1 to 20 carbon atoms.
preferably. Also, A ¹ , A ² , and A ³
are respectively -O-, -S-, or -N(R ³ )- (however,
R ³ represents a hydrogen atom or a lower alkyl group)
From the viewpoint of availability, -O- is preferred. Next, Y ¹ and Y ² are divalent organic groups, and those with carbon numbers of 24 or less, especially 6 to 15, are selected to stiffen the urethane molecule and improve the durability of its antifouling performance. Those containing at least one aromatic ring or aliphatic ring are preferably employed.
Z in the urethane compound is a non-hydrophilic monovalent organic group, and examples include those containing an alkyl group, an aryl group, a hetero atom, and -X ¹ -R _f ¹ . From the viewpoint of antifouling performance, a lower alkyl group having 1 to 4 carbon atoms is preferably employed. W in the urethane compound is a hydrophilic group, -( _CH2CH2O ) ^-R4 (where m is an integer of 1 _to 50, ^R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) Nonionic groups represented by -
(CH ₂ CH ₂ O) _n -SO ₃ M (where M represents one of a hydrogen atom, an alkali metal, or an ammonium group), -
(CH ₂ CH ₂ O) _n −PO ₃ M, − CH ₂ CH ₂ SO ₃ M, −
Anionic groups such as CH ₂ CH ₂ COOM, and -CH ₂ CH ₂ NR′R″RX (where R′, R″, R are alkyl groups, aryl groups, X is Cl, Br, I, OCOCH ₃ Various examples include cationic groups such as -(CH ₂ CH ₂ O) ₂₀ -CH ₃ from the viewpoint of compatibility with other processing agents. etc. can be preferably adopted. In the present invention, R _f ¹ and R _f ² , X ¹ and X ² , A ¹ and
A ³ , Y ¹ and Y ² do not necessarily have to match. Moreover, the urethane compound and may each be a mixture. For example, it is also possible to use a mixture of a plurality of urethane compounds having different numbers of carbon atoms, R _f ¹ and R _f ² , respectively. In the present invention, when dispersing the urethane compound in a medium mainly composed of water, it is important to allow the urethane compound to coexist. When a urethane compound is not coexisting, that is, when the urethane compound is used alone for dispersion, or when the urethane compound is replaced by a common surfactant, such as sodium lauryl sulfate, alkylphenol polyglycol ether, ammonium perfluorooctanoate, etc. dispersion may be difficult or water repellent, oil repellent,
There is a tendency for dry soil resistance to decrease. The coexistence ratio (weight ratio) of urethane compound/urethane compound is not particularly limited, but if the ratio is too small, the stability of the dispersion will decrease, and if it is too large, the water repellency will tend to decrease. Usually, it can be selected from the range of 99/1 to 25/75, preferably 95/5 to 50/50. In the present invention, the medium mainly composed of water includes the case of water alone, but it is a more preferable embodiment that a water-soluble organic solvent coexists. Addition of a water-soluble organic solvent lowers the interfacial tension of the medium, lowers the melting point of the urethane compound, and increases the solubility, making dispersion easier. Various organic solvents can be used, including dioxane, tetrahydrofuran, ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether,
Ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, etc. Water-soluble ethers, formamide, dimethylformamide, acetamide, and other water-soluble amides can be preferably employed. The amount of the water-soluble organic solvent added is usually 10 to 300 parts by weight, preferably 20 to 150 parts by weight, based on 100 parts by weight of the total amount of the urethane compound.
It can be selected from a range of parts by weight. In the present invention, the urethane compound is usually a diisocyanate (CON-Y ¹ -NCO), a fluorine-containing compound R _f ¹ -X ¹ -A ¹ -H (for example, 2-perfluoroalkylethanol), and a compound Z- ^A2 -H
(for example, methanol). Similarly, urethane compounds are made by combining diisocyanate (OCN-Y ² -NCO) with a fluorine-containing compound R _f ² -X ² -A ³ -H (e.g. 2-perfluoroalkylethanol) and a compound W-H (e.g. polyoxy It can be produced by addition reaction with ethylene glycol monomethyl ether). In the present invention, the dispersion of the urethane compound and the water-based medium can be carried out in various ways. For example, the mixture of the urethane compound and the aqueous medium is stirred at high speed under heating, and then cooled to room temperature. method, a method in which a solution of a water-soluble organic solvent of a urethane compound is dropped into an aqueous solution of a urethane compound under stirring, or a method in which an aqueous solution of a urethane compound is dropped into a solution of a urethane compound in a water-soluble organic solvent while stirring; Possible methods include dropping a water-soluble organic solvent solution into water while stirring, or conversely dropping water dropwise. The water-repellent, oil-repellent and antifouling agent of the present invention is prepared by adding and mixing an R _f- containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer to the above-mentioned urethane compound as a blender. In the specific blender copolymer, R _f- containing vinyl monomer/branched butyl methacrylate/
The molar ratio of methyl methacrylate is 0.1~
10/5~89.9/5~89.9 Especially 1~5/25~69/25
Selected from a range of ~69. As R _f group-containing vinyl monomers, conventionally known or well-known ones, etc.
Various types can be mentioned without particular limitation. For example, CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ OCOCH=
CH ₂ CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₁₁ OCOCH=CH ₂ , CF ₃
(CF ₂ ) ₈ (CH ₂ ) ₂ OCOC(CH ₃ )=CH ₂ CF ₃
(CF ₂ ) ₄ CH ₂ OCOC (CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ OCOC (CH ₃ )=CH ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ ) ₂ 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 (CH ₂ ) ₃ COOCH=CH ₂ , These are unsaturated esters represented by acrylates or methacrylates containing perfluoroalkyl groups having 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms. Branched butyl methacrylate includes isobutyl methacrylate and tertiary butyl methacrylate, and isobutyl methacrylate is usually preferably employed. In addition to the above two types of components, the specific blender copolymer also contains acrylamide, methacrylamide, N-methylol acrylamide, alkyl methacrylate, vinyl chloride, styrene, vinyl acetate vinyl propionate,
It may contain one or more types of additive monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. as a structural unit. The content of the added monomer is selected from a range of 20 mol% or less. The ratio (weight ratio) of urethane compound/specific blender copolymer can be varied, but is usually 1/100 to 100/1, preferably 1/10 to 10/1.
In particular, it may be selected from the range of 1/2 to 2/1. By using such a mixture, dry soil resistance is improved compared to when each is used alone. If the amount of the specific blender copolymer is too large, the water repellency and oil repellency will be impaired, and if the amount is too small, the effect of improving dry soil resistance will not be recognized. When adding and mixing the specific blender copolymer, an aqueous dispersion of the urethane compound is employed in a preferred embodiment of the present invention, so it is preferable to use the blender in the form of an aqueous dispersion. . The aqueous dispersion of the specific blender copolymer can be mixed well with the aqueous dispersion of the urethane compound in a wide range of proportions, and can be mixed within the above-mentioned urethane compound/specific blender copolymer ratio range. In the aqueous dispersion which is a preferred embodiment of the water- and oil-repellent stain-proofing agent of the present invention, the solid content (urethane compound + urethane compound + specific blender copolymer) concentration is not particularly limited, but is usually 5 to 5.
60% by weight, preferably 15-50% by weight,
For antifouling treatment, remove the solid content with water.
It is used diluted to about 0.1 to 4% by weight.
Aqueous dispersions have advantages over organic solvent-based ones, such as a higher flash point of the stock solution and the ability to increase the solid content concentration, and are also easier to use in the working environment during antifouling processing. Advantages such as the ability to reduce pollution are also recognized. The water-repellent, oil-repellent and antifouling agent of the present invention is made of polyamide,
It can be advantageously applied to various articles made of polyester, leather, wood, etc., such as interior products such as carpets, reception sets, curtains, wallpaper, and vehicle interior items, as well as outdoor tents. The stain-proofing method for carpets, etc. using the water- and oil-repellent stain-proofing agent of the present invention is not particularly limited, and various known means can be employed, such as coating such as dipping, spraying, and coating. Examples of known processing methods include attaching the material to the surface of the object to be processed and drying it. In addition, for antifouling processing, we use antistatic agents, insect repellents, flame retardants, dye stabilizers,
It is also possible to appropriately use various treatment agents such as anti-wrinkle agents, additives, and the like. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by this description. In addition, in the following Examples and Comparative Examples, water repellency, oil repellency, and dry soil resistance were measured as follows. That is, water repellency is determined by using a mixed solution consisting of 20 parts by volume of isopropanol and 80 parts by volume of water.
A few drops are placed on two locations on the sample carpet, and the time taken for the solution to penetrate is also expressed. Oil repellency was determined by placing a few drops (approximately 4 mm in diameter) of the test solution shown in Table 1 below on the sample carpet in two places.
Judgment is made based on the penetration state after seconds (AATCC-
TM118−1966).

[Table] Dry soil resistance is measured using 5x7 sample carpets.
Cut into cm pieces, place in a container with the dry soil shown in Table 2 below (twice the weight of the sample), and mix and stir vigorously for 3 minutes to contaminate. After contamination, remove excess dirt with a vacuum cleaner, measure reflectance, and evaluate the degree of contamination. The degree of contamination is calculated using the following formula. Contamination degree (%) = [(R _p − R _p ) ÷ R _p ] × 100 R _p : Reflectance of uncontaminated sample R _p : Reflectance of contaminated sample

[Table] Examples 1 to 3 72.0g (0.1 mol) of 14.4 g (0.009 mol), 80 g deionized water, and 20 g ethylene glycol monomethyl ether,
Pour into a three-necked flask with an internal volume of 300ml equipped with a thermometer, cooling tube, and vacuum stirrer, and bring the temperature to approx.
Raise to 100℃. After high shear stirring for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. CF ₃ (CF ₂ ) ₈ CH ₂ CH ₂ OCOCH=10g of CH ₂
(0.02 mol), 60 g (0.6 mol) of methyl methacrylate
mole), 20 g of isobutyl methacrylate (0.21
mol), 5 g of emulsifier C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₃₀ H,
200 g of deionized water and 0.1 g of azobisamidine hydrochloride were placed in the same three-necked flask as above, and polymerized at 60° C. for 10 hours to obtain a dispersion. / were mixed in the proportions shown in Table 3 below, and the mixture was diluted with deionized water so that the solid content was 0.5% by weight. This diluted solution was evenly sprayed onto a nylon rubber carpet (50% wet pick-up) and dried at 130 DEG C. for 20 minutes. The water repellency, oil repellency, and dry soil resistance of the thus obtained treated carpet were measured. Comparative Examples 1 to 3 Dispersions were obtained by polymerizing 50 g of methyl methacrylate and 50 g of isobutyl methacrylate in the same manner as in Examples. / were mixed in the proportions shown in Table 3 below and processed into carpets in the same manner as in the Examples (Comparative Examples 2 and 3).
Similar measurements were performed on untreated carpet (Comparative Example 1).

【table】 Example 4

20g (0.04 mol) of [formula], 50g (0.5 mol) of methyl methacrylate
mole), 28 g (0.20 mole) of isobutyl methacrylate
mol), 2 g of N-methylolacrylamide
(0.02 mol), emulsifier C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₃₀ H 5
g, 0.1 g of azobisamidine hydrochloride, and 200 g of deionized water were charged into a three-necked flask similar to that in Example 1, and polymerized at 60° C. for 10 hours to obtain a dispersion. / were mixed at a ratio of 1/1 (weight ratio), and dilution and treatment were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 4. Example 5 CF ₃ (CF ₃ ) ₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC (CH ₃ )
= 20 g (0.03 mol) of _CH2 , 40 g (0.40 mol) of methyl methacrylate, 40 g (0.28 mol) of t-butyl methacrylate, _{emulsifier C18H35O}
5 g of (CH ₂ CH ₂ O) ₃₀ H, 0.1 g of azobisamidine hydrochloride, and 200 g of deionized water were placed in the same three-necked flask as in Example 1, and polymerized at 60° C. for 10 hours to obtain a dispersion. . / were mixed at a ratio of 1/1 (weight ratio), and dilution and treatment were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 7. Example 6 72.0g _{( 0.1} ^mol ₎ of 14.4 g (0.009 mol) of ethylene glycol monomethyl ether, 80.0 g of deionized water, and 20.0 g of ethylene glycol monomethyl ether
g into a three-necked flask with an internal volume of 300 ml equipped with a thermometer, condenser, and vacuum stirrer, and raise the temperature to approximately 100°C. After stirring under high shear for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. The dispersion liquid and the dispersion liquid were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 7. Example 7 Example 6 Instead of 85.5g (0.1 mol) of Instead of A dispersion was obtained in the same manner as in Example 4, except for using 15.4 g (0.009 mol) of . The dispersion liquid and the dispersion liquid were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 6. Example 8 Example 6 Instead of 73.2g (0.1 mol) of Instead of A dispersion was obtained in the same manner as in Example 4, except that 13.9 g (0.009 mol) of . The dispersion liquid and the dispersion liquid were mixed at a ratio of 1/1 (weight ratio) to prepare a sample. Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 6, and a dry soil resistance of 6. Example 9 25.0g (0.35mol) 75.0 g (0.05 mol) of water, 80.0 g of deionized water, and 20.0 g of ethylene glycol monomethyl ether were placed in a three-necked flask with an internal volume of 300 ml equipped with a thermometer, cooling tube, and vacuum stirrer, and the temperature was adjusted to about 100 ml.
Raise to ℃. After stirring under high shear for 30 minutes, the mixture was cooled to room temperature to obtain a dispersion. The dispersion liquid and the dispersion liquid were mixed at a ratio of 1/1 (weight ratio) to prepare a sample.
Dilution and processing were performed in the same manner as in Example 1. The resulting treated carpet had a water repellency of 3 minutes or more, an oil repellency of 5, and a dry soil resistance of 5.

Claims (1)

[Claims] 1 General formula Rf ¹ −X ¹ −A ¹ −CONH−Y ¹ −NHCO
-A ² -Z (However, Rf ¹ is a polyfluoroalkyl group having 4 to 16 carbon atoms, and X ¹ is -R ¹ -, -CON
( ^R2 ) ^-Q1- , or _-SO2N ( ^R2 ) ^-Q1- , where ^R1 is an alkylene group, ^R2 is a hydrogen atom or a lower alkyl group, and ^Q1 is an alkylene group. , A ¹ and A ² are each -O-, -S-, or -N(R ² )-
, R ² is a hydrogen atom or a lower alkyl group, Y ¹ is a residue obtained by removing the isocyanate from an aromatic or alicyclic diisocyanate, and Z is an alkyl group, an aryl group, or -X ¹ −Rf ¹ ), a urethane compound represented by the general formula Rf ² −X ² −
A ³ -CONH-Y ² -NHCO-W (however, Rf ² is a polyfluoroalkyl group having 4 to 16 carbon atoms,
X ² is −R ¹ −, −CON(R ² )−Q ¹ −, or −SO ₂ N
(R ² )-Q ¹ -, R ¹ is an alkylene group,
R ² is a hydrogen atom or a lower alkyl group, Q ¹ is an alkylene group, and A ₃ is -O-, -S-, or -N
(R ³ )-, R ³ is a hydrogen atom or a lower alkyl group, Y ² is a residue obtained by removing the isocyanate from an aromatic or alicyclic diisocyanate, and W is a hydrophilic group. Hydrophilic group-containing urethane compound and Rf-containing vinyl monomer represented by
A water- and oil-repellent stain-proofing agent characterized by comprising a branched butyl methacrylate/methyl methacrylate copolymer. 2. The processing agent according to claim 1, which is employed in the form of an aqueous dispersion in which the urethane compound and the urethane compound are dispersed in a medium mainly consisting of water. 3. The processing agent according to claim 2, wherein the urethane compound/urethane compound ratio (weight ratio) is from 99/1 to 25/75. 4 The ratio (weight ratio) of (urethane compound)/(Rf-containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer) is 1/
The processing agent according to claim 1, which has a ratio of 100 to 100/1.