JPS6317108B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antifouling agent composition, and more specifically, to an antifouling agent composition comprising a specific urethane compound base containing a polyfluoroalkyl group and a specific blender polymer. 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,
Japanese Patent Publication No. 50-40200 and others propose stain-proofing 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. . The present inventor has discovered that a polyfluoroalkyl group (hereinafter referred to as
As a result of various studies and studies on antifouling treatment using urethane compounds containing Rf groups (sometimes abbreviated as Rf groups), we have found that by using a specific Rf group-containing urethane compound in combination with an ammonium methacrylate salt polymer, carpet It has been found that the antifouling performance against dry stains can be improved in treatments such as the following. In particular, good results can be obtained with an antifouling agent in which a specific Rf 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 Rf ¹ −X ¹ −A ¹ −
The object of the present invention is to provide a novel antifouling agent composition comprising a urethane compound represented by CONH- ^Y1 -NHCO- ^A2 -Z and an ammonium methacrylate salt polymer. 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,
In the coexistence of a hydrophilic group-containing urethane compound represented by ^Rf2 - ^X2 - ^A3 -CONH-Y2 ^- NHCO-W,
The urethane compound is dispersed in a medium mainly consisting of water. Therefore, the urethane compound and Rf ¹ and
Rf ² is a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and usually the terminal end is a perfluoroalkyl group, but the terminal end is a hydrogen atom or a chlorine atom. Atom-containing groups or oxyperfluoroalkylene-containing groups can also be used. A preferred embodiment of Rf ¹ and Rf ² is a perfluoroalkyl group, and those having 6 to 12 carbon atoms are particularly preferred. X ¹ and X ² are respectively −R ¹ −, −CON(R ² )−Q ¹ −, and −SO ₂ N
(R ² )-Q ¹ - (wherein -R ¹ - is an alkylene group, R ² is a hydrogen atom or a lower alkyl group, and Q ¹ is a divalent organic group), and is an alkylene group, especially Those having 1 to 20 carbon atoms are preferred. Also, A ¹ ,
A ² and A ³ are each -O-, -S-, or -N
(R ³ ) - (where R ³ represents a hydrogen atom or a lower alkyl group), and from the viewpoint of easy 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 antifouling performance. In view of this, 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, including an alkyl group, an aryl group, a hetero atom, and even -X ¹
-Rf ¹ can be exemplified, but lower alkyl groups having 1 to 4 carbon atoms are preferably employed from the viewpoint of water repellency, oil repellency, and antifouling performance. W in the urethane compound is a hydrophilic group, -(CH ₂ CH ₂ O) _n -R ⁴ (where m is an integer of 1 to 50, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) ), -(CH ₂ CH ₂ O) _n -SO ₃ M (however,
M represents one of a hydrogen atom, an alkali metal, or an ammonium group), -(CH ₂ CH ₂ O) _n -PO ₃ M, -
Anionic groups such as CH ₂ CH ₂ SO ₃ M, −CH ₂ CH ₂ COOM, and even −CH ₂ CH ₂ NR′R″RX
(However, R', R'', R is an alkyl group, aryl group, X is Cl, Br, I, OCOCH ₃ , etc.). From the viewpoint of compatibility with the agent, nonionic groups such as -(CH ₂ CH ₂ O) ₂₀ -CH ₃ can be preferably employed. In the present invention, Rf ¹ and Rf 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 carbon numbers, such as Rf ¹ and Rf 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 present, that is, when a urethane compound is used alone for dispersion, or when a urethane compound is used, ordinary surface active substances such as natonium/lauryl sulfate, alkylphenol/polyglycol ether, ammonium perfluorooctanoate, etc. are used. 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 99/1 to 25/75, preferably 95/5 to 50/50
can be selected from the range of 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
Diisocyanate (OCN-Y ¹ -NCO), fluorine-containing compound Rf ¹ -X ¹ -A ¹ -H (for example, 2-perfluoroalkylethanol) and compound Z-A ² -
It can be produced by addition reaction with H (for example, methanol). Similarly, urethane compounds include diisocyanate (OCN-Y ² -NCO) and fluorine-containing compounds Rf ² -X ² -A ³ -H (for example, 2-
perfluoroalkylethanol) and compound W-
It can be produced by addition reaction with H (for example, polyoxyethylene 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. In the antifouling agent composition of the present invention, an ammonium methacrylate salt polymer is added and mixed as a blender to the urethane compound as described above. The ammonium methacrylate salt polymer may usually be a homopolymer, but may include acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, N-methylol acrylamide, N-
It may also be a copolymer with one or more of methylolmethacrylamide, alkyl acrylate, alkyl methacrylate, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, styrene, and the like. In the case of a copolymer, one in which the content of ammonium methacrylate salt is 1 mol % or more, particularly 20 mol % or more is preferably employed. The ratio (polymerization ratio) of urethane compound/ammonium methacrylate salt polymer can be varied, but is usually 1/100 to 100/1, preferably 1/10 to 10/1, particularly 1/2 to 1/2. It can be selected from the range of 2/1. By using such a mixture, dry soil resistance is improved compared to when each is used alone. If the amount of the ammonium methacrylate salt polymer 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 ammonium methacrylate salt-based polymer as a blender to the urethane compound, an aqueous dispersion form of the urethane compound is adopted in a preferred embodiment of the present invention, so the blender is also an aqueous solution. Alternatively, it is preferred to use an aqueous dispersion form. The aqueous solution or aqueous dispersion of the specific blender can be mixed well in a wide range of ratios with an aqueous dispersion of a urethane compound dispersed in an aqueous medium in the presence of a urethane compound, and the above-mentioned urethane compound/methacrylic acid The ammonium salt-based polymers may be mixed in a range of proportions. In the aqueous dispersion that is a preferred embodiment of the antifouling agent composition of the present invention, the solid content (urethane compound + urethane compound + ammonium methacrylate salt polymer) concentration is not particularly limited, but
It is usually prepared in a concentration of 5 to 60% by weight, preferably 15 to 50% by weight, and for antifouling treatment, it is used after being diluted with water to a solid content of 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 solids 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 antifouling agent composition of the present invention can be applied to various articles made of polyamide, polyester, leather, wood, etc., such as interior products such as carpets, reception sets, curtains, wallpaper, and vehicle interior parts. It can also be advantageously applied to outdoor tents. The stain-proofing method for carpets and the like using the stain-proofing agent composition of the present invention is not particularly limited, and various known means can be employed.
For example, the coating may be applied to the surface of the object to be treated by known coating methods such as dipping, spraying, or coating, and then dried. 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, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. 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 expressed by placing several drops of a mixed solution consisting of 20 parts by weight of isopropanol and 80 parts by weight of water on two places on a sample carpet, and measuring the time taken for the solution to soak into the sample. Oil repellency is determined by placing a few drops (approximately 4 mm in diameter) of the test solution shown in Table 1 below on two locations on the sample carpet and determining the state of penetration after 30 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 (%) = [(Ro-Rp) ÷ Ro] × 100 Ro: Reflectance of uncontaminated sample Rp: Reflectance of contaminated sample

[Table] Examples 1 to 3 and Comparative Examples 1 to 3 72.0g (0.1 mol) of 14.4 g (0.009 mol) of , 80 g of deionized water, and 20 g of ethylene glycol monomethyl ether
into a three-necked flask with an internal volume of 300 ml equipped with a thermometer, cooling tube, and vacuum stirrer, and raise the temperature to approximately 100°C. After high shear stirring for 30 min,
A dispersion was obtained by cooling to room temperature. 100 g (0.98 mol) of ammonium methacrylate salt, 0.1 g of azobisamidine hydrochloride, and 300 g of deionized water were placed in the same three-necked flask as above, and polymerized at 60° C. for 10 hours to obtain an aqueous polymer solution. / 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 loop tufted carpet (wet pick-up 50%) and dried at 130°C for 20 minutes. The water repellency, oil repellency, and dry soil resistance of the thus obtained treated carpet were measured. Similar measurements were also carried out on carpets treated with a solution diluted to a solids content of 0.5% by weight (Comparative Examples 2 to 3) and untreated carpets (Comparative Example 1). These measurement results are summarized in Table 3 below.

[Table] Comparative example 4 In Example 1 The dispersion was prepared in the same manner as in Example 1 except that
A dispersion liquid was also obtained in the same manner as in Example 1. '/ are mixed at a ratio of 1/1 (weight ratio),
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 4, and a dry soil resistance of 8. Example 4 50 g (0.49 mol) of ammonium methacrylate salt, 50 g (0.70 mol) of acrylamide, 0.1 g of azobisamidine hydrochloride, and 300 g of deionized water
g was placed in the same three-necked flask as in Example 1, and polymerized at 60°C for 10 hours to obtain a polymer solution. / 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 5 50 g (0.49 mol) of ammonium methacrylate salt,
48 g (0.67 mol) of acrylamide, 2 g (0.02 mol) of N-methylolacrylamide, 0.1 g of azobisamidine hydrochloride, and 300 g of deionized water were placed in a three-necked flask similar to Example 1, and heated at 60°C.
Polymerization was carried out for 10 hours to obtain a polymer solution. / 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 6. Example 6 Ammonium methacrylate salt 50g (0.49mol),
48 g (0.48 mol) of methyl methacrylate, 2 g (0.02 mol) of N-methylolacrylamide, 0.1 g of azobisamidine hydrochloride, and 300 g of deionized water.
g was polymerized in the same manner as in the above example to obtain a polymer solution. / 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 6.

Claims (1)

[Claims] 1 General formula R _f ¹ −X ¹ −A ¹ −CONH−Y ¹ −NHCO
-A ² -Z (However, R _f 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 a divalent is an organic group, and A ¹ and A ² are each -O-, -S-, or -N(R ³ )-;
, R ³ is a hydrogen atom or a lower alkyl group, Y ¹ is a divalent organic group, and Z is a non-hydrophilic monovalent organic group), a urethane compound represented by the general formula R _f ² −X ² −A ³ −CONH−Y ² −
NHCO-W (where R _f ² is a polyfluoroalkyl group having 4 to 16 carbon atoms, and X ² 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 a divalent is an organic group, A ³ is one of -O-, -S-, or -N(R ³ )-,
R ³ is a hydrogen atom or a lower alkyl group, Y ² is a divalent organic group, and W is a hydrophilic group). Characteristic antifouling agent composition. 2. The composition 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 composition according to claim 1, wherein the urethane compound/urethane compound ratio (weight ratio) is from 99/1 to 25/75. 4 The ratio (weight ratio) of urethane compound/ammonium methacrylate salt polymer is 1/100 to 100/
1. The composition according to claim 1, which is