JPS6317109B2 - - 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. 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 groups (sometimes abbreviated as R f groups), we have found that a specific R _f group-containing urethane compound is combined with a branched butyl methacrylate/methyl methacrylate copolymer. It has been found that by doing so, it is possible to improve the antifouling performance against dry stains in the treatment of carpets and the like. In particular, certain
Good results can be obtained with an antifouling agent prepared by dispersing an R _f group-containing urethane compound 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 −
The present invention provides a new water-repellent, oil-repellent and stain-proofing agent characterized by comprising a urethane compound represented by CONH-Y ¹ -NHCO-A ² -Z and a branched butyl methacrylate/methyl methacrylate copolymer. . 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 form, it is desirable to perform the dispersion in the coexistence of a specific hydrophilic group-containing urethane compound. That is, the general formula,
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 R _f ² -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 ⁴
- (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 oil and stain resistance, a lower alkyl group having 1 to 4 carbon atoms is preferably employed. 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) ) and other nonionic groups,
−(CH ₂ CH ₂ O) _n −SO ₃ M (where M is a hydrogen atom,
alkali metal, one of the ammonium groups), -
(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 (however, R′, R″, R
is an alkyl group, an aryl group, X is Cl, Br, I,
_Various examples include cationic groups such as
(CH ₂ CH ₂ O) ₂₀ −CH ₃ etc. can be preferably employed. 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 liquid will decrease, and if it is too large, the water repellency will tend to decrease. Therefore, usually 99/1 to 25/75, preferably 95/5 to 50/
May be selected from a range of 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 300 parts by weight, per 100 parts by weight of the urethane compound.
It may be selected from a range of 150 parts by weight. In the present invention, the urethane compound is usually a diisocyanate (OCN-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 include diisocyanate (OCN-Y ² -NCO), fluorine-containing compound R _f ² -X ² -A ³ -H (for example, 2-perfluoroalkylethanol and compound W-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 by various methods. A method in which a mixture of , and an aqueous medium is stirred at high speed under heating and then cooled to room temperature, a method in which a solution of a urethane compound in a water-soluble organic solvent is dropped into an aqueous solution of the urethane compound under stirring, or a method in which a solution of a urethane compound in a water-soluble organic solvent is added dropwise to an aqueous solution of the urethane compound under stirring Possible methods include dropping an aqueous solution of a urethane compound into a solution while stirring, dropping a solution of a urethane compound and a water-soluble organic solvent into water while stirring, or conversely dropping water dropwise. The water-repellent, oil-repellent and antifouling agent of the present invention has a branched butyl methacrylate/branched butyl methacrylate/
A methyl methacrylate copolymer is added and mixed as a blender. In the specific blender copolymer, the molar ratio of branched butyl methacrylate/methyl methacrylate is 95/5 to 5/
95, especially selected from the range of 70/30 to 30/70.
Branched butyl methacrylate includes isobutyl methacrylate and tertiary butyl methacrylate, and isobutyl methacrylate is usually preferably employed. In addition to the above two components, the specific blender copolymer also contains acrylamide,
It may contain one or more types of additive monomers such as methacrylamide, N-methylolacrylamide, alkyl methacrylate, vinyl chloride, styrene, vinyl acetate, vinyl propionate, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. as a constituent 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.
1, particularly from 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.
Adjusted to 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 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 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 well-known or publicly known means can be adopted, 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. Furthermore, in the antifouling process, various processing agents and additives such as antistatic agents, insect repellents, flame retardants, dye stabilizers, and antiwrinkle agents can be used in combination as appropriate. 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 such 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 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. Water 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 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 liquid was obtained by cooling to room temperature. 50 g (0.5 mol) of methyl methacrylate, 50 g (0.35 mol) of isobutyl methacrylate, 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.
into a three-necked flask similar to the above, and heated at 60°C.
A dispersion liquid was obtained by polymerizing for 10 hours. / 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 shown in Section 3 below.
They are summarized in the table.

[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 (0.5 mol) of methyl methacrylate, 48 g (0.34 mol) of isobutyl methacrylate, N-
2 g (0.02 mol) of methylol acrylamide,
5 g of emulsifier C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₃₀ H, 0.1 g of azobisamidine hydrochloride, and 200 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 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 50 g (0.50 mol) of methyl methacrylate, t
- 50 g (0.35 mol) of butyl methacrylate, 5 g of emulsifier C ₁₈ H ₃₅ O (CH ₂ CH ₂ O) ₃₀ H, 0.1 g of azobisamidine hydrochloride, and 200 g of deionized water were placed in a three-necked flask similar to that in Example 1, and 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.

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), and a branched butyl methacrylate/methyl methacrylate copolymer. A water- and oil-repellent antifouling agent. 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 1, wherein the urethane compound/urethane compound ratio (weight ratio) is from 99/1 to 25/75. 4. The processing agent according to claim 1, wherein the ratio (weight ratio) of (urethane compound)/(branched butyl methacrylate/methyl methacrylate copolymer) is 1/100 to 100/1.