JPS59109575A - Stainproof finishing agent - Google Patents

Abstract

PURPOSE:To provide a stainproof finishing agent consisting of a specified urethane compd. and an Rf group-containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer and giving high water and oil repellency and resistance to dry stain. CONSTITUTION:100pts.wt. mixture of (A) 99-25wt% urethane compd. of formula I [where Rf<1> is 4-16C polyfluoroalkyl; X<1> is -R<1>-, a group of formula II or III; R<1> is alkylene ; R<2> is H or lower alkyl; Q<1> and Y<1> are each a divalent organic group; A<1> and A<2> are each -O-, -S- or -N(R<2>)-; Z is a non-hydrophilic univalent organic group] and (B) 1-75wt% hydrophilic group-containing urethane compd. of formula IV (where Rf<2> is Rf<1>; X<2> is X<1>; A<3> is A<1>; Y<2> is H<1>; W is a hydrophilic group) and 10-300pts.wt. medium consisting mainly of water, are mixed by stirring under heat for dispersion and (C) a copolymer of an Rf group- containing vinyl monomer, branched butyl methacrylate and methyl acrylate in the molar ratio of 0.1-10:5-89.9:5-89.9 is added to the resultant dispersion in the (A)/(C) ratio of 1/100-100/1 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-repellent, oil-repellent and stain-proofing agent, and more specifically, a water-repellent, oil-repellent and stain-proofing agent comprising a specific urethane compound containing a polyfluoroalkyl group and a specific blender copolymer. Regarding processing agents.

Various polyfluoroalkyl group-containing urethane compounds have been proposed as substances useful for antifouling treatment of interior products such as carpets. For example, US Patent No. 5,398,182, US Patent No.! 148428
1 specification, JP-A-53-112855, JP-A-54-74000, etc. And, JP-A-4
No. 7-7600 and other publications propose stain-proofing carpets by using a combination of a polyfluoroalkyl group-containing main agent and a water-insoluble addition polymer blender having a specific main transition temperature and solubility parameter. .

However, hydrocarbon blenders are water repellent.

There is a problem that oil repellency is inhibited.

As a result of repeated research and consideration on antifouling treatment using polyfluoroalkyl group (hereinafter sometimes abbreviated as Rf group)-containing urethane compounds, the present inventor discovered that a specific Rf group-containing urethane compound contains Rf. We have discovered that by using a vinyl monomer/branched butyl methacrylate/methyl methacrylate 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 prepared by dispersing a specific Rf group-containing urethane compound in an aqueous medium in the coexistence of a specific hydrophilic group-containing urethane compound.

Thus, the present invention relates to the general formula Rf''-X''-A1-C
A new water-repellent, oil-repellent and stain-proofing agent characterized by comprising a urethane compound 1 represented by ONH-Y'-NHOO-A''-Z and an Rf-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 form, it is desirable to perform the dispersion in the coexistence of a specific hydrophilic group-containing urethane compound. That is, the general formula, Rf2-X"-A"0OHH-Y2-
The urethane compound 1 is dispersed in a medium mainly consisting of water in the coexistence of a hydrophilic group-containing urethane compound (2) represented by NHOO-W.

Therefore, Rfl and Rf2 in urethane compounds 1 and 2 are each a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and those whose terminal end is a perfluoroalkyl group are usually used. However, those containing a hydrogen atom or a chlorine atom at the terminal end, or a group containing oxyperfluoroalkylene can also be used. A preferred embodiment of Rrl and Ht2 is a perfluoroalkyl group, and those having 6 to 12 carbon atoms are particularly preferred. Xi and χ
2 digits each h -R1-, -coN (Rly-Ql-2 and -
8O2N (R") 1 to 20 is suitable.Also, AI,
A2. and A3 are respectively -o-, -s-, or -N(
R3)- (where BS represents a hydrogen atom or a lower alkyl group), and 10- is preferred from the viewpoint of easy availability. Next, yl and Y2 are divalent organic groups, and those having 24 or less carbon atoms, especially 6 to 15 carbon atoms, are selected from the viewpoint of making the urethane molecule rigid and improving the durability of the antifouling performance. Those containing at least one aromatic ring or aliphatic ring are preferably employed. 2 in the urethane compound 1 is a non-hydrophilic monovalent organic group, and is an alkyl group,
Aryl groups, those containing a petero atom, and even -XI
-Rfl and the like can be exemplified, but lower alkyl groups having 1 to 4 carbon atoms are preferably employed from the viewpoint of water/oil repellency and antifouling performance. W in urethane compound ① is a hydrophilic group, -(0H20H20)-R4 (where m is 1 to
an integer of 50, R4 represents a hydrogen atom or an alkyl I having 1 to 4 carbon atoms;
OH20HfiO)m-8o3M (where M represents one of a hydrogen atom, an alkali metal, or an ammonium group)
, -(C1120H,O)m-P03M, -OH,O
E2SOsM, Φ anionic groups such as -〇H2OH2O00M, and -OH, Cj NR'R "R"
XO (However, R', R', R'' are alkyl groups, aryl groups, X is 01, Br, I, 0O
Various examples include cationic groups such as OCH3, etc.; however, from the viewpoint of compatibility with other processing agents, nonionic groups such as -(cl(,o)I2o) can be used.
, o-Ca3, etc. can be preferably employed.

In the present invention, R, I and Rf2, Xi and X2
, AI and A3, and yl and Y2 do not necessarily have to match. Also, urethane compounds 1 and I
Each l may be a mixture. For example, for the urethane compounds I and (2), it is also possible to use a mixture of a plurality of compounds having different carbon numbers, such as Htl and Rf2, respectively.

In the present invention, when dispersing the urethane compound 1 in a medium mainly composed of water, it is important that the urethane compound 1 is allowed to coexist.

When the urethane compound (■) is not present, when the dispersion is carried out by the urethane compound (2) alone, or when the urethane compound (2) is used, ordinary surfactant substances such as sodium 2-1-norsulfate, alkylphenol φ-1-1-no-col are used When ether, ammonium perfluorooctanoate, etc. are used, there is a tendency for dispersion to be difficult or for water repellency, oil repellency, and dry fill resistance to deteriorate. The coexistence ratio (weight ratio) of urethane compound l/urethane compound ■ is not particularly limited, but
If the reading ratio is too small, the stability of the dispersion liquid tends to decrease, and if it is too large, the water repellency tends to decrease.
/1~25/75 preferably 9515~s o/s o
The range 751 et al.

In the present invention, the medium mainly consisting of water includes cases where water is used alone, but it is a more preferable embodiment that a water-soluble organic solvent coexists.

By adding the water-soluble organic solvent, the interfacial tension of the medium is lowered, and the melting point and solubility of the urethane compound 1 are lowered and the solubility thereof is increased, 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, and ethylene glycol monomethyl ether. Butyl 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 monoethyl ether, triethylene Water-soluble ethers such as glycol monoethyl ether, and water-soluble amides such as formamide, dimethylformamide, and acetamide can be preferably employed. The amount of the water-soluble organic solvent added is usually selected from the range of 10 to 300 parts by weight, preferably 20 to 150 parts by weight, per 100 parts by weight of the total amount of urethane compound 1 and urethane compound 2. obtain.

In the present invention, the urethane compound 1 is usually a diisocyanate (ocN-yl-NCo) containing a fluorine-containing compound R.
It can be produced by addition reaction of fl -XI -AI -H (for example, 2-)-fluoroalkylethanol) and compound Z-A"-I (for example, methanol). It can also be used for urethane compounds. Similarly diincyaner) (0CN-Y2-Neo) K fluorine-containing compound R
f2-y, Z -A3-H (e.g. 2~)-fluoroalkylethanol) and compound w -H (e.g. tJd:
It can be produced by addition reaction with polyoxyethylene glycol monomethyl ether).

In the present invention, the dispersion of urethane compounds 1 and 2 into a medium mainly composed of water can be carried out by various methods.
For example, a method in which a mixture of urethane compound 1, ① and an aqueous medium is stirred at high speed under heating and then cooled to a cold temperature, a method in which a solution of urethane compound 1 in a water-soluble organic solvent is dropped into an aqueous solution of urethane compound ① with stirring, or Urethane compound 1
A method of dropping an aqueous solution of urethane compound H into a water-soluble organic solvent solution under stirring, or dropping a water-soluble organic solvent solution of urethane compounds 1 and 1 into water with stirring, or conversely, dropping water dropwise. methods etc. can be adopted.

The water-repellent, oil-repellent and antifouling agent of the present invention is prepared by adding and mixing an R8-containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer to the urethane compound 1 described above as a blender. In the specific blender copolymer, the molar ratio of R2-containing vinyl monomer/branched butyl methacrylate/methyl methacrylate is 0.
．． 1-1015-89.9 / 5-899 especially 1-5
Selected from the range /25 to /19 /25 to 69. As the Rf group-containing vinyl monomer, various types can be mentioned without particular limitation, including conventionally known and well-known ones. For example, CF3(at2)8(CF2
)2oaocH=an2C! F3((!F2), (O
H2),,ocau=CH2,0F3((IF,)8
(CF2)2ococ (CF3)=cn, ay3(
OF,)4ccocH=cH,,0F3(cp゛, :
) 7S O2N CO3 Engineering 17 ) (CR2) 2000
0H=CH2, (,R3(CF2)7SO2N(C!
H,) (OH2)2ococ(aH3door OH2, (0
000H3) ococ(CR3) = unsaturated esters represented by acrylates or methacrylates containing a perfluoroalkyl group having 3220 carbon atoms, preferably 4 to 16 carbon atoms, such as cn2. Branched butyl methacrylate includes isobutyl methacrylate and tertiary butyl methacrylate, but in-butyl 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 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.

Urethane compound 1/4? Percentage of constant blender copolymer (
The weight ratio) can be changed in various ways, but is usually 1/100.
~100/1, preferably 1/10 to 10/1, especially 1/1
It can be selected from the range of 2 to 2/1. By using such a mixture, dry soil resistance is improved compared to when each is used alone. If the specific blender copolymer is used in too much amount, 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.

Therefore, when adding and mixing the specific blender copolymer, an aqueous dispersion form of the urethane compound I is adopted in a preferred embodiment of the present invention, so it is preferable to use the blender in the form of an aqueous dispersion. preferable. The aqueous dispersion of the specific blender copolymer can be mixed well with the aqueous dispersion of the urethane compound I in a wide range of proportions, and is mixed within the above ratio range of urethane compound summer/specific blender copolymer. obtain.

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 I + urethane compound u-1-% constant blender copolymer) concentration is not particularly limited, but It is usually prepared to 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. Any advantage that can reduce contamination is recognized.

The water- and oil-repellent stain-proofing agent of the present invention can be applied to various articles made of polyamide, polyester, leather, wood, etc., such as carpets, reception sets, curtains, wallpaper, and interior products such as vehicle interior items. , it can also be advantageously applied to outdoor tents and the like.

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 employed, such as dipping, spraying,
For example, the coating may be applied to the surface of the object to be treated by known coating methods such as coating and then dried. Furthermore, in the antifouling process, various processing agents and additives such as antistatic agents, insect repellents, RT fuel dye stabilizers, and antiwrinkle agents can be appropriately used in combination.

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 the following Examples and Comparative Examples, water repellency, oil repellency, and dry soil resistance were measured as follows.

That is, the water repellency is determined by 20 parts by volume of isopronol and 8 parts by volume of water.
A few drops of a mixed solution consisting of 0 parts by volume are placed on two locations on a sample carpet, and the time required for the solution to soak in is expressed as the time taken. In addition, oil repellency is determined by placing a few drops (approximately 4 squares 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 1 4 Dry Soil Properties
K cut, put into a container together 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 lightning cleaner, measure reflectance, and evaluate the degree of contamination. The degree of contamination is calculated using the following formula.

Contamination degree (%) -C (Ro - Rp) ÷ Ro:]X100
R8 = Reflectance of uncontaminated sample Rp: Reflectance of contaminated sample Table 2 Examples 1 to 3 14, 4 Li! (0,9 moles of G O), 80 y of deionized water, 202 y of xo::ry-lene glycol monomethyl ether, and an internal volume of 5 C1Om equipped with a thermometer, cooling tube, and vacuum stirrer! , into a Mitsuro flask, and raise the temperature to about 100°C. After stirring under high shear for 60 minutes, the mixture was cooled to room temperature to obtain a dispersion liquid (■).

C! F3(aF2)8an2an2ococn=ca2
1 o y (o, 02 mol) of methyl methacrylate, 60 t (o, 6 mol) of methyl methacrylate, 2C 7 (0, 21 mol) of inbutyl methacrylate, emulsifier OtgHa
52 of sO ((J(20H20)s.
The dispersion ■ is prepared by polymerization for a period of time.

■/■ are mixed in the ratio shown in Table 3 below, and the solid content is 0.5
Dilution was adjusted with deionized water to give a weight percent. This diluted solution was evenly sprayed onto a nylon loop tufted carpet (50% wet pickup) and dried at 130° C. for 20 minutes. The water repellency, oil repellency, and dry fill resistance of the thus obtained treated carpet were measured.

Comparative Examples 1 to 3 Methyl methacrylate 50t, inbutyl methacrylate 50? A dispersion (2) was obtained by polymerizing in the same manner as in the example.

■/■ 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 3 Example 4 OH3 negative ay3(clF2)l, (CB, )2000(!=
2 Of (n, 04 mol) of OH2, 501 (0,5 mol) of methyl methacrylate, 28? of isobutyl methacrylate. (0,20 mol), 29 (0,02 mol) of N-methylolacrylamide, emulsifier 0xsH
5f of ssO(CHzc Tlz O)3oH, 0.12 of azobisamidine hydrochloride, and 200 of deionized water.
7 was placed in the same Mitsuro flask as in Example 1, and 60
Polymerization was carried out at ℃ for 10 hours to obtain a dispersion liquid (■).

■/■ were mixed at a ratio of 1/1 (weight ratio) and diluted and treated 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 splash/r soil resistance of 4.

Example 5 Cr2(ay2)7so2N(aH,)cH2cH2o
coc(aH3)=20 of cn2? (0,03 mol), 4 C1t of methyl methacrylate (0,40 mol), 4or of t-butyl methacrylate (o2 s mol), emulsifier c, 81 (350 (OH2C!H20)3
5f of oH, 0.1f of azobisamidine hydrochloride, and 2002 of deionized water were charged into a Mitsuro flask similar to that in Example 1, and polymerized at 60°C for 10 hours to obtain a dispersion (2).

■/■ were mixed at a ratio of 1/1 (weight ratio) and diluted and treated in the same manner as in Example 1. The resulting treated carpet had water repellency of 3 minutes or more, oil repellency of 6, and dry rifle resistance of 7.

Claims (1)

[Claims] 1. General formula RfI -XI -A'-00HH-Yl-
HHOO-A2-Z (However, Rfl is a polyfluoroalkyl group having 4 to 16 carbon atoms, and XI is -R1-, -
0ON(R2)-Ql-2 or -8O2N(R2)-Q
l-, R1 is an alkylene group, R2 is a hydrogen atom or a lower alkyl group, Ql is a divalent organic group, A
l and A2 are each -o-, -B-, or -N(R”)-
1 is a hydrogen atom or a lower alkyl group, yl is a divalent organic group, and 2 is a non-hydrophilic monovalent organic group. and R
A water-repellent, oil-repellent and antifouling agent comprising a vinyl monomer containing f/branched butyl methacrylate/methyl methacrylate copolymer. 2. The processing agent according to claim 1, wherein the urethane compound 1 is employed in the form of an aqueous dispersion in which the urethane compound 1 is dispersed in a medium mainly consisting of water. 3. The urethane compound 1 has the general formula Rf2-X2-A3-0ONH-Y2-NHOO- in a medium mainly composed of water.
W (However, Rf2 is a polyfluoroalkyl group having 4 to 16 carbon atoms), 12 is -i't''-, -0ON
(R2)-Ql-, or -8o, N(R2)-Q'- R1 is an alkylene group 12 is a hydrogen atom or a lower alkyl group Ql is a divalent organic group A3 is 10 -, -S-, or " is one of -N(R3)- R
3 is a hydrogen atom or a lower alkyl group, υ y2 is a divalent organic group, and W is a hydrophilic group. A processing agent according to scope 2. 4. The ratio (weight ratio) of urethane compound I/urethane compound II is 99/1 to 25. /75 The processing agent according to claim 6. 5. The ratio (weight ratio) of (urethane compound/(Rf-containing vinyl monomer/branched butyl methacrylate/methyl methacrylate copolymer)) is 1/100 to 100/
1. The processing agent according to claim 1, which is