JPS59109574A - Stainproof finishing agent composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which can impart high water repellent and oil repellent performance as well as stainproof performance against dry staining to carpet, etc., consisting of specified urethane compds. and an acrylate (co)polymer. CONSTITUTION:A urethane compd. of formula I [wherein Rf<1> is a 4-16C polyfluoroalkyl ; X<1> is -R<1>-, a group of formula II or III ; R<2> is H, lower alkyl; Q<1>, Y<1> are each a bivalent org. group; A<1>, A<2> are each -O-, -S-, -N(R<2>)-; Z is a monovalent hydrophobic org. group], a hydrophilic group-contg. urethane compd. of formula IV (wherein Rf<2> is Rf<1>; X<2> is X<1>; A<2> is A<1>; A<3> is R<3>; Y<2> is Y<1>; W is a hydrophilic group) and a medium mainly composed of water are stirred at a high speed to obtain a dispersion. An acrylate (co)polymer contg. an unsaturated ester of formula V (wherein Rf is a 4-16C branched or straight- chain perfluoroalkyl; R is a 1-10C branched or straight-chain bivalent alkylene; R' is H, methyl) as a structural unit is added to the dispersion.

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 Pat. No. 3,398,182, US Pat. No. 3,484,281
specification, JP-A-53-112855, JP-A-Sho 5
See Publication No. 4-74000, etc. And, JP-A-47
In Japanese Patent No. 7600, etc., it has been proposed to antifouling treatment of Shikabet by using a polyfluoroalkyl group-containing main agent and a water-insoluble addition polymer blender having a specific main transition temperature and solubility parameter. .

As a result of various studies and studies on antifouling treatment using urethane compounds rich in polyfluoroalkyl groups (hereinafter sometimes abbreviated as Rf groups), the present inventors have found that a specific Rf group-containing urethane compound contains an Rf group. It has been found that by using an acrylate compound in combination, it is possible to improve the antifouling performance against dry stains in the treatment of carpets and the like, as well as imparting a high degree of water and oil repellency. especially,
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 E4'-X'-A''-001
(This item provides a new water-repellent, oil-repellent, and stain-resistant finishing agent characterized by comprising a urethane compound I represented by H-Y'4HOO-A2-Z and an acrylate compound represented by the general formula RfROOOOR'=OH2. be.

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 new water group-containing urethane compound. That is, the general formula, Rf2-X2-13-00 group H-Y2
The urethane compound (1) is dispersed in a medium mainly consisting of water in the coexistence of the hydrophilic group-containing urethane compound (1) represented by the group HCo-w.

Therefore, Rfl and Rf2 in the urethane compounds (1) and (2) are each a linear or branched polyfluoroalkyl group having 4 to 16 carbon atoms, and usually the terminal end is a perfluoroalkyl group. However, those containing a hydrogen atom or a chlorine atom at the end, or a group containing oxyperfluoroalkylene can also be used. A preferred embodiment of Rf1 and Rf2 is a perfluoroalkyl group, and those having 6 to 12 carbon atoms are particularly preferred. Xl and x
2 are respectively -R1-, -aoi(R2)-Q'-+ and -
802 anti(R2)-Q'- (wherein -Bl- is an alkylene group, R2 is a hydrogen atom or a lower alkyl group, Ql is a divalent organic group), and an alkylene group, especially a carbon A number of 1 to 20 pieces is suitable. Also, AI
, A2. and A3 are each -o-, -s-, or -N
(R3)- (However, R3Jd 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 to make the urethane molecule rigid and improve the durability of the antifouling performance. Those containing at least one aromatic ring or aliphatic ring are preferably employed. Urethane compound I
2 is a non-hydrophilic monovalent organic group, including an alkyl group, an aryl group, a heteroatom-containing group, and -X
Examples include l-Rfl, 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, typically represented by -(OH20H20)m-R' (where m is an integer of 1 to 50 and R4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). nonionic group, -
((:!H20H20)m-so3M (where M represents one of a hydrogen atom, an alkali metal, or an ammonium group),
-(OH2CH20)m-PO3M, -CH20H2
Anionic groups such as So3M, -OH20H2000M, and -0H2CH2HR'R'R"'XO (however, R
〆 Ej, RILL is an alkyl group, an aryl group,
is 01. Br, ■.

Various examples include cationic groups such as OCOCH3, etc.; however, from the viewpoint of compatibility with other processing agents, nonionic groups such as -(aH2aH,, o)
2o-an3 etc. can be preferably adopted.

In the present invention, Rfl and Rf2, Xl and X2, AI
and A3, and Yl and Y2 do not necessarily have to match. Further, urethane compounds I and (1) may each be a mixture. For example, urethane compounds ■ and ■
It is also possible to use a mixture of a plurality of Rr1 and Rf2 having different numbers of carbon atoms, respectively.

In the present invention, when dispersing urethane compound I in a medium mainly composed of water, it is important to coexist with urethane compound (I).

When urethane compound ① is not present, that is, when urethane compound I is used alone for dispersion, or when urethane compound ① is used, ordinary surface active substances such as sodium lauryl sulfate, alkylphenonyl polyglycol ether, perfluorooctane are used. When ammonium acid or the like is used, dispersion is difficult and water repellency, oil repellency, and dry soil resistance tend to decrease. The coexistence ratio (weight ratio) of urethane compound I/urethane compound H is not particularly limited, but if the nucleation is too small, the stability of the dispersion will decrease, and if it is too large, the water repellency will tend to decrease. Therefore, usually 99/1-25
/75 preferably from the range of 9515 to 50150.

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.

By adding a 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, making it easier to disperse. Various organic solvents can be used, including dioxane, tetrahydrofuran, ethylpropyl ether,
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, ethylene glycol motsubutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Water-soluble ethers such as diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol motubutyl ether, water-soluble amides such as formamide, dimethylformamide, acetamide, etc. is preferable and can be adopted. The amount of the water-soluble organic solvent added can be selected from the range of 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 urethane compound I and urethane compound I.

In the present invention, the urethane compound I is usually a diisocyaner (0CN-Yl-tJOo), a fluorine-containing compound B, rl -x'-A' -H (for example, 2-) (
-fluoroalkylethanol) and compound z-A2-F
It can be produced by addition reaction with i (for example, methanol). Similarly, urethane compound (2) is a combination of diisocyanate (oci-yl FICO), fluorine-containing compound Rf2-x2-A3-H (e.g. 2-/<-7 fluoroalkylethanol) and compound W-H (e.g. polyoxyethylene glycol monomethyl ether).

In the present invention, dispersion of urethane compounds I and +1 into a medium mainly composed of water can be carried out by various methods. A method of cooling to room temperature, a method of dropping a solution of urethane compound I in a water-soluble organic solvent into an aqueous solution of urethane compound 5IIX with stirring, or a method of stirring an aqueous solution of urethane compound II in a solution of urethane compound II in a water-soluble organic solvent. Possible methods include dropping a solution of urethane compounds I and (2) in a water-soluble frame 1 solvent into water while stirring, or conversely dropping water dropwise.

In the fountain and oil-repellent and anti-fouling agent of the present invention, a water- and oil-repellent agent containing a fluoroalkyl group is added and mixed as a blender to the above-mentioned urethane compound (1).

In the present invention, various fluoroalkyl group-containing water and oil repellents may be used without particular limitation, including those that are conventionally known or well known. for example,
0F3(OF2)8(OH2)20000H=OH2,
0F3(OF2)7(OH2)410000H=OE2
．． 0F3(OF2)8(OH2)20000((5H3
)=0)I2.0F3(OF2)40H20000(O
H3)-COH2)30COCH-J3H2,0F3(
OF2)6(OH2)2000C! (OH5)=so2
i(c3H,)(anz),,ococH=cu2
, 0F3(cF2)7sO2[(CI(3)(aH2
)2ococ(aH3'+=cH,,,0F3(OF2
)7('0H2)3COOOH=polymer of unsaturated esters represented by acrylates or methacrylates containing fluoroalkyl groups having 3 to 20 carbon atoms, preferably 4 to 16 carbon atoms, or such unsaturated esters Examples include copolymers of esters and one or more polymerizable compounds that do not contain fluoroalkyl groups. In this case, examples of polymerizable compounds that do not include fluoroalkyl groups include ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene rogenide, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic Acids and their alkyl esters, methacrylic acid and their alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide or methacrylamide, vinyl alkyl ethers, vinyl alkyl ketones, butadiene, imbrene, chloroprene, glycidyl acrylate, anhydrous There is something like maleic acid. By copolymerizing these polymerizable compounds that do not contain fluoroalkyl groups, it is possible to impart a high degree of water and oil repellency in addition to the ability to repel dry stains. , ”0F(CF2)70
0bIHOOOF3” 00H=OH2, CF201(C!F2)1oO1(2
0000(OHJ=OHz, H(OF2), OC!H2
QC! Also included are water and oil repellents made of polymers or copolymers of fluoroalkyl group-containing polymerizable compounds such as 0OH=OH2. However, as the water and oil repellent, it is preferable to use a polymer or copolymer containing a perfluoroalkyl group as described above. Therefore, if ease of acquisition and other factors are taken into account, the general formula RfROCOC
R'=CH3 (wherein Rf is a straight-chain or branched chain having 4 to 16 carbon atoms) -fluoroalkyl group, R is a straight-chain or branched chain having 1 to 10 carbon atoms A polymer or copolymer containing as a constituent unit an ester of acrylic acid or methacrylic acid containing a monofluoroalkyl group represented by a branched divalent alkylene group (R' is a hydrogen atom or a methyl group) It can be said that the adoption of a water and oil repellent having a specific composition is especially advantageous for a wide range of commercial applications.

To prepare the polymer or copolymer for water and oil repellent used in the method of the present invention, various combination reaction methods and conditions can be arbitrarily selected, and bulk polymerization, solution polymerization, suspension polymerization, etc. ,
Any of the various polymerization methods such as emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, a method in which a compound to be polymerized is emulsified in water in the presence of a surfactant or the like and polymerized while stirring, or a method in which a compound to be polymerized as a raw material is emulsified in water and polymerized while stirring,
A method may be adopted in which the material is dissolved in an appropriate organic solvent and subjected to solution polymerization under the action of a polymerization initiator (a polymerization initiator such as a peroxide or an azo compound, or ionizing radiation).

The ratio (weight ratio) of urethane compound I/specific blender copolymer can be varied, but is usually 1/100 to 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, the dry fill properties are 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 fill 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 co-claw coalescence can be mixed well with the aqueous dispersion of the urethane compound I in a wide range of proportions, and should be mixed in such a way that the proportion range of the urethane compound (1)/specific blender copolymer is achieved. 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 + urethane compound + specific blender copolymer) concentration is not particularly limited, but usually 5-60% by weight, preferably 15
-50% by weight, and for antifouling treatment, it is used after being diluted with water to a solid content of about 0.1-4% by weight. Aqueous dispersions have advantages over organic solvent-based ones, such as a higher flash point and higher solids concentration, and are also suitable for use in antifouling processing. Advantages such as being able to reduce pollution of the working environment are also 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 interior products such as carpets, reception sets, curtains, wallpaper, and vehicle interior parts. In addition, it can 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 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 and dried by a known coating method such as coating. Furthermore, in the antifouling process, various processing agents and additives such as antistatic agents, insect repellents, )/][flame 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 fill resistance were measured as follows.

That is, water repellency is 20 parts of Impropanol and 8 parts of water.
A few drops of a mixed solution consisting of 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. In addition, oil repellency was determined by placing several drops (approximately 4 in diameter) of the test solution shown in Table 1 below on two locations on the sample carpet.
Determine the penetration state after 30 seconds (AATOO-T
M 118-1966).

Table 1 [ [ Dry soil resistance is determined by cutting the sample carpet into 5 x 7 cm pieces, placing them in a container with the dry smoke stains shown in Table 2 below (twice the weight of the sample), and mixing vigorously for 3 minutes. Stir and 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.

Pollution level ($;) - [(Ro-Rp) ÷ Ro] x 100
Fo: Reflectance of uncontaminated sample Rp: Reflectance of contaminated sample 1'4.4 y (o, o o q mol) of Table 2 Examples 1 to 3 and Comparative Examples 1 to 3, 802 of deionized water , and 2Of of ethylene glycol monomethyl ether are charged into a 300 ml Mitsuro flask equipped with a thermometer, condenser and vacuum stirrer, and the temperature is raised to about 100°C.

After high-shear stirring for 30 minutes, cool to room temperature and prepare the dispersion.
I got it.

0H2=CH000(OH2)3(OF2), 0F31
50 f, deoxygenated pure water 6001, acetone 100 ml, n-hexadecyl mercaptan 2 F, azobisisobutyramidine dihydrochloride 42.017H33COO (C!
H20H20)! A thermocouple thermometer and an electromagnetic stirrer were installed at 4H1,O. The mixture was placed in a pressure-resistant container (inner volume: 2 tons) made of 5 US-27, and thoroughly emulsified and dispersed using a stirring wheel under a nitrogen stream. Furthermore, after cleaning by nitrogen blowing for about 1 hour, vinyl chloride 50 with a purity of 99.9% was washed.
A stable emulsified latex solution (2) was obtained by adding F and polymerizing at 50° C. for 7 hours while stirring slowly. The resulting stable emulsion latex had a copolymer solids content of 21.3%.
It contained. The elemental analysis value of the copolymer is F4 & 8%, and the calculated value from the reaction raw material is F4 & 5%. In addition, this copolymer was heated at 30°C in pensitrifluoride.
, 0.50 f The intrinsic viscosity of a 7100 ml solution is 0.
It was 58.

■/■ are mixed in the ratio shown in Table 3 below, and the solid content is 0.
Dilution was adjusted with deionized water to a weight of 5%. Spray this diluted solution evenly onto a nylon carpet with a wet pickup (5 o'clock), 130'
It was dried at C for 20 minutes. The water repellency, oil repellency, and dry fill resistance of the thus obtained treated carpet were measured. In addition, carpets treated with a liquid diluted to a solid content of 05% by weight using only ■ or ■ (Comparative Examples 2 to 3)
) and untreated carpet (Comparative Example 1). These measurement results are summarized in Table 3 below.

Table 3 Example 4 Glass autoclave equipped with a stirrer (inner volume 1 t)
) inside C! H2=O(0HJOOOOOH2CH20nF
2n+ j (n=16-12, average 9) 1401, vinylidene chloride 56fS K-methylolacrylamide 4
? , t-dodecyl mercaptan2. s y, deoxidized pure water 4002, acetone 100%, ■ 0nH2n-kI HH(OH3)2・0H3COOO
(n = 8-16, average 13) 6 f XC1a
, H3r■[(2.0HsOOOOe6 F, azobisisobutyramidine dihydrochloride 32 is added and thoroughly emulsified and dispersed by stirring under a nitrogen stream.Next, the temperature of the reaction vessel is gradually raised, and under stirring A copolymerization reaction was carried out at 60°C for 15 hours to obtain an emulsified dispersion liquid.The obtained latex had a solid content concentration of 26.5%.When the polymer was separated from this latex and dissolved in pensitrifluoride, [η] at 60°C was [1070].

■/■ were mixed at a ratio of 1/1 (pi 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 dry soil resistance of 6.

Example 5 Glass autoclave equipped with a stirrer (inner volume 1 t)
) in 0H2=OHOOOOOH20H2C! nF2H+
1 (n = 6-12, average 9) 112 f1 stearyl methacrylate) 44 f, R-methylolacrylamide 4 f, deoxygenated pure water 280 f, acetone 120
f, azobisisobutyramidine-dihydrochloride 3.2fX
ORB C! xsH3a(CHzOHO)s(OHzC!H20
)2oH162,0nH2n4-1 tl(OH3)z
・Add 2 g of CH3CO0e (n-8 to 16, average 13) and stir under a nitrogen stream to fully evaporate the pores.Next, press-fill vinyl chloride 40, and gradually lower the temperature of the reaction vessel. A copolymerization reaction was carried out at 50° C. for 20 hours under stirring to obtain emulsification solution 9. The resulting latex had a solid content concentration of 34.5%.

■/■ were mixed at a ratio of 1/1 (weight B ratio) and diluted and treated in the same manner as in Example 1. The water repellency of the coated treated carpet was 3 minutes or more, the oil repellency was 6, and the dry vine resistance was 5.

Within the agent [“1 Akira” Agent Ryo Hagiwara

Claims (1)

[Claims] 1. General formula Rf'-X'-A''-0ONH=Y'-RH
OO-12-Z (However, RfI is a polyfluoroalkyl group having 4 to 16 carbon atoms, and X! is -1'-, -0O
N('R2)-ql-2 or -E102 RCR2)
-Q' (7) 1, R1 is an alkylene group, R2 is a hydrogen atom or a lower alkyl group, Ql is a divalent organic group, AI and A2 are each 'l''-1
or -N (R2)-, R2 is a hydrogen atom or a lower alkyl group, yl is a divalent organic group, and 2 is a non-hydrophilic monovalent organic group]. Urethane compounds expressed! and the general formula R, r ROOOOR' = OR2 (however, R in the formula
f is a linear or branched fluoroalkyl group having 4 to 16 carbon atoms, R is a linear or branched divalent alkylene group having 1 to 10 carbon atoms, and R' is 1. A water- and oil-repellent and stain-proofing agent, characterized in that it is made from an acrylate compound which is a polymer or copolymer containing as a constitutional unit an unsaturated ester represented by a hydrogen atom or a methyl group. 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 l has the general formula Rf2-X2-A3-00 H-Y2-1(H(:!
0-W (However, B f2 is a polyfluoroalkyl group having 4 to 16 carbon atoms, and X2 is -R'-, -co+q(
R2) -Ql-2 or -El o2N (R2) -Q
l-, R1 is an alkylene group, R2 is a hydrogen atom or a lower alkyl group, Ql is a divalent organic group, and A3 is -o-, -8-, or -N(R3)-. and R3 is a hydrogen atom or a lower alkyl group, Y2
3. The processing agent according to claim 2, wherein the processing agent is dispersed in the coexistence of a hydrophilic group-containing urethane compound (2) represented by (1) is a divalent organic group, and W is a hydrophilic group. 4. The processing agent according to claim 3, wherein the ratio (weight ratio) of urethane compound (1)/urethane compound (2) is from 99/1 to 25/75. 5. The processing agent according to claim 1, wherein the ratio (weight ratio) of urethane compound (1)/acrylate polymer or copolymer is 1/100 to 100/1.