JPH02252787A - Stainproof, water-and oil-repellent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent both in stainproofness and in water and oil repellency by using a fluoroalkylated water-and oil-repellent and a silane or titanate coupling agent as constituents. CONSTITUTION:The title composition consists of a fluoroalkylated water-and oil-repellent [e.g. a polymer consisting of a compound of formula I (wherein n is 3 to 7), vinyl chloride, and 2-ethylhexyl methacrylate] and a silane or titanate coupling agent (e.g. a compound of formula II).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an antifouling water and oil repellent composition, and more specifically, a water and oil repellent composition containing a fluoroalkyl group and a silane-based or titanium-based composition. The present invention relates to a water and oil repellent composition that exhibits high stain resistance and is composed of a coupling agent.

[Conventional technology]

Conventionally, esters of 1,1,2,2-tetrahydro-perfluoroalkanols of acrylic acid or methacrylic acid,
N-alkyl perfluoroalkanesulfonic acid amide A polymer of a polymerizable compound containing a fluoroalkyl group, such as an ester of acrylic acid or methacrylic acid, or such a polymerizable compound and an acrylic ester, a methacrylic ester, or a vinyl chloride. ,styrene,
Copolymers of maleic anhydride with other polymerizable compounds such as vinyl acetate, chlorobrene, butadiene and methyl vinyl ketone are known as water and oil repellents. Also,
It is known that phosphoric acid esters of 1,1,2,2-tetrahydro-perfluoroalkanol, chromium complex salts of perfluoroalkylcarboxylic acids, and the like can also be used as water and oil repellents.

[Problem to be solved by the invention]

Water and oil repellency as well as stain resistance are important performances in the field of interior products such as carpets. However, conventional water and oil repellents containing fluoroalkyl groups have been found to have a drawback in their antifouling properties, that is, their repellency against dirt containing water or oil, or against dry dirt. In order to improve stain resistance, water and oil repellents made of copolymers of fluoroalkyl group-containing monomers and hydrophilic monomers have been proposed, but satisfactory results have not been obtained.

An object of the present invention is to provide a water and oil repellent composition that has excellent stain resistance as well as water and oil repellency.

[Means to solve the problem]

The gist of the present invention resides in an antifouling water- and oil-repellent composition comprising a fluoroalkyl group-containing water- and oil-repellent compound and a silane-based or titanium-based coupling agent.

In the present invention, various fluoroalkyl group-containing water- and oil-repellent compounds can be used without particular limitation, including conventionally known compounds. The fluoroalkyl group-containing water- and oil-repellent compound is a fluoroalkyl group-containing polymer or a fluoroalkyl group-containing urethane compound.

The fluoroalkyl group-containing polymer has, for example, the general formula: % formula % () [wherein Rf is a polyfluoroalkyl group having 3 to 20 carbon atoms, and R1 is a hydrogen atom, a fluorine atom or a methyl group] , R8 is -R'--CON(R')-Q'- or -8o!
N (R -Q'- (wherein, R3 is an alkylene group, R4 is a hydrogen atom or a lower alkyl group, and Ql is a divalent organic group). A fluoroalkyl group-containing unsaturated ester represented by , at least one selected from the group consisting of esters of acrylic acid, α-fluoroacrylic acid or methacrylic acid.
A fluoroalkyl group-containing polymer having structural units formed from various monomers is preferred. The fluoroalkyl group-containing unsaturated esters (I) are easy to handle and are particularly advantageous for a wide range of commercial applications. The fluoroalkyl group-containing unsaturated ester (I) has 3 to 3 carbon atoms.
Particular preference is given to unsaturated esters containing 20, preferably 4 to 15 perfluoroalkyl groups. Examples of perfluoroalkyl group-containing unsaturated esters are CF3(CPz)7(CHt)*0COCH=CHt,
CPa(CFt)acHtOcOc(CHs)CHt,
CP s (CF *) s (CHl) to 'OOC (C
Hs)=Cf-It, CFa(CFz), 5OJ(C
J7XCHt)tOcOcH-cHt, CP, (CP
yo)t(CHJtOCOCH= CH-1CFaCP*
(CP*CPt)icHtcHzOcOcF= CHt
It is.

Unsaturated esters containing perfluoroalkyl groups are preferred, but unsaturated esters containing no perfluoroalkyl groups, such as CF.C(CFtCI2(CFt)+oCHtOCOC(CHs)
=CHt, H(cpt)+. CHt OCOCH=C
Ht etc. can also be used.

The fluoroalkyl group-containing polymer includes a homopolymer consisting of one kind of fluoroalkyl group-containing unsaturated ester, a copolymer consisting of at least two kinds of fluoroalkyl group-containing unsaturated ester, and at least one kind of fluoroalkyl group-containing unsaturated ester. These include copolymers consisting of saturated esters and copolymerizable monomers that do not contain at least one fluoroalkyl group.

Copolymerizable monomers that do not contain fluoroalkyl groups include, for example, ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, vinylidene halides, acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, acrylic acid and its alkyl ester, methacrylic acid and its alkyl ester, acrylamide, methacrylamide,
These are diacetone acrylamide, methylolated diacetone acrylamide or methacrylamide, vinyl alkyl ether, vinyl alkyl ketone, butadiene, isoprene, chloroprene, lysidyl acrylate, and maleic anhydride. By copolymerizing these copolymerizable monomers that do not contain fluoroalkyl groups,
In addition to water and oil repellency, the fluoroalkyl group-containing polymer can appropriately improve various properties such as stain resistance, dry cleaning resistance, washing resistance, solubility, hardness, and texture. For example, a fluoroalkyl group-containing polymer consisting of a copolymer of a fluoroalkyl group-containing unsaturated ester, vinyl chloride, and an alkyl ester of styrene or acrylic acid or methacrylic acid has excellent stain resistance, etc. , has selective solubility in organic solvents such as trichlorotrifluoroethane, and can be advantageously used as an aerosol type or an organic solvent type. The amount of the copolymerizable monomer that does not contain fluoroalkyl groups is preferably 6 to 6 %, based on the weight of the fluoroalkyl group-containing polymer.
It is 0% by weight or less, more preferably 50% by weight or less.

Examples of the fluoroalkyl group-containing urethane compound used in the present invention include the following general formulas (1) to (4):
Compounds represented by the following can be mentioned.

Indicates an organic group. In addition, in the general formula (4), R8 represents an organic group with a valent value, and R1 represents a lower alkyl group (having 1 to 5 carbon atoms).
), n represents an integer from 3 to lO, m represents n>m≧1
Indicates an integer that satisfies ] In the above fluorine-containing urethane compounds (1) to (4),
As the divalent organic group that is Y, for example, [wherein Rf
represents a fluoroalkyl group having 4 to 20 carbon atoms;
is a hydrogen atom, a lower alkyl group (1 to 5 carbon atoms), a hydroxyl group, or a lower alkylcarbonyloxy group (1 to 5 carbon atoms)
, j represents an integer of θ to 4, k and p represent integers of 1 to 4, and R represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms). ), Y represents a divalent organic group, and Z represents 1
W represents a valent organic group, and examples include divalent (CH*)s- and the like.

As the monovalent organic group that is Z, for example, CaHta+
+ O (a = 1 to 7), HOCHtCH! O- CH3COCHt CH(CHs) 0-CHsCO
CHtC(CH-)to- CaHta++0(CHI)a'0-(a=1-4.
4), as a divalent organic group where a=2 to W, for example, -O(CH*
)bo (b= 2~6), 0 (CF(t)bN
H(b=2~6), -NH(CHribNH-(b=2
~6), [R1 and R' are the same or different oxygen atoms,
It represents an imino group or an oxyalkyl group having 1 to 6 carbon atoms (the oxygen atom is not directly bonded to the benzene nucleus) or an iminoalkyl group (the imino group is not directly bonded to the benzene nucleus). ko, CaHta++ NH (a = 1 to 3), CaHta++
000 (a=1-3), (R1 and R' are the same as above), -0(CHtCH,O)b'-(b'=2-100), and the like.

Further, as the n-valent organic group that is R1, for example, (CH
=)s etc.

The above-mentioned fluorine-containing urethane compounds (1) to (4) are all known compounds, and include JP-A-58-110555, JP-A-58-111898, JP-A-59-31751,
It is described in US Pat. No. 3,398,182 and US Pat. No. 3,484,281.

Various types of silane-based or titanium-based coupling agents may be used in the water- and oil-repellent composition of the present invention. Examples of the silane coupling agent include NHzCsHeSt(OCIH5)l, N Ht CH
t CHt N HCHt CHt CHt S i
(OCHs) s, (CI(s)3si NH5i
(CH3)3, CH3S i(OCR3)3, CH35t(QC)ItCH*)3, CHt=CH9+(OCtHs)*, C(IC3811S L(OCR3)t, Ci2' C
HtCHtCHtSi(OCHs)s, CHz=CH8
i(OCHtCHtOCH3)3, CHt-CCHsC
OOCsHeSi(OCHs)*, HS C3H1lS
i(OCI(3)s, CHz=CHSi(OCHtC
HtOCH3)s, etc. Of course, the silane coupling agents may be used alone or in combination of two or more.

Examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, and isopropyl tris (dioctyl pyrophosphate).
Titanate, Tetraisopropylbis(dioctylphosphite) titanate, Tetraoctylbis(ditridecylphosphite)titanate, Tetra(2,2-diallyloxymethyl-1-butyl)
Bis(di-tridecyl)phosphite titanate, Bis(dioctylpyrophosphate)oxyacetate titanate, Bis(dioctylpyrophosphate)ethylene titanate, Isopropyltrioctanoyltitanate, Isopropyldimethacrylylisostearoyltitanate, Isopropylisostearoyldiacryltitanate, Isopropyl These are tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and isopropyl tri(N-aminoethyl-aminoethyl) titanate.

In the present invention, the weight ratio of the water- and oil-repellent compound and the silane-based or titanium-based coupling agent is not particularly limited, and depends on the type of water- and oil-repellent compound and the silane-based or titanium-based coupling agent, the purpose of use, etc. It can be changed within a wide range depending on the situation. Usually, the weight ratio of the water- and oil-repellent compound to the silane-based or titanium-based coupling agent is 99.9.
It is about 9910°001 to 90/10. When the amount of the silane-based or titanium-based coupling agent added is more than 10 parts by weight, the water and oil repellency of the resulting composition is low. Moreover, when the amount added is less than 0.001 part by weight, the antifouling property is low.

The water and oil repellent composition of the present invention may contain a polymer that does not contain fluoroalkyl. The polymer containing no fluoroalkyl group is 30% by weight of methyl methacrylate.
It is preferable that the content is more preferably 70% by weight or more. Polymers containing no fluoroalkyl groups are
It may be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and at least one other monomer not containing fluoroalkyl groups. Other monomers not containing fluoroalkyl groups include glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, alkyl acrylate, alkyl methacrylate, acrylamide, methacrylamide, N-methylol acrylamide, vinyl chloride, styrene, acetic acid. Examples include monomers such as vinyl and vinyl propionate. The antifouling, water- and oil-repellent composition of the present invention comprises 10 to 99.999 parts by weight of a fluoroalkyl group-containing water- and oil-repellent compound, more preferably 30 to 80 parts by weight, and 0 parts by weight of a copolymer that does not contain a fluoroalkyl group. ~90 parts by weight, more preferably 20 to 60 parts by weight, and 0.001 to 10, more preferably 0, silane-based or titanium-based coupling agent.
．． It is preferable that the amount is 0.5 to 1 part by weight.

In order to obtain the polymers used in the present invention, that is, fluoroalkyl group-containing polymers and fluoroalkyl group-free polymers, various polymerization reaction methods and conditions can be arbitrarily selected, such as bulk polymerization, solution polymerization, etc. Any of various polymerization methods such as , suspension polymerization, emulsion polymerization, radiation polymerization, and photopolymerization can be employed. For example, raw material monomers are emulsified in water in the presence of a surfactant and polymerized while stirring, or raw material monomers are dissolved in a suitable organic solvent and polymerization initiation sources (peroxides, A method of solution polymerization using the action of a polymerization initiator such as an azo compound or ionizing radiation (such as ionizing radiation) can be adopted.

The water and oil repellent composition of the present invention contains an additive having a polyfluoroalkyl group having 3 to 5 carbon atoms and an adhesive group to the surface of the object to be treated, such as a phosphoric acid ester, a carboxylic acid complex salt, etc. Good too. That is, examples include phosphoric acid esters, mono- or polycarboxylic acids or salts thereof, urethane compounds, cyanurates, isocyanurate compounds, and the like having polyfluoroalkyl groups. A preferred additive has the general formula: % formula % [wherein Rf' is a polyfluoroalkyl group having 4 to 16 carbon atoms, and xi is -R'--CON (R -Q'- or S OtN
(R-Q'- (where R1 is an alkylene group, R2 is a hydrogen atom or a lower alkyl group, and Ql is a divalent organic group), and AI and A1 are each -〇--S- or N(R')- (wherein R3 is a hydrogen atom or a lower alkyl group), yl is a divalent organic group, and Z is a non-hydrophilic monovalent organic group.] This additive may be added to the water and oil repellent composition after polymerizing the fluoroalkyl group-containing polymer, but before preparing the fluoroalkyl group-containing polymer, the monomer of the fluoroalkyl group-containing polymer is added. It is preferable to add it to the polymer.

The antifouling water- and oil-repellent composition of the present invention can be prepared in any form such as an emulsion, a solvent solution, or an aerosol according to a conventional method.

For example, in a solvent solution type, the antifouling water and oil repellent composition of the present invention can be mixed with acetone, methyl ethyl ketone, diethyl ether, methyl chloroform, trichloroethylene,
It can be prepared by dissolving it in one or a mixture of two or more suitable organic solvents such as tetrachloroethylene and salt fluorinated hydrocarbons such as tetrachlorodifluoroethane and trichlorotrifluoroethane. In addition, when adding and mixing a silane-based or titanium-based coupling agent to a water- and oil-repellent compound, if this is done in an organic solvent,
A solvent-solubilized solution type is directly prepared by adding a surfactant at the same time. For the aerosol type, prepare a solution type solvent solubilizer as described above, and add dichlorodifluoromethane, monofluorotrichloromethane,
A propellant such as dichlorotetrafluoroethane may be added and the mixture may be filled into a suitable container. In the present invention, by appropriately selecting one water- and oil-repellent compound, it is possible to produce a water- and oil-repellent composition that can be dissolved in a relatively wide range of organic solvents. It can be easily prepared in the following forms and is inexpensive, making it suitable for widespread commercial use.

The antifouling water and oil repellent composition of the present invention can be applied to the article to be treated by any method depending on the type of article to be treated and the preparation form (emulsion type, solvent solution type, aerosol type, etc.). can be applied to For example, in the case of an aqueous emulsion or a solvent-solubilized type, a method is adopted in which the coating is applied to the surface of the article to be treated by a known coating method such as dip coating and then dried.

Further, if necessary, curing may be performed using a suitable crosslinking agent. In the case of an aerosol type, it is sufficient to simply spray it onto the article to be treated, and it dries immediately to exhibit sufficient water and oil repellency.

Furthermore, it is of course possible to add and use other water and oil repellents, insect repellents, flame retardants, antistatic agents, dye fixing agents, anti-wrinkle agents, etc. to the water and oil repellent composition of the present invention. It is.

Various examples of articles that can be treated with the antifouling water and oil repellent composition of the present invention are not particularly limited. Examples include textiles, glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster. Fiber fabrics include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, and polytetrafluoroethylene, rayon, and acetate. Examples include semi-synthetic fibers, glass fibers, and woven fabrics of mixed fibers thereof.

The stain-proofing water- and oil-repellent composition of the present invention has excellent stain-proofing properties as well as water- and oil-repellent properties, so it is particularly suitable for stain-proofing interior products such as carpets, reception sets, curtains, wallpaper, and car interior products. It can be suitably employed as a processing agent. It can also be applied to the aforementioned various fiber fabrics, outdoor tents, and the like. In addition, there are various examples in terms of the material of the article, including interior products made of polyamide, polyester, leather, wood, and the like.

〔Effect of the invention〕

The water and oil repellent composition of the present invention has the following advantages.

Compared to conventional means for improving stain resistance, silane-based or titanium-based coupling agents are easily available, and stain resistance can be improved by using water- and oil-repellent compounds without the need for complicated copolymerization reactions. by simply mixing with a coupling agent. Furthermore, the amount of expensive water- and oil-repellent compounds used can be reduced.

It is thought that the remarkable antifouling effect against various stains is produced by the synergistic action of the water and oil repellent effect of the fluoroalkyl group and the crosslinking effect and antistatic effect of the silane-based or titanium-based coupling agent.

[Preferred embodiment of the invention]

Next, the present invention will be explained in more detail by showing production examples, examples, and comparative examples. It goes without saying that the following examples do not limit the invention.

Water repellency, oil repellency, stain resistance, and friction durability were determined according to the following criteria.

A liquid is prepared by mixing water-repellent isopropyl alcohol and water at a certain ratio as shown in Table 1 below, and small droplets of this liquid (approximately 4 in diameter) are prepared.
11IIll) on the surface of the sample cloth and judge the water repellency based on the state of penetration after 1 minute. That is, for liquids of various compositions, among the water repellency values shown in Table 1 corresponding to the compositions for which no penetration into the sample cloth is detected when observed after 1 minute, the maximum value is determined and displayed as that value.

Table 1: Oil repellency A few drops (about 4 mm in diameter) of the test solution shown in Table 2 below are placed on the test object, and the oil repellency is determined by the state of penetration after 30 seconds. In other words, for each test solution, find the maximum value among the oil repellency values shown in Table 2 that correspond to test solutions for which no penetration into the test object is detected when observed after 30 seconds, and display that value. .

Contaminates the second surface oil repellency (AA TCCTM 118-1966). After contamination, excess contaminants are removed using a vacuum cleaner, reflectance is measured, and the degree of contamination is determined and evaluated using the following formula.

R.

Ro: Reflectance R of uncontaminated cloth/Reflectance of contaminated cloth Table 3 Cut the antifouling sample cloth into 5 x 7 cm+ pieces and add the dry contaminants (twice the weight of the sample cloth) shown in Table 3 below. Place the sample fabric in a container, mix and stir vigorously for 3 minutes, and place the sample fabric on the test stand using a Gakushin type dyed fabric abrasion fastness tester (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). Judgment is made by pasting with double-sided tape and rubbing 500 times back and forth with a friction element attached with white line cloth, and measuring water repellency and oil repellency.

Hereinafter, when parts or % are simply used, they represent parts by weight or % by weight, respectively.

Production example (1) Production of polymers (A-1, A-2, B-1 and B-2) Glass autoclave equipped with a stirrer (inner volume 30
Monomer (A-
1, A-2, B-1 and B-2) 100g, emulsifier (Nonion HS220 1.4g, Nonion LT221 1
．． 4g and Naimeen 5220 3.2g: both manufactured by NOF Corporation), a chain transfer agent (lauryl mercaptan 0.15g), and a solvent (ethylene glycol 11.2g).
3g of acetone, 48g of acetone, and 112.5g of water).

After purging the inside of the autoclave with N, the temperature inside the tank was raised to 60°C while stirring, and azobisisobutyramidine hydrochloride 0
．． 6 g was charged and subjected to addition polymerization reaction for 3 hours to obtain a polymer. Monomer composition of A-1, A-2, B-1 and B-2 (
Polymers having a weight ratio) were produced respectively.

SPA/ BuM/ CHM/ Tobolen M/NMAM
/ Evolite 4000 (65/14.5/14.5/
L /'l/ 3) Weight average molecular weight 60,
000 SPA/EB/2EHM (90/5/5) Weight average molecular weight 60,000 MMA/GMA/NMAM (90/6/4) Weight average molecular weight 100,000 MMA/CHM/) Borene M (70/2B/2 ) Weight average molecular weight 100,000 SFA: CF, CF, (CrtCF,)nc
Il, C1,0COCR=CH.

[However, the fluorine-containing compound composition is 55 mol% for n=3, 28 mol% for n=4, and 11 mol% for n=5.
The mol% is 4 mol% for n=6 and 1 mol% for n=7. ] BuM Nibutyl methacrylate, C) IM: Cyclohexyl methacrylate, Tobolene M: 2-Hydroxy-3-chloropropyl methacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.), NMAM: N-
Methylacrylamide Evolite 4000: Glycerin diglycidyl ether (manufactured by Kyoeisha Co., Ltd.), EB: Vinyl chloride, 2EHM: 2-ethylhexyl methacrylate MM
A: Methyl methacrylate, GMA: Glycidyl methacrylate (2) emulsion (
Preparation of A-3) 500 - In a container, 50g and emulsifier (Nonion H82202, 4g, Nonion LT221 2.4g and Nymeen 5220 6.
4 g (both manufactured by NOF Corporation) and a solvent (11.3 g of acetone, 48 g of methyl ethyl ketone) were added, and stirred for 5 minutes at 300 Orpm using a homogenizer (two-way).Then, the stirring speed was increased to 800 Orpm, and water was added using a dropping funnel. 200 g was charged over 5 minutes and stirred for an additional 10 minutes to produce emulsion A-3.

Examples 1 to 8 and Comparative Examples 1 to 6 Fluoroalkyl group-containing polymers (A-1-A-3), fluoroalkyl group-free polymers (B-1 and B-
2), and a silane-based or titanium-based coupling agent are mixed in the proportions shown in Table 4 below, and the solid content is 0.7% by weight.
It was diluted with deionized water so that This diluted solution was sprayed uniformly onto a nylon tufted carpet (product name: Margaret, color: Mo2, manufactured by Suminoe Textile Co., Ltd.) (wet pickup 50%) and dried at 150° C. for 20 minutes. Water repellency, oil repellency of treated carpet,
Friction durability and stain resistance were measured.

In addition, carpets treated with a liquid diluted to a solid content of 0.7% by weight using only a fluoroalkyl group-containing polymer, a polymer not containing a fluoroalkyl group, or a silane-based or titanium-based coupling agent; Similar measurements were made on untreated carpet. These measurement results are summarized in Table 4 below.

The silane-based and titanium-based coupling agents used are as follows.

Claims (1)

[Scope of Claims] 1. An antifouling water and oil repellent composition comprising a fluoroalkyl group-containing water and oil repellent compound and a silane-based or titanium-based coupling agent. 2. An antifouling water- and oil-repellent composition comprising a water- and oil-repellent compound containing a fluoroalkyl group, a polymer not containing a fluoroalkyl group, and a silane-based or titanium-based coupling agent. 3. The fluoroalkyl group-containing water- and oil-repellent compound is a fluoroalkyl group-containing polymer, and the fluoroalkyl group-containing polymer has the general formula: Rf-R^2-OCOCR^1=CH_2 [wherein, Rf is carbon It is a polyfluoroalkyl group of several 3 to 20 pieces, R^1 is a hydrogen atom, a fluorine atom, or a methyl group, and R^2 is -R^3-, -CON(R^4)-Q^1- or -SO_2N(R^4)-Q^1- (where R^3 is an alkylene group, R^4 is a hydrogen atom or a lower alkyl group,
Q^1 is a divalent organic group. ). ] The antifouling water and oil repellent composition according to claim 1 or 2, which has a structural unit formed from at least one monomer selected from the group consisting of fluoroalkyl group-containing unsaturated esters represented by the following. 4. The water- and oil-repellent compound containing a fluoroalkyl group is a urethane compound containing a fluoroalkyl group, and the urethane compound containing a fluoroalkyl group has a general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲Mathematical formulas, chemical formulas , tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) [In the formula, Rf is a fluoroalkyl group having 4 to 20 carbon atoms , and X is -CH_2CH(A)CjH_2j-, -CkH_2k
- or -SO_2N(R)CpH_2p- (wherein A represents a hydrogen atom, a lower alkyl group, a hydroxyl group, or a lower alkylcarbonyloxy group, j represents an integer of 0 to 4, and k and p represent an integer of 1 to 4. (represents an integer of 4, R represents a hydrogen atom or a lower alkyl group), Y represents a divalent organic group,
Z represents a monovalent organic group, and W represents a divalent organic group. Further, in the general formula (4), R_1 represents an n-valent organic group, R_2 represents a lower alkyl group, n represents an integer of 3 to 10, and m represents an integer satisfying n>m≧1. ] The antifouling water and oil repellent composition according to claim 1 or 2, which is at least one selected from the group consisting of urethane compounds represented by the following. 5. The weight ratio of the fluoroalkyl group-containing water- and oil-repellent compound to the silane-based or titanium-based coupling agent is 99.
The antifouling water- and oil-repellent composition according to claim 1, which has a molecular weight of 99910.001 to 90/10. 6. Fluoroalkyl group-containing water- and oil-repellent compounds 10-9
The antifouling water and oil repellent composition according to claim 2, comprising: 9.999 parts by weight, 0 to 90 parts by weight of a polymer not containing a fluoroalkyl group, and 0.001 to 10 parts by weight of a silane-based or titanium-based coupling agent. thing.