TW200424304A - Water-repellent and oil-repellent aqueous dispersion composition - Google Patents

Abstract

The present invention is related to a water-repellent and oil-repellent aqueous dispersion composition, comprising: (A) a fluorine-containing polymer; and (B) a non-ionic surfactant, which is a copolymer having a structure wherein the polyoxyalkylene block (wherein said alkylene has 3 or more carbon atoms) exists outwardly with respect to the polyoxyethylene block, accordingly said polyoxyalkylene block at the outer side of the molecule and said polyoxyethylene block at the inner side of the molecule. The water-repellent and oil-repellent aqueous dispersion composition according to the present invention, compared to the previous water-repellent and oil-repellent aqueous dispersion compositions, is more excellent in water-repellent and oil-repellent properties as well as in processing stability.

Description

200424304 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a water-dispersible water-repellent and water-repellent manufacturing method that can significantly improve the water- and oil-repellency of synthetic fibers (especially the oil-repellency of nylon). w and its [prior art] It is known that a polymer having a perfluoroalkyl or perfluoroalkenyl and acrylic or methacrylic polymerizable compound can be used as a water and oil repellent for fiber textiles, especially the polymer. The aqueous f dispersion liquid dispersed in an aqueous medium by an emulsifier can be widely used in industry. In wooo / 37583, a method for providing a water-dispersible water- and oil-repellent agent capable of retaining an organic solvent, having durable water- and oil-repellency, and excellent storage stability is proposed. In Japanese Patent Application Laid-Open No. 2002-275453, in order to obtain a water-dispersible water- and oil-repellent composition that exhibits good water- and oil-repellency and is excellent in manufacturing stability and product storage stability, the use of specific emulsifiers (that is, A block copolymer of polyoxyethylene chain at both ends of an oxyalkylene chain) and a method for producing a specific polymerization initiator. However, even on the above water- and oil-repellent composition, with the diversification of water- and oil-repellent processing in recent years, it is not always possible to provide sufficient water- and oil-repellency, especially oil-repellency. [Summary of the Invention] The purpose of the present invention is to provide a water-dispersed water- and oil-repellent agent that is superior in water- and oil-repellency (particularly oil-repellency) and has excellent processing stability in order to solve the above-mentioned problems. Aqueous dispersion composition. The present invention relates to a water- and oil-repellent agent aqueous dispersion composition, which is characterized by 315469 5 ^ 00424304 containing: (A) a fluoropolymer, which is at least one item of seven people per kg. A homopolymer or copolymer of a fluoroalkenyl group, an acrylic group, a methyl acrylic group, a polymer, or an α-substituted acrylic polymer compound, 痞 p A may be a polymer A copolymer of a copolymerizable polymerizable compound; and (B) a non-ionic surfactant, which is a copolymer whose structure includes: polyoxyalkylene groups in a manner from the polyoxyethylene ethyl block toward the outside of the molecule The existence of f is such that the polyoxyalkylene enemy segment (the carbon number of the alkylene group is 3 or more) is outside the molecule and the polyoxyethylene block is inside the molecule. The present invention also provides a method for treating a substrate, which is characterized in that the water-repellent and oil-repellent agent aqueous dispersion composition is used for the substrate and the polymer is attached to the substrate; and a treatment is provided using the water-repellent and oil-repellent agent. A substrate obtained by treating an aqueous dispersion composition. [Embodiment] In the ll-containing polymer (A), for example, it can be copolymerized with a defeaturable polymerizable compound having a perfluoroalkyl group or a perfluoroolefin% group and an acrylic group, a methacrylic group, or an α-substituted acrylic group. In the case of copolymers of other polymerizable compounds, the former accounts for at least 25% by weight of the copolymer and more preferably 40% by weight. As an example of a fluorine-containing polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic group, a fluorenyl acrylate group, or an α-substituted acrylate group, the system I ^ is a (fluorenyl) acrylate represented by the following structural formula · 6 315469 200424304

Rf-S02JjR20C0CR3 = CH2 ⑴

Rf. (CH2) nOCOCR3 = CH2 (2) R1

Rf-CO-NR2OCOCR3 = CH2 (3)

? H

Rf-CH2CHCH2OCOCR3 = CH2 (4) OCOR3

Rf-CH2CHCH2OCOCR3 = CH2 (5)

Rf-0-Ar-CH2OCOCR3 = CH2 (6) [In the formula, the lamp represents a perfluoroalkyl group or a perfluoroalkenyl group having a carbon number of 1 to 21 (for example, 3 to 21); a hydrogen or an alkyl group of a carbon number of 1 to 10 R2 represents an alkylene group having a carbon number of 1 to 10; R3 represents a hydrogen atom, a methyl group, a fluorine atom, a gas atom, a bromine atom, a hertom atom, CFXH (the restriction is that x2 is a nitrogen atom, a gas atom ,, Gas atom, bromine atom or iodine atom), cyano group, straight or branched gas alkyl group of main carbon number 1 to ^^ 21, substituted or unsubstituted benzyl group, or group; Replace stupid

Ar is an aryl group which may have a substituent; and n represents an integer of 1 to 10]. 315469 7 200424304 In the above formula, the Rf group is preferably a perfluorinyl group. The carbon number of the Rf group is r 1 to 21, preferably 2 to 20, more preferably 4 to i 6, and particularly, ‘6 to 14 is particularly preferable. The carbon number of Rf may also be 1 to 6, especially i to 4.

Examples of Rf bases are as follows: -cf3, -cf2cf3, -CF2CF2CF3, a CF (CF3) 2, -CF2C f2cf2cf3, -cf2cf (cf3) 2, -c (cf3) 3,-(cf2) 4cf3,

One (cf2) 2cf (cf3) 2, --cf2c (cf3) 3, one cf (cf3) cf2cf2cf3, one (cf2) 5cf3, one (cf2) 3cf (cf3) 2,-(cf2) 4cf (cf3) 2, One (cf2) 7cf3, one (cf2) 5cf (cf3) 2, one (cf2) 6cf (cf3) 2,-(CF2) 9CF3 Specific examples of the fluorine-containing polymerizable compound having an acrylic group or a fluorenyl acrylic group are as follows Show:

8 315469 200424304 cf3 (cf2) 7 (ch2) ococh = ch2, cf3 (cf2) 6 (ch2) ococ (ch3) = ch2, (CF3) 2CF (C F2) 6 (CH2) 2OCOCH = CH2n cf3 (cf2) 7 (ch2) 2ococ (ch3) = ch2, cf3 (cf2) 7 (CH2) 2OCOCH = CH2n cf3 c f2 (ch2) 2ococh = ch2, cf3 (cf2) 3 (ch2) 2ococ = ch2, cf3 (cf2) 7 s〇2n (ch3) (ch2) 2ococh = ch2, cf3 (cf2) 7 s〇2n (c2h5) (ch2) 2ococ (ch3) = ch2, (cf3) 2cf (c f2) 6ch2ch (ococh3) ch2ococ (ch3) = ch2n (cf3) 2cf (c F2) 6CH2CH (OH) CH2OCOCH = CH2n C8Fi7-〇 ~ ^^ CH20-C0CH = CH2 c5f] ch2o-coc (ch3) = ch2 C8Fi7-〇 * " < (^ > _C00CH2 (j: HCH20C0C (CH3) = CH2

OH C9F17-〇-^^ > -CH2〇-COCH = CH2

CgF CH2〇-COC (CH3) = CH2 In the a-substituted acrylic group, examples of the a-substituent are _ prime atom, halogen atom (such as carbon number 1 to 2 1) alkyl group (such as mono Fluorofluorenyl and difluoromethyl), cyano or aromatic (such as substituted or unsubstituted benzyl, substituted or unsubstituted phenyl). An example of the fluorine-containing polymerizable compound having an a-substituted acrylic group is shown in 315469 9 200424304.

OF II l_

Rf—CH2CH2—〇—C—C—CH2 0 F

II I

Rf- < ^ _ y—-o-c—c = ch2

O F ^ II! _ O—C-C—CH2

Rf-CH2CH2——0—C—0 = 0¾

Ef- CH2CH2 -Rf—CH2CH2 oJ-t 0 I II I-0—c-c ch2 10 315469

I 200424304 〇 cf3

Rf-CH2CH2—〇—C—C ~ CH2

〇 CN

Rf-CH2CH2-0-C ~ C ~ CR2 Rf-CH2CH2 〇-C-C ~ CH2 〇 CH2-c6H5

Rf — CH2CH2 O C -C CH2 200424304 ch3 of

-s〇2nch2ch2—〇-c_ (l—CH 9¾ o ci

I η I

-SO2N CH2CH2 〇-q-C ^^ CH 2 c2h5 Rf-S02NCH2CH2-CA Rf — S02NCH2CH2-ch3 Rf — S02NCH2CH2-

II

F 'O—C-C ^ CHs 0 ClJ 丨 i -〇 ~ c_c—〇ΙΪ2

II cf3 OH I Rf — CH2CHCH2-OHI Rf- CH2CHCH2- OCOCH3 -ch2chch2— OCOCH3 -o—c—c = ch2 0 ϋ L -o—c—c = ch2 O Cl ^ II I -〇—cc = ch2 OF ^ II l_ '0 ~ c--C ^ CHg

II

Cl

Rf-CH2CHCH2-'O-C-C ^ CH2 [wherein Rf is a linear or branched perfluoroalkyl group or a completely random group having 1 to 21 carbon atoms]. There are various types of other copolymerizable polymerizable compounds, examples of which are shown below: (1) acrylic acid and methacrylic acid and their methyl, ethyl, butyl, isobutyl, third butyl, Propyl, ethylhexyl, hexyl, decyl, lauryl, stearyl, isobornyl, p-hydroxyethyl, glycidyl, phenyl, benzyl or 4-cyanophenyl esters; 12 315469 200424304 (2) Vinyl esters of fatty acids such as acetic acid, propionic acid, caprylic acid, lauric acid or stearic acid; (3) Styrene compounds such as styrene, α-methylstyrene, or p-methylstyrene; (4) Halogenated vinyl or vinylidene compounds such as fluoroethylene, vinyl chloride, bromoethylene, vinylidene fluoride or vinylidene difluoride; (5) Propyl heptanoate, allyl octanoate or caproate Dilute propyl esters of aliphatic acids such as propyl esters; (6) Vinyl alkyl ketones such as vinyl methyl ketone or vinyl ethyl ketone; (7) N-methacrylamide or N-hydroxymethyl Acrylamides such as methacrylamide; and (8) 2,3-digas-1,3-butylated other polymerizable compounds to contain gas-containing polymerizable compounds (such as Vinyl or vinylidene gas) (for the polymer, for example, to i / amount of square) by weight is preferred ❶. The average molecular weight of the fluoropolymer (A) is from 1,000 to 1,000, 000, and may be, for example, 1,000 to 1,000,000. The composition of the present invention contains a surfactant (B). The structure of the surfactant (B) = includes: the polyoxyethylene base block exists from the polyoxyethylene base block toward the outer side of the sub-block, so that the polyoxygen base block (the carbon number of the carbonization group) Only the polyoxyethylene block on the outside of the ice molecule is inside the molecule. The number of polyoxyethylene blocks is ^, and the number of polyoxyethylene blocks is 2 or more. For example, 'Interfacial activity Agent (b) can be a polyoxyethylene block in the center of the knife, and polyoxyethylene amps & 315469 13 200424304 at both ends. A diblock copolymer, or (2) in the molecule The center has a 2 to 6 valence ancient molybdenum 4j- '' base (for example, it is a 4-valence ethylene diamine group), and the organic group is bonded to & Copolymer of oxyalkylene blocks. Ψί y »

The ethyl group is hydrophilic, and the polyoxyalkylene block (the inverse number of the alkylene group is 3 to μ, & ^ L) is & water. The number of carbons in the oxyalkylene group may be, for example, 3 oxyalkylene group may be oxypropyl group or oxybutyl group, etc., of which oxypropyl group is preferred. An example of 4 ^ "facial / tongue agent (B) is a copolymer represented by the following formula (1):

An〇'i〇) a- (CH2CH2〇V (Ri2〇) c_Ai2 ⑴ '[wherein, Λ 1 1 jx λ 1 2 ν »is a hydrogen atom, an alkyl group of 1 to 22, a carbon number of 2 to Alkenyl group of 22 or R13C (= 0)-(1113 is carbon number! Alkyl group to 22 or alkenyl group of 2 to 22 carbon number), R and R are elongation group having 3 or more carbon number, and c is 2 The above number, and b is a number that can make the weight-to-weight ratio of the polyoxyethylene block and the co-watering substance 5 to 80% by weight]; and the copolymer represented by formula (2) ·· A21— ( 〇R21) r (〇H4C2) xX / (C2H4O) x— (R2i0) y—A23 ⑵ A22— (ΟΚ21) γ (〇η4〇2 ^ N 〇2Η4 Nc2H40) j- (R21〇) -A24 [wherein , AA, A23 and A24 are hydrogen atom, alkyl group with carbon number i to 22, alkenyl group with carbon number 2 to 22 or ri3C (= 〇) _ (ri3 is carbon number) to 22 alkyl group or carbon number 2 Alkenyl to 22), 315469 14 200424304 Each R21 may be the same or different, and is an elongation group having 3 or more carbon atoms,

Each of X and y may be the same or different, and the weight ratio of the L-oxyethylene segment to the copolymer is 5 to ^ to make the polymer number]. . The surface active agent (B) has a good agreement; Den &M.; The distance from 500 to 20000, for example, 1000 to 5000. The average molecular weight of the copolymer of formula (1) is 10 to 100,000. The average molecular weight of the copolymer of formula (2) is preferably 200 to 150000. The average molecular weight is based on gel permeation (GPC: Gel Permeation)

Chromatography) Specific examples of the surfactant (B) are shown below. 15 315469 200424304 HO- (C3 H6 0) a-(CH2 CH2 0) b-(C3 He 0) c -HG 〇H210- (C3H60) e- (CH2CH20) b- (C340) cH Cx 2 H2 5 〇- (C3 H6 0) a-(CH2 CH2 0) b-(C3 He 0) c -H Cx 6 H3! 〇- (C3 H6 0) a-(CH2 CH2 0) b-(C3 H6 0) c -H C16H330- (C3H60) a- (CH2CH20) b- (C3H60) cH C12H25〇- (C3H60) a- (CH2CH20) b- (C3H60) c- C12H25 G 6 H3 i 0- (C3 H6 0) a-(CH2 CH2 0) b-(C3 He 0) c-G 6 H3 r C16H33〇- (C3H60) a- (CH2CH2O) b- (C3H6O) c- C16H33 H— (OHeC3) 7 (OH4C2) x \ Η- (ΟΗ6 〇3)-(〇Η4〇2) ^

/ (〇21140 ^ (C3H60) y—Η N-C2H4—,

x (C2H4〇) — (C3H60) —H / (C2H40) — (C3H60) y-C12H25 / N-C2H4 ~ n Η25〇12- (〇Η6〇3)-< 〇Η4 ^ 2) x x (c2h4o) — (C3h6o) -c12h25 H3iC16- (〇H6C3) 3r (〇H4C2) 3K (C2H40) x— (C3H60) 3rC16H31

Ν ~ 〇2Η4-N

HaiCxe-COHeC ^ -toH ^^ x N (C2H4〇)-(C3H60) -C16H31 ϋ / (C2H4〇) 3 ^ — (〇3Η6〇) ^ 〇 I6H33 n (C2H40) — (C3H60) -C16H33

HaaCxe-iOHeC ^ iOH ^^ H33C16- (OH6C3) y- (OH4C? [Wherein, a, b, c, x and y are 2 or more]. About polyoxyethylene block and surfactant ( B) The proportion in the molecule of (copolymer) may have a lower limit of 5% by weight (for example, 7% by weight, and 10% by weight is particularly preferred). On the other hand, an upper limit is 80% by weight (for example, 50% by weight). 40% by weight is preferred, and 35% by weight is particularly preferred.) 315469 16 200424304 The surfactant (B) may be used alone or in combination of two or more. Surfactant (B) : In order to provide the stability of the emulsion, it can be added to the polymerization solution before the emulsification of the emery body, the polymerization after the emulsification, or the polymerization of the monomers = for protection 7. For every 100 parts by weight of polymer ⑷, the surfactant ( The amount of B) may be 0.01 to 30 parts by weight, for example, 0 to M by weight. However, increasing the amount does not impair storage stability and feel. In the present invention, in addition to the surfactant (B), it may be used in combination. Surfactants other than Surfactant (B) (0. Surfactant ⑹ can be cationic, anionic or nonionic emulsified , But cationic or non-ionic etiquette, or a mixture of the two is preferred. Cationic emulsifiers include dodecyltrimethylsulfonium, decyl sulfonium hydration, hexadecyl trimethyl Methyl sulfide, trimethyl octadecyl ammonium gas, (twelve dimethyl a " ^,-, earth) dimethyl chloride, benzyl dodecyl methoxide, methyl Dodecyl bis (hydrogen polyoxyethyl) ammonium chloride fluorenyl ten—graft bis (hydrogen polyoxyethylene) ammonium chloride, di-hardened tallow alkyl di-kidden gas and N-diethyl diethyl Amino) ethyl] oil amine hydrochloride. Non-ionic reducing agents include ethylene oxide and hexyl pentamate, isooctyl powder, ten yuan 酉 '酉 夂, (Cl2-Ci6) thiol, Sorbose mono- (c7-cl9) fatty acid ester or condensation product of (C12-C | 8m-based amine, etc.). (C) can be used before monomer emulsification, before emulsification polymerization, or monomer After polymerization, it is added to the polymerization solution. The polymer (A) of +, square and mother is 100 parts by weight, and the amount of the surfactant (C) is 40 parts by weight or less, preferably 0.01 to 30 parts by weight. E.g. 315 469 17 200424 304 is 1 to 20 parts by weight. The purpose of the present invention is to increase the polymer's monthly average, and it is also possible to add organic solvents as required. Examples of organic solvents, such as ketones such as keto ethyl ketones, etc. Ethylene glycol derivatives such as ethylene glycol, polyethylene glycol, and polyethylene glycol derivatives such as polyethylene glycol, polyethylene glycol dimethyl light, polyethylene glycol monobutane, etc. , Propylene glycol, dipropylene glycol, propylene glycol and other propylene glycol derivatives, cyclodextrins and polyethers such as dextrin, methyl ethyl acetate and

^ Acids such as acetic acid, or N-alkenylpyridinone. The amount of the organic solvent is 5 to 200 parts by weight, for example, 10 to 100 parts by weight, and 20 to 80 parts by weight is particularly preferred with respect to the polymer by weight. In the production of the aqueous dispersion of the present invention, a polymerizable compound is subjected to emulsion polymerization in the presence of a polymerization initiator and an optional surfactant in an organic solvent to obtain an emulsion of a polymer. If necessary, water and / or a surfactant may be added to the emulsion. In addition, if necessary, an organic acid of 0 W may be used. In addition, a cross-linking agent, other polymers, other water-repellent agents, oil-repellent agents, antifouling agents, insect repellents, flame retardants, and antistatic agents may be further included according to the purpose. , Dye stabilizer, anti-wrinkle agent, anti-shrinkage agent, touch processing agent, softener or defoamer and other additives. The cross-linking agent may be a block isocyanate compound, a melamine resin compound, a glyoxal-based resin compound, a urea-based resin compound, or a cross-linkable monomer (N-hydroxymethyl acrylamide, methyl Based on the block product of acrylic acid (2-isocyanate ethyl vinegar) as a necessary polymer, etc., the block isocyanate compound or melamine resin compound is 18 315469 200424304 Chevrolet. Among them, the block isocyanate compound is preferably a compound having no polymerizable unsaturated group and a structure in which an isocyanate group of a polyisocyanate is converted with a blocker. Examples of the melamine resin compound include 1-methyl melamine and hexamethylol melamine. Suitable substrates for the aqueous dispersions of the present invention, such as films, fibers, fabrics, felts, and filaments, fibers, or yarns obtained from natural polymer materials, modified natural polymer materials, or synthetic polymer materials Decoration made of thread. Fibrous products in the form of fibers, yarns or cloth are preferred as the base system. The substrate is preferably composed of nylon fibers alone or a mouthpiece of nylon fibers and other fiber materials. Although several types of nylons are sold by this manufacturing method, they are not limited to this manufacturing method and can be used arbitrarily. For example: Nylon 6, Nylon 66, Nylon 610, Nylon 12, and copolymerized nylon with raw material components used in such manufacturing can be used. The mixture of nylon fiber and other fiber materials may be exemplified by a mixture of nylon and polyester, a mixture of nylon and cotton, a mixture of nylon and polyurethane, a mixture of nylon and cotton and polyurethane, Mixtures of nylon and wool, blends of nylon and acrylic and polyurethane, or blends of nylon and polyester and hemp. A method of appropriately applying the aqueous dispersion to the substrate, such as coating, dipping, spraying, padding, or roller coating, or a combination of these methods is preferable. For example, the solid content of the infusion solution is adjusted to 0.01 to 10% by weight as the infusion solution. The substrate is immersed in the liquid, and then the excess liquid is removed with a common winch, and the absorption after drying (weight of the dry polymer on the substrate) 315469 19 200424304 * ,,, about 0.0 1 to 1% by weight of the substrate . The treated substrate can then be heated to 100 to 200 ° C. The preferred examples and comparative examples are described below to explain the present invention in more detail. The characteristics are measured as follows. J ^ L · Water and oil repellent The polymer dispersion was diluted with water to prepare a treatment solution having a solid content concentration of 0 $ H% by weight. A nylon taffetas cloth (NATURE NU manufactured by Zhongfang Co., nylon 6, blue dyed cloth) is immersed in the treatment solution, and embossed with a cloth rolling machine to make the wet pick-up rate of wet picking Operation 〇, • After drying at 100.0 for 2 minutes and heat treatment at 160t for 1 minute, the water- and oil-repellency of the treated cloth was evaluated. The water-repellency is the water-repellency obtained by the spray method according to JIS-L-1 092. Grade indication (refer to Table 1 below). Six oil resistance is based on AATCC_TMi 18, the test g shown in the following Table 2 each liquid on the test cloth 2 drops of each drop, watch the penetration state after 30 seconds, :: The highest point of oil resistance provided by the test solution that does not exhibit impregnation is the anti-grade and isotropic water repellent. The wet person is wet and wet, and the wet is wet and the writing is wet. Weakly present < | No slightly present I surface surface surface surface surface | j Table Table Table Table Table 315469 20 200424304 Table 2 Surface tension of oil proof speech test solution ^ (dyne / cm, 25 〇C) 8 G 20.0 7 it octane 21.8 6 it decane 23.5 5 n-dodecane 25.0 4 n-tetradecane 26.7 3 n-hexadecane 27.3 2 N-hexadecane 35 / liquid stone * mixed 65 mixed solution 29.6 1 liquid paraffin 31.2 0 less than 1-H oil-resistant polyester durability is repeatedly washed 3 times according to JIS L_0217-103 method, and then evaluated ^ Water and oil resistance (HL-3). Storage stability The aqueous dispersion (solid content 30% by weight) was stored at 4 (rc for i month, and the generation of precipitation was observed. 〇: No precipitation at all △: Slight precipitation X: Many precipitations The following criteria are used to judge the difference between the 5% -concentrated nylon (Ny) fabric and the like. Touch it with your hand and follow △. It is almost the same as the untreated cloth. It is slightly harder than the untreated cloth, but it is not a problem. Tendency 3 15469 21 200424304 χ · Member is harder than untreated cloth. Example 1 In a 1L flask, Cn wH2CH2〇c〇CH = CH2 (n = 6, 8, 10, 12 and i4 (n The average is 8) of a mixture of compounds) 100 g, 50 g of acrylic stearin, 2 g of N-hydroxymethacrylamide, 200 g of pure water, 50 g of dipropylene glycol monomethyl ether, and 0.3 g of acetic acid. 4g polyoxyethylene lauryl ether, 10g polyoxyethylene ethyl fluorenated ether, and polyoxyethylene polyoxyethyl-polyoxyethylene triphenylene Segment copolymer ^ rib ^ do ⑶ ⑶ / 仏 ⑺ factory (C3H60) cH (a, b and c are 2 or more), (average molecular weight is 3100, the proportion of oxyethyl group is 20% by weight) 4g, dispersed by ultrasonic emulsification at 6 ° C for 15 minutes with stirring. Add 0.75 g of 2,2, _azobis (2-fluorenylpropane) dihydrochloride to 60. (; The reaction was carried out for 5 hours to obtain an aqueous dispersion of the polymer. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. ^ Example 2 In a 1 L flask, CnF2n + iCH2CH2 0c0CH = CH2 (n = 6, 8 10, 12 and 14 (mixture of compounds with an average n of 8)) 100 g, 50 g of stilbyl acrylate, 2 g of (3_gas_2_hydroxypropyl) methacrylate, 200 g of pure water , 40g of tripropylene glycol, 0.3g of acetic acid, 4g of octadecyltrimethylammonium gas and 10g of polyoxyethylene ethyl lauryl ether, and dispersed by ultrasonic emulsification at 60 ° C under stirring for 5 minutes .75 g of 2,2, _azobis ()-fluorenylpropion k) monohydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous polymer dispersion. Polyoxypropylene_polyoxyethylene 315469 22 200424304-polyoxypropylene triblock copolymer [H0- (C3H60) a- (CH2CH20) b- (C3H60) cH ( a, b and (: is a number of 2 or more), (average molecular weight is 3100, and the proportion of oxyethylene is 20% by weight)] 3g, and stirred for 1 hour to obtain an aqueous dispersion ° Evaluation of the characteristics of the aqueous dispersion The results are shown in Table 3. Example 3 In a 1 L flask, CnF2n + 1CH2CH2OC0CH = CH2 (a mixture of compounds of n = 6, 8, 10, 12, and 14 (average of n is 8)) 1 〇〇g, 25g of acrylic stearin, 25g of 2-ethylhexyl methacrylate, 1.2g of diacetone acrylamide, 8g of methacrylic acid (3-gas-2-hydroxypropyl), 200g of pure water, 80 g of tripropylene glycol, 0 g of acetic acid, 4 g of octadecyl trimethyl ammonium gas, 6 g of polyoxyethylene ethyl ether, and polyoxyethylene_polyoxyethylene-polyoxyethylene Segment copolymer [11〇-((: 31 ^ 〇) ^ (: :) 9 ^ Chemical_ (C3H6〇) eH (a, b and c are numbers of 2 or more) (average molecular weight is 2800, The proportion of oxyethyl group is 10% by weight)] 4 g, with stirring at 60. 〇c was dispersed by ultrasonic emulsification for 15 minutes. 0.75 g of 2,2, -azobis (2-amidinopropane) dihydrochloride was added and reacted at 60 ° C. for 5 hours to obtain an aqueous polymer dispersion. To this dispersion was added polyoxypropylene-polyoxyethylene-polyoxypropylene difluorene copolymer (a 13 and c are 2 or more), (average molecular weight is 2800, oxygen The ratio of ethylenic group is 10% by weight)] 3g, and stirred for 1 hour to obtain an aqueous dispersion. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. CnF2n was added to a 1L pressure cylinder (autoclave). +】 CH2CH2〇c〇315469 23 200424304 CH = CH2 (n = 6, 8, ίο, 12 and I4 (an average of 8) compound) 15g, 75g stearyl acrylate, diacetone propylene 3 g of ammonium amine, 300 g of purified water, 75 g of dipropylene glycol monofluorenyl ether, 0.45 g of acetic acid, 6 g of di-hardened tallow tallow diammonium ammonium chloride, 9 g of polyoxyethylene ethyl ether and 9 polyoxypropylene -Polyoxyethylene-polyoxypropylene triblock copolymer [H〇- (C3H60) a- (CH2CH2〇) b- (C3H6〇) cH (a, b and c are 2 or more) ( The average molecular weight is 3 100, the proportion of oxyethyl groups is 20% by weight _%)] 6g 'with ultrasonic emulsification and dispersion at 60 ° C for 15 minutes under stirring. After emulsification, 1.5 g of n-undecyl mercaptan was added, and then 4 5 g of gaseous ethylene is pressed in and filled. Then, 2,2 azobis (2-fluorenylpropane) dihydrochloride i.i2g was added and reacted at ′ 60 ° C for 5 hours to obtain an aqueous polymer dispersion. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. Example 5 Add 1L | Li Da to CnF2n + iCH2CH2〇c0CH = CH2 (n = 6, 8, 10, 12, and 14 (mixture of n = 8) compound) 15 g 37.5 g of stearyl acrylate, 37.5 g of lauryl acrylate, 1.8 g of N-hydroxymethacrylamide, 1.2 g of (3-chloro_2-hydroxypropyl) methacrylate, 300 g of pure water, 75 g of tripropylene glycol, 15 g of diol, 0.45 g of acetic acid, 6 g of mono-hardened tallow difluorenyl ammonium vapor and 15 g of polyoxyethylene lauryl ether were dispersed and dispersed by ultrasonic emulsification at 60 t under stirring for 15 minutes. After the emulsification, 1.5 g of n-dodecyl mercaptan was added, and then 45 g of vinyl chloride was pressed into the filling. Then, 112 g of 2,2 azobis (2-fluorenylpropane) dihydrochloride was added, and reacted at 60 ° C for 5 hours to obtain an aqueous polymer dispersion. Polyoxyethylene-polyoxyethylene-polyoxyethylene triblock 315469 24 200424304 copolymer [HO_ (C3H60) a- (CH2CH2O) b- (C3H6O) cH ( a, b, and c are 2 or more) (average molecular weight is 2800, and the proportion of oxyethyl is 10% by weight)] 4.5 g, and stirred for 1 hour to obtain an aqueous dispersion. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. Comparative Example 1 CnF2n + 1CH2CH2OCOCH = CH2 (mixture of compounds of n = 6, 8, 10, 12, and 14 (average of n) 8) was put into a 1L flask, 100 g of acrylic stearin, 50 g of N- Hydroxymethacrylamide i.2g, methacrylic acid (3-Gas-2-acryl) S | 0.8g, pure water 200g, dipropylene glycol monomethyl myrtle 30g, acetic acid 0.3g, octadecyldifluorene 4 g of base gas and 10 g of polyoxyethylene lauryl ether were dispersed and dispersed by ultrasonic emulsification at 60 ° C for 15 minutes under stirring. 5 g of 2,2, -azobis (2-fluorenylpropane) dihydrochloride was added and reacted at 60 ° C for 5 hours to obtain an aqueous polymer dispersion. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. Comparative Example 2 In a 1 L flask, 100 g of CnF2n + 1CH2CH2OCOCH = CH2 (a mixture of compounds of n = 6, 8, 10, 12, and 14 (n is an average of 8)), 50 g of stearyl methacrylate, 2 g of methacrylic acid (3-gas-2_hydroxypropane), 200 g of purified water, 40 g of tripropylene glycol, ojg of acetic acid, 4 g of octadecyl trimethylammonium chloride, 6 g of polyoxyethylene ethyl ether And polyoxyethylene-polyoxypropylene-polyfluorene triblock copolymer [] 9 [0-((::) ^ 2 (^ 2〇) 13- (C3H6〇) q- ( CH2CH2〇) rH (P, q, and r are 2 or more) (average molecular fluorene is 2900, and the proportion of oxyethyl groups is 40% by weight)] 4g, with ultrasonic emulsification and dispersion at 60C by stirring 15 minutes. Add 2,75 g of 2,2 azobis (2_25 315469 200424304 fluorenylpropane) dihydrochloride, and react at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. • Evaluate the aqueous dispersion The results are shown in Table 3. Comparative Example 3 A 1L flask was charged with cnF2n + 1CH2CH2OCOCH = CH2 (n = 6, 8, 10, 12, and 14 (a mixture of n with an average of 8)) 100 g, acrylic acid 25g stearyl ester, methacrylic acid (2- 25 g of ethylhexyl ester, Ug of diacetone φ acrylamide, 0.8 g of methacrylic acid (3-chloro-2-hydroxypropyl) S, 200 g of pure water, 80 g of dipropylene glycol, 0.3 g of acetic acid, two Hardened tallow alkenyl difluorenyl: 4 g of ammonium gas and 10 g of polyoxyethyl lauryl ether, dispersed by ultrasonic emulsification at 60 ° C. for 15 minutes under stirring. Add 2,2, -coupling Nitrobis (2-fluorenylpropane) dihydrochloride, 0.75 g, was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. Polyoxyethylene-polyoxypropylene was added to the dispersion. -Polyoxyethylene triblock (CH2CH20) rH (p, q and r are 2 or more) (average molecular weight is 2900, the proportion of oxyethylene is 40% by weight, and stirred for 1 hour to obtain water Dispersion liquid. The characteristics of the aqueous dispersion liquid were evaluated. The results are shown in Table 3. Comparative Example 4 In a 1 L autoclave, CnF2n + 1CH2CH2OCOCH = CH2 (n = 6, 8, 10, 12, and 14 (average of n is 8) ) Compound mixture) 150g, 75g stearyl acrylate, 3g diacetone acrylamide, 300g pure water, 75g dipropylene glycol monomethyl ether, 0.45g acetic acid, dihardened tallow alkyl dimethyl ammonium 6 g of gaseous substance and 15 g of polyoxyethylene ethyl ceryl ether, under stirring 26 315469 200424304 at 601: emulsified and dispersed by ultrasonic for 15 minutes. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and then 4 5 g of chloroethene was pressed into the filling. Then, 1.12 g of azobis (2-fluorenylpropane) dihydrochloride was added and reacted at 60 t for 5 hours to obtain an aqueous dispersion of the polymer. The characteristics of the aqueous dispersion were evaluated. The results are shown in Table 3. Comparative Example 5 In a 1-liter autoclave (n = 6, 8, 10, 12, and 14 (a mixture of n with an average of 8) of the compound) i50 g, 37.5 g of stearyl acrylate, 37.5 g of lauryl acrylate, 1.8 g of N-hydroxymethacrylamide, 1.2 g of (3-gas-2-hydroxypropyl) methacrylate, 300 g of purified water, 75 g of tripropylene glycol, ethylene glycol, acetic acid 0 ·%, and a hardened tallow alkyl group 6 g of dimethyl ammonium chloride and 15 g of polyoxyethylene lauryl ether were dispersed by ultrasonic emulsification at 6 ° C for 15 minutes. After emulsification, 5 g of n-undecyl mercaptan was added, and then Gas ethylene 458 is pressed into the filling ... Then add 2,2, -dioxopropane) dihydrochloride i i2g, react at 60 C for 5 hours, and pay the polymer aqueous dispersion. Polyoxyethylene · polyoxypropylene_polyoxyethylene triblock co-hydrate [HO ~ (CH2CH2〇) p ^ H6〇wH2CH2〇) _h (p, q and ^ are the numbers, (average molecular weight is 2900, and the ratio of oxyethyl groups is 40% by weight, and an hour is obtained to obtain an aqueous dispersion. "The characteristics of the aqueous dispersion of flat j shell. 27 315469 200424304 Table 3 Water- and oil-repellent storage Stability initial touch Water and oil repellency Water and oil repellency Example Θ 5 5 4 4 Δ 〇 Example 2 5 6 4 5 〇 Example 3 5 6 4 4 〇〇 Implementation of J 4 5 5 5 4 〇Δ Example 5 5 6 5 5 〇Δ Comparative Example 15 1 4 1 〇〇 Comparative Example 2 5 2 4 0 〇〇 Comparison queue 3 5 2 4 0 〇〇 Y to 4 5 1 5 1 〇Δ Compare 4 rows 5 5 2 4 1 〇Δ Effects of the invention According to the present invention, water and oil repellency (especially oil repellency) of the conventional water and oil repellent aqueous dispersion composition can be obtained. ) Water-dispersible water- and oil-repellent agent aqueous dispersion composition which is excellent and has excellent processing stability.

28 315469

Claims (1)

200424304 Scope of patent application: 1 · A water- and oil-repellent agent aqueous dispersion composition, which is characterized by containing: (A) a fluoropolymer, the fluoropolymer having at least a perfluorenyl or perfluoroalkenyl group And acrylic, fluorenyl, or ^; homopolymers or copolymers of polymerizable compounds substituted with acrylic groups, or copolymers of polymerizable compounds copolymerizable with these polymers; and (B) nonionic Surfactant. This nonionic surfactant is a copolymer. Its structure includes: the polyoxyalkylene block exists from the rear end of the polyoxyethylene to the outside of the molecule, so that the polyoxyalkylene block (Carbofluorene of the elongation group is 3 or more) is outside the molecule and the polyoxyethylene block is inside the molecule. 2. The composition according to item 1 in the scope of the patent application, wherein the surfactant (B) is a polyoxyethylene-based block with a polyoxyethylene-based block structure at the center of the molecule Triblock copolymer. 3. The composition according to item 2 of the scope of patent application, wherein the surfactant (B) is a copolymer represented by the following formula (1): A110- (R ^ 〇) a- (CH2CH2O) b- (R12 〇) c.A12 (1) [In the formula, A11 and A12 are a hydrogen atom, a carbon group with 1 to 22 carbon atoms, an alkenyl group with 2 to 22 carbon atoms, or R13C (= 0)-(Ri3 is a carbon number from 1 to Alkyl group of 22 or dilute carbon group of 2 to 22); R11 and R12 are alkylene groups of 3 or more carbon atoms; a, b and c are numbers of 2 or more, and b is a polyoxyethylene block and The weight ratio of the copolymer becomes a number of 5 to 80% by weight]. 29 315469 200424304 4. The composition according to item 1 of the scope of patent application, wherein the surfactant (B) is an organic group having 2 to 6 valences in the center of the molecule, and the organic group has polyoxyethylene Block-polyoxyalkylene block-bonded copolymers. 5. The composition as claimed in claim 4 of the patent scope, wherein the surfactant (B) is a copolymer represented by the following formula (2): Α21— (〇Κ21) _ (〇Η4〇2) ^ / (C2H40) x ~ (R21〇) y-A23 ⑵ A22- (〇R21) y- (〇H4C2 ^ NC # 4 N \ (C2H4〇V ~ (R21〇) y-A24 [wherein A21, A22, A23 and A24 are a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or R13C (= 0)-(R13 is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms) Each R21 may be the same or different, and is an elongation group having a carbon number of 3 or more; each X and y may be the same or different, each being a number of 2 or more, and X is the polyoxyethylene group and the copolymer The weight ratio becomes a number from 5 to 80% by weight]. 6 · The composition according to item 1 of the scope of patent application, wherein the polyoxyalkylene block of the surfactant (B) is polyoxyalkylene Section 7. A method for treating a substrate, which is characterized in that the water- and oil-repellent agent aqueous dispersion composition of the scope of patent application No. 1 is applied to the substrate, and the fluoropolymer (A) is attached to the substrate. For example, the method of claim 7 of the patent scope, wherein the substrate is a separate Nylon fiber or a mixture of nylon fiber and other fibers. 30 315469 200424304 9. The method according to item 7 of the scope of patent application, wherein a surfactant (B) is added to the liquid of the fluoropolymer (A). 1 0. A treatment product, which is a treatment product obtained by treating a substrate with the water- and oil-repellent agent aqueous dispersion composition of the scope of patent application, wherein the substrate is a single nylon fiber or nylon fiber and other Mixture of fibers. 31 315469 200424304 柒. Designated representative drawing: No plan in this case (1) The designated representative drawing in this case is: () (2) Brief description of the element representative symbols in this representative drawing: 捌 If the case has a chemical formula Please reveal the chemical formula that best shows the characteristics of the invention: An0- (Ru0) a- (CH2CH20) b- (R12〇) c-A12 (1) A21— (01 ^) 7 (04 (¾ ^ / (C2H40) x— (R210) Factory A23 ⑵ A22— (OR21)-(OH4C2) ^ N 〇2ΐΪ4 Nns (C2H40) — (R210) —A24 4 315469